(B.K. Parekh and J.G. Groppo (Eds.) ) Processing An

COAL SCIENCE AND TECHNOLOGY
Series Editor:
Larry L. Anderson
Department of Fuels Engineering, University of Utah, Sah Lake City, UT 84112, U.S.A.
Vol. 1: Geochemistry of Coal (Bouska)

Vol. 2: Fundamentals of Coal Benefication and Utilization (Tsai)
Vol. 3: Coal: Typology, Chemistry, Physics and Constitution (Van Krevelen)
Vol. 4: Coal Pyrolysis (Gavalas)
Vol. 5: Free Radicals in Coals and Synthetics Fuels (Petrakis and Grandy)
Vol. 6: Coal Combustion Chemistry-Correlation Aspects (Badin)
Vol. 7: The Chemistry of Coal (Berkowitz)
Vol. 8: Natural Gas Substitutes from Coal and Oil (Qader)
Vol. 9: Processing and Utilization of High-Sulfur Coals (Attia, Editor)
Vol. 10: Coal Science and Chemistry (Volborth, Editor)
Vol. 11: 1987 International Conference on Coal Science (Moulijn, Nater and Chermin,
Editors)
Vol. 12: Spectroscopic Analysis of Coal Liquids (Kershaw, Editor)
Vol. 13;Ênergy Recovery from Lignin, Peat and Lower Rank Coals (Trantolo and Wise,
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Vol. 14: Chemistry of Coal Weathering (Nelson, Editor)
Vol. 15: Advanced Methodologies in Coal Characterization (Charcosset, Editor -
assisted by Nickel-Pepin-Donat)
Vol. 16: Processing and Utilization of High-Sulfur Coals III (Markuszewski and
Wheelock, Editors)
Vol. 17: Chlorine in Coal (Stringer and Banerjee, Editors)
Vol. 18: Processing and Utilization of High-Sulfur Coals IV (Dugan, Quigley and Attia,
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Vol. 19: Coal Quality and Combustion Performance: An International Perspective
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Vol. 20: Fundamentals of Coal Combustion for Clean and Efficient Use
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Vol.21: Processing a n d Uiili/aiion of High-Sulfur Coals V (Parekh and Groppo, Editors)
COAL SCIENCE AND TECHNOLOGT 21
PROCESSING AND
UTILIZATION OF
HIGH-SULFUR
COALS V
Proceedings of the Fifth International Conference on Processing and
Utilization of High-Sulfur Coals, October 25-28,1993, Lexington,
Kentucky, U.S.A.
edited by
B.K. PAREKH and J.G. GROPPO

Center for Applied Energy Research, University of Kentucky, Lexington, KY 40511, U.S.A.
ELSEVIER, Amsterdam London ^ New York Tokyo 1993

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T H I S B O O K IS B A S E D O N
T H E FIFTH INTERNATIONAL CONFERENCE
O N PROCESSING A N D UTILIZATION OF HIGH-SULFUR C O A L S ,
O C T O B E R 2 5 - 2 8 , 1 9 9 3 , L E X I N G T O N , K E N T U C K Y U.S.A.
S p o n s o r e d by
Center for A p p l i e d Energy Research
University of K e n t u c k y
VI
T H E FIFTH INTERNATIONAL CONFERENCE
O N P R O C E S S I N G A N D UTILIZATION OF HIGH-SULFUR C O A L S ,
O C T O B E R 2 5 - 2 8 , 1 9 9 3 , L E X I N G T O N , K E N T U C K Y , U.S.A.
Dr. B.K. P a r e k h , C o - C h a i r m a n
University of K e n t u c k y C A E R , L e x i n g t o n , KY
Dr. J . G . G r o p p o , C o - C h a i r m a n
University of K e n t u c k y C A E R , L e x i n g t o n , KY
ORGANIZING AND ADVISORY COMMITTEE
Dr. Y o s r y A . A t t i a Clark Harrison

1445 Summit Street C Q , Inc.
Columbus, OH 43201 H o m e r City, PA 15748-0280
Dr. D a n B a n e r j e e Dr. G . P . H u f f m a n
Illinois C l e a n C o a l Institute University of K e n t u c k y
C a r t e r v i l l e , IL 62918-0008 Lexington, KY 40506
W i l l i a m P. B a r n e t t R i c h a r d P. K i l l m e y e r
U S D e p a r t m e n t of E n e r g y / P E T C U S Dept. of E n e r g y / P E T C
Pittsburgh, PA 15236 Pittsburgh, PA 15236
Prof. S u b a s h C h a n d e r Dr. C . W . K r u s e
P e n n State University Illinois G e o l o g i c a l S u r v e y
University Park, PA 16802 U r b a n a , IL 61820
Dr. Y . P . C h u g h Prof. J a n u s z S . L a s k o w s k i
S o u t h e r n Illinois University Univ. of British C o l u m b i a
C a r b o n d a l e , IL 62901 Vancouver V6T 1W5, C A N A D A
Prof. R a i m o n d o C i c c u Mel Laurila

University of C a g l i a r i P r o c e s s T e c h n o l o g y , Inc.
Cagliari 09123, ITALY Calumet, Ml 49913-1951
Dr. P.R. D u g a n Dr. R. M a r k u s z e w s k i

INEL/EG&G Idaho Institute of G a s T e c h n o l o g y
I d a h o F a l l s , ID 83401 C h i c a g o , IL 60616
Dr. A n t h o n y G . F o n s e c a Dr. J a n D. M i l l e r
C o n s o l Inc. University of U t a h
Library, PA 15129 Salt L a k e City, U T 84112
Prof. M e n g X i o n g G u o Dr. R . H . Y o o n
Beijing Graduate School VPI & State University
Beijing, C h i n a 10083 Blacksburg, VA 24061
vil
ACKNOWLEDGEMENTS
T h e c o n t r i b u t i o n s of t h e f o l l o w i n g p e r s o n s w h o h e l p e d m a k e t h e c o n f e r e n c e a s u c c e s s a r e gratefully
acknowledged.
CONFERENCE COORDINATORS
Teresa Epperson
Janetta Johnson
TOUR ORGANIZERS
M a r y b e t h McAllister
Kathy Sauer
PROCEEDINGS TYPIST
Janetta Johnson
W e g r a t e f u l l y a c k n o w l e d g e t h e s u p p o r t p r o v i d e d b y Dr. F r a n k J . D e r b y s h i r e , D i r e c t o r , C e n t e r f o r
A p p l i e d E n e r g y R e s e a r c h ( C A E R ) a n d t h e C A E R staff.
Vlll
PREFACE
U t i l i z a t i o n o f h i g h s u l f u r c o a l s is b e c o m i n g d i f f i c u l t i n v i e w o f t h e t i g h t e n v i r o n m e n t a l
regulations being imposed around the world. T o m e e t t h e c h a l l e n g e of utilizing h i g h sulfur c o a l s
without d a m a g i n g t h e e n v i r o n m e n t , c o u n t l e s s n u m b e r s of scientists a n d e n g i n e e r s a r o u n d t h e w o r l d
are e n g a g e d in d e v e l o p i n g n o v e l t e c h n o l o g i e s . In t h e U.S.A. a l o n e , t h e f e d e r a l g o v e r n m e n t h a s s p e n t
a b o u t five billion d o l l a r s in s u p p o r t of d e v e l o p i n g t e c h n o l o g i e s t h a t will allow s a f e u s a g e of h i g h sulfur
coals.
T h i s c o n f e r e n c e , like t h e p r e v i o u s f o u r c o a l utilization c o n f e r e n c e s , e m p h a s i z e s d e s u l f u r i z a t i o n
with papers o n physical a n d chemical cleaning as well as post-treatment a n d fluid-bed c o m b u s t i o n
technologies. Of t h e 4 5 p a p e r s submitted, 15 p a p e r s deal with physical cleaning a n d s e v e n with
c h e m i c a l c l e a n i n g o f c o a l , w h i c h s u g g e s t s t h a t a m a j o r e m p h a s i s is still b e i n g p l a c e d i n p r e - c l e a n i n g
of c o a l . T h e p o s t - t r e a t m e n t t e c h n o l o g i e s , b e i n g d e v e l o p e d w i t h t h e s u p p o r t of U.S. f e d e r a l a n d s t a t e
g o v e r n m e n t a g e n c i e s , e m p h a s i z e s r e m o v a l o f b o t h SO^^ a n d NO^^ g a s e s .
Finally, w e w i s h t o e x p r e s s o u r g r a t i t u d e t o t h e a u t h o r s a n d t h e r e v i e w e r s for p r o v i d i n g their
v a l u a b l e t i m e in i m p r o v i n g t h e q u a l i t y of p a p e r s . W e a l s o t h a n k all o f t h o s e w h o a g r e e d t o s e r v e a s
session chairs at t h e c o n f e r e n c e .
B.K. P a r e k h J.G. G r o p p o
Conference Co-Chairman Conference Co-Chairman
Processing and Utilization of High-Sulfur Coals V
edited by B.K, Parekh and J.G. Groppo
Further sulfur speciation studies by sulfur K-edge XANES

spectroscopy
G.P. Huffman, N. Shah, F.E. Muggins, F. Lu, and J. Zhao
University of Kentucky, Lexington, KY 40506-0107
ABSTRACT
Sulfur K-edge XANES spectroscopy has been shown to be an excellent

technique for quantitative speciation of sulfur in fossil fuels. Earlier studies focussed
on establishing the method and applying it to sulfur speciation in coal. More recently,
it has been applied to a variety of additional problems, including investigation of coal
desulfurization processes, and speciation of sulfur in materials derived from coal and
oil, such as asphalts, coal liquefaction resids, and rubber. Some of the more
interesting results from this research will be presented. Additionally, a comparison will
be made of sulfur K-edge and L-edge XANES results for the same coal.
INTRODUCTION
Sulfur K-edge x-ray absorption fine structure (XAFS) spectroscopy has been
shown to be an excellent method of speciating the sulfur in coal and related materials.
Two methods have developed for sulfur speciation which involve analysis of the x-ray
absorption near-edge structure (XANES) region of the XAFS spectrum. The method
developed by Gorbaty and coworkers^^"^^ analyzes the XANES by a third derivative
method, which yields peaks whose heights are proportional to the percentages of
sulfidic and thiophenic sulfur. In the method developed by our group,^"*^^ a direct least
squares analysis of the XANES is carried out by fitting it to a series of mixed
Lorentzian-Gaussian peaks. The peak areas are then used to determine the
percentages of different sulfur forms present, using empirically determined calibration
constants.
In the current article, we briefly review some recent applications of this technique;
speciation of sulfur in desulfurized coals, coal liquefaction resids, asphalts and rubber.
A comparison of sulfur speciation by sulfur K-edge and L-edge XANES spectroscopy
for one coal is also presented.
EXPERIMENTAL PROCEDURE
The experimental XAFS spectroscopy procedures have been discussed in detail

elsewhere.^"^"^^ Briefly, all XAFS measurements were carried out using beamline X-19A
at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory.
The spectra were taken in the fluorescent mode, using an ionization detector, and
maintaining a helium filled pathway for the x-ray beam. A double crystal Si(111)
monochromator was used to vary the x-ray energy from 100 eV below the sulfur
absorption edge(2472 eV) to approximately 400 eV above it. For calibration
purposes, all energies were measured relative to the s->p transition peak of elemental
sulfur.
The XANES spectra were analyzed using a program called EDGEFIT, which
deconvolutes the spectra into a series of 50% Lorentzian-50% Gaussian peaks,
representing s-^p transitions and scattering peaks, and one or two arctangent step
functions, representing the transition of the photoelectrons to the continuum. A
detailed discussion of this method and how the resulting s-*p peak area percentages
are transformed into percentages of the total sulfur associated with different sulfur
functional forms is given in our earlier papers.^"^"^^
RESULTS AND DISCUSSION
Desulfurized coals
Reagent treated samples: Chatterjee and Stock have discussed the removal
of organic sulfur from coal by treatment with SET^ and strongly basic r e a g e n t s . A
suite of these desulfurized coals were previously examined by XANES spectroscopy
by Chatterjee et al. using the third derivative method of XANES analysis developed by
Gorbaty et al.^^^ We have examined the same suite of samples independently using
the least squares analysis approach for deconvolution of the XANES. The results are
summarized in Table 1. Some typical XANES fits are shown in Figure 1. As
discussed elsewhere, s-*p peaks from different phases are identified on the basis of
their energies.^'^'^
The results for the raw Illinois # 6 coal, obtained from the Argonne Premium Coal
Sample Bank, are similar to those we have reported e a r l i e r , e x c e p t for the presence
of some sulfate. After treatment with lithium aluminum hydride (LAH), all of the pyrite
and most of the sulfate have disappeared; additionally, the percentage of organic
sulfide appears to have decreased relative to thiophenic sulfur. Following the SET
treatment, the thiophenic sulfur percentage is significantly decreased, while the BASE
treatment produces a substantial decrease in the sulfidic sulfur. This is as proposed
by Stock and Chatterjee^^ and similar to the results obtained by the third derivative
treatment of the XANES data of Gorbaty.^^^ However, the results are obscured
somewhat by the appearance of an unidentified sulfide which gives an s-*p peak at
'^-0.5eV. Presumably, this is a potassium sulfide, in view of the nature of the
chemical treatment. Since we have not conclusively identified this phase and have not
determined a coefficient for conversion of its peak area percentage to sulfur
Table 1
Percentages of total sulfur contained in different functional forms ( 5-1 0%).
Inorganic Elemental Organic Thiophenic

Sample Sulfide Sulfur Sulfide Sulfur Sulfoxide Sulfone Sulfate
Illinois No.6
raw coal 48 - pyrite 0 18 26 0 0 9
Lithium aluminum
hydride (LAH)
treated coal 0 0 25 66 4 3 2
SET-treated coal 15 - unk. 0 25 36 5 15 4
BASE-treated coal 18 - unk. 0 13 49 7 8 5
SET, then BASE 21 - unk. 0 24 21 11 13 10
BASE, then SET 0 9 26 36 7 9 13
o = not included in fit, below detection limit. For nonoxidized sulfur forms, d.1. = 10%, for oxidized sulfur forms = 5%
w
J LAH treated,
Depyritized III #6
2
c
o
o
(O

<
^ 1
(

i

. .. 111111 77:: t i ; *. lltî:ttifn*/J*0^sm^m^.
I 1 1 - 1 1 1 1 1
-10 -6 -2 2 6 10 14
Energy (eV)
2 Base treated,
Depyritized III #6
C
O
o
0)
<
(O
i
o
-6 -2 2 6 " 14
Energy (eV)
Figure 1. Fitted XANES spectra of LAH depyritized Illinois # 6 coal, before and after
BASE treatments.
percentage, we have simply assumed a conversion coefficient of 1.0 to derive the
values in Table 1. This should not significantly affect the relative percentages of the
other functional forms of sulfur, however.
For the samples treated with SET then BASE, and with BASE then SET, the
thiophenic sulfur is markedly decreased in both cases, but there does not appear to
be any decrease in the organic sulfide. In this regard, however, it should be noted
that the accuracy of our method with an unknown inorganic sulfide present is not
better than about 10%.
Biologically Desulfurized Samples: Previously, we have used XANES to

examine a number of biologically solubilized and desulfurized samples.^^^ The
primary conclusion of that earlier work was that biological agents did not discriminate
greatly between different functional forms of sulfur, and little if any organic sulfur was
removed by biological treatment. More recently, however, XANES has been used to
examine several samples subjected to biotreatment using the microbe Rhodococcus
rhodochrous, as discussed in detail elsewhere by Kilbane.^^^^ Prior to treatment, most
of the pyrite was removed from the coal. The results obtained by analysis of the
XANES spectra are summarized in Figure 2. The results for total sulfur in Figure 2
were taken from Kilbane's paper.^^^^ For both samples, the total sulfur values would
appear to indicate that a substantial reduction in organic sulfur was accomplished.
However, it is evident from Figure 2 that the relative amounts of the different functional
forms of organic sulfur were essentially unchanged, within the standard error (5%).
It therefore appears that all of the organic sulfur functional forms were affected
approximately equally by the treatment.^^^^
Coals Subjected to Molten Caustic Leaching: A molten caustic leaching

process for removal of both ash and sulfur from coal has been developed by TRW
Corporation.^^^^ The fitted XANES obtained from a Kentucky # 9 coal subjected to this
process is shown in Figure 3. It is evident that the sulfur has undergone considerable
oxidation. The results obtained by quantitative analyses of the XANES are
summarized for three coals in Table 2: a Kentucky # 9 coal and a Pittsburgh # 8 coal
subjected to the molten caustic leaching process, and the results for a raw, fresh
Pittsburgh # 8 coal.^"*^ It is evident that the forms of sulfur are drastically changed and
reduced by this rather severe process. In particular, no pyrite or organic sulfide
remain, and thiophenic sulfur, which is the dominant organic sulfur form in the original
coals is reduced to only about 0.1% in the treated coals. Elemental sulfur, sulfone,
and sulfate are the dominant sulfur species remaining, indicating severe oxidation.
Treatment with perchloroethylene(PCE):The forms-of-sulfur present in a

number of coals before and after extraction with perchloroethylene (PCE) at its boiling
point (121" C) for up to an hour have been examined by a combination of sulfur XAFS
and Mossbauer spectroscopies and standard chemical methods. A hybrid forms-of-
sulfur analysis was devised that included determinations of pyritic sulfur, elemental
sulfur, organic sulfide, thiophene, oxidized organic sulfur forms, and sulfate. Of these
forms of sulfur, only elemental sulfur was shown to be extracted by PCE. Except for
4
c
o
o
3
to

<

,
2

i_

1
-1
Energy, eV
Figure 2. Percentages of organic functional forms of sulfur in control and biotreated

Illinois # 6 samples as determined from the S K-edge XANES analyses. Total sulfur
contents are indicated.
4
C
O
3

O
0)
<
2

TS
1
\_

-1
-2 2 6
Energy, eV
Figure 3. KY # 9 coal cleaned by gravimelt process.
Table 2
Sulfur Forms in Gravimelt Coals from XANES Analysis
(% of Total Sulfur in Different Forms)
Pittsburgh # 8 Gravimelt Pgh # 8 Gravimelt KY # 9

2.19 w t % S 0.43 wt% S 0.70 wt% S
Pyrite 52
Elem. Sulfur 28 37
Org. sulfide 13
Thiophene 35 19 16
Sulfonate 16 14
Sulfate 37 33
= not included in fit, below detection limit. For nonoxidlzed sulfur forms,
d.i. = 10%, for oxidized sulfur forms = 5%
complications involving pyrite segregation during the extraction process in certain
experiments, changes in all other sulfur forms were less than experimental
uncertainties with respect to the extraction. A more detailed summary of these results
will be published elsewhere.^^^^
Sulfur speciation in coal liquefaction resids

The sulfur forms in direct coal liquefaction resids is of interest because recycled
resid could constitute 50-70% of the feed in the first stage of a two stage liquefaction
process, the balance being coal. We have examined five resids from the Wilsonville
pilot plant, provided to us by CONSOL, Inc., using both XANES and Mossbauer
spectroscopies. In all of the samples, pyrrhotite was the dominant component,
accounting for 75 to 99% of the sulfur present. The primary interest in the XANES
data was to determine the organic forms of sulfur. Because of the dominance of
pyrrhotite, however, this could only be done semiquantatively from the XANES of the
raw resid samples. Consequently, tetrahydrofuran(THF) extracts of four of the resids
were prepared and re-examined by XANES. The results are summarized in Table 3
and a typical fitted XANES spectrum is shown in Figure 4. Although we did not have
samples of the actual coals used in these liquefaction runs, we have included in Table
3 the organic sulfur speciation determined by XANES spectroscopy^"*^ for the Illinois
#6, Pittsburgh, and Wyodak coals from the Argonne Premium Coal Sample Bank
(APCSB). While the total organic sulfur content is substantially decreased from that
of the original coals, sizeable percentages of both sulfidic and thiophenic sulfur are
observed in the resids. Assuming that the APCSB coals are not too different in their
sulfur forms from the coals used for the present runs, it is of interest to compare the
sulfide to thiophene ratios of the resids to those of the coals. It is seen that this ratio
has decreased markedly for the Wyodak resid and by a factor of two for the Illinois
resid, and while it has increased for the Pittsburgh resid.
Comparison of sulfur K-edae and L-edge results

Recently, Brown et al.'^'*^ have examined the sulfur in coal by sulfur L-edge
XANES spectroscopy. Analysis of the sulfur forms in Mequinenza lignite^^^^ by L-edge
XANES gave the following results: 40% thiophenic(4.0 wt%), 20% aryl sulfide, 20%
aliphatic sulfide, and 20% disulfide(2.0 wt.% for each sulfide form). The K-edge
spectrum of this sample is shown in Figure 5. The major white line component was
fitted to three peaks that correspond, with increasing energy, to di/polysulfide, organic
sulfide, and thiophenic sulfur. Minor amounts of sulfoxide and sulfate are also
observed. The results for the percentages of total sulfur and the wt.% of sulfur in
each sulfur form identified are summarized in Table 4. Generally speaking, the results
for sulfur speciation by K-edge and L-edge XANES spectroscopy agree within the
error of the measurements if the aryl and aliphatic sulfide categories of the L-edge
measurement are combined for comparison to the K-edge organic sulfide category.
White et al.^^^^ have prepared an extensive paper summarizing the results obtained for
this interesting coal using a wide range of analytical techniques.
Table 3
XANES results for THF extracts of Wilsonville coal liquefaction resids.
Sulfur form percentage

Total
Sulfur Thio Sulf Sulfide/
Sample (wt.%) Sulfidic phenic oxide Sulfone Sulfate Thio.
Illinois # 6 ,
second
stage C/C* 0.15 16 61 8 6 10 0.26
Illinois # 6 ,
interstage,
C/C 0.26 16 66 5 5 7 0.25
Pittsburgh,
interstage,
C/C 0.63 35 62 0 2 1 0.56
Wyodak
Anderson,
interstage,
T/C* 0.10 7 90 0 2 1 0.08
Illinois # 6 ,
APCSB 2.51 37 63 0 0 0 0.58
Pittsburgh,
APCSB 1.05 27 71 0 2 0 0.38
Wyodak
APCSB 0.49 39 61 0 0 0 0.64
0 = below detection limit, approximately 5% for oxidized sulfur forms.

10
c
o
Q-
O
1
i
1
1
\ "
O
-10 -2 2 10 14
E n e r g y (eV)
Figure 4. Least squares analysis of the XANES of the THF extract of a coal liquefaction
resid. THF soluble. Pittsburgh, Run 259, C/C, Interstage
1.5 - Data
Fit
Edge
Peaks
c
s
1 -
Thiophene
o
I 1! /
Org. Sulfide ff /V i . . / ^^9
(0

b 0.5
A
: \ /: / \ Sulfoxide +
Di/Polysulfide # / . . . \1 Thiophene
... y/-
' * " \ Sulfate
'*.. **..
12 16
E n e r g y (eV)
Figure 5. Least-squares fitted sulfur K-edge XANES spectrum of Mequinenza Lignite

11
Table 4
Results of Least-Squares Fitting of Sulfur K-edge Spectrum of Mequinenza Lignite
Sulfur Form % of Total Sulfur Wt% S in Lianite^
Pyritic Sulfur nd (<0.5)

Di-sulfide 10 1.0
Sulfide 33 3.3
Thiophenic 42 4.2
Sulfoxide 9 0.9
Sulfone 0 <0.5
Sulfate 5 0.5
^ Based on 10.0 wt% (dry) non-pyritic sulfur in lignite, nd - Not determined

0 = below detection limit, 5% of total sulfur
Sulfur speciation in other types of materials

As discussed in more detail elsewhere,^^^ we have recently investigated the
sulfur functional groups present in a number of asphalt samples by least-squares
analysis of their sulfur K-edge XANES spectra. In unoxidized asphalts, oxidized sulfur
forms are generally absent, and the principal sulfur form observed is thiophenic.
Thiophenic sulfur varied from 54% to 78% of the total sulfur, with the balance being
primarily sulfidic. Oxidation tests aimed at mimicking asphalt ageing were carried out
at the Western Research Institute. Comparison of the sulfur forms before and after
oxidation shows that only the aliphatic sulfur oxidizes to sulfoxide.
There is currently much interest in using waste rubber tires in combustion and
coliquefaction operations with coal. It is therefore important to know the disposition
of sulfur in such rubber. Recently, we completed an XANES analysis of the sulfur
forms in rubber tread material from tires made by several manufacturers. The
principal sulfur species observed are polysulfides, monosulfides, and thiophenes, with
minor oxidized sulfur forms present. Polysulfides are the dominant species observed,
but significant amounts of sulfides and thiophenes are observed for some samples.
The polysulfides are believed to be the sulfur links formed between polymer chains
during vulcanization. While the percentages observed are not unreasonable, there is
more sulfidic and thiophenic sulfur present than expected, and further work will be
carried out to try to understand this apparent discrepancy.
12
SUMMARY AND CONCLUSIONS
Sulfur K-edge XANES spectroscopy has matured to the point where it can be
considered to be a reliable, albeit not routine, method of speciating the forms of sulfur
in coal and other fossil energy materials. Coal desulfurization is an area where this
technique will undoubtedly be frequently applied. In the current article, a number of
examples of the use of sulfur XANES to speciate the sulfur forms in desulfurized coals
are presented. These examples include coals treated with single electron transfer and
basic reagents, coals treated in perchloroethylene, coals subjected to molten caustic
leaching, and biodesulfurized coals. Examples are also given of the application of this
method to determination of the sulfur forms in coal and oil-derived materials, including
coal liquefaction resids, asphalts, and rubber. Finally, it is shown that the sulfur forms
in a lignite determined by sulfur L-edge XANES spectroscopy agree fairly well with
those determined by sulfur K-edge XANES spectroscopy.
Acknowledgement
This research was supported by the Office of Exploratory Research of the

Electric Power Research Institute under EPRI Contract No. RP-8003-20. We are
grateful to Prof. Leon Stock, Dr. Kuntal Chatterjee, Prof. Sunyu Lee, Dr. Melissa Chou,
Dr. John Kilbane, Mr. Phil Goldberg, Dr. Malvina Farcasiu, Prof. Ted Eyring, and Mr.
Jack Youtcheff for providing samples for this investigation.
REFERENCES
1. George, G.N.; Gorbaty, M.L JAm.Chem.Soc. 1989, 111, 3182.

2. Gorbaty, M.L; George, G.N.; Kelemen, S.R. Fuel, 1990, 69, 1065.
3. George, G.N.; Gorbaty, M.L; Kelemen, S.R.; Sansone, M. Energy & Fuels, 1991,
5, 93.
4. Huffman, G.P.; Mitra, S; Huggins, F.E.; Shah, N.; Vaidya, S; Lu, F. Energy & Fuels,
1991,5, 574-581.
5. Huggins, F.E.; Mitra, S.; Vaidya, S.; Taghiei, M.; Lu, F.; Shah, N.; Huffman, G.P.
Processing and Utilization of High Sulfur Coals IV, 1991, Elsevier Sei. Pub.. 13-42.
6. Taghiei, M.M.; Huggins, F.E.; Shah, N.; Huffman, G.P.; Energy & Fuels, 1992, 6,
293-300.
7. Chatterjee, K.; Wolny. R.; Stock, L M . Energy & Fuels, 1990, 4, 402.
8. Chatterjee, K.; Stock, L M . Energy & Fuels, 1991, 5, 704-707.
9. Chatterjee, K.; Stock, L.M.; Gorbaty, M.L; George, G.N.; Kelemen, S.R. Energy
& Fuels, 1991, 5. 771-773.
10. Huggins, F.E.; Mitra, S.; Vaidya, S.; Taghiei, M.M.; Lu, F.; Shah, N., Huffman, G.P.
Processing and Utilization of High Sulfur Coal IV, Dugan, P.R.; Quigley, D.A.; Attia,
Y.A.; Eds.; Elsevier Sei. Pub., 1991, 4, 13.
13
11. Kilbane, J.J.; Proceedings: 1991 Second International Symposium on the

Biological Processing of Coai Ed., S. Yunker; EPRI GS-7482,1991, pp. 5-1-5-18.
12. Anastasi, J.L; Barrish, E.M.; Coleman, W.N.; Hart, W.D.; Jonis, J.F.; LedgenAôod,
L; McClanathan, L.C.; Meyers, R.A.; Shih, C.C.; Turner, W.B. Processing and
Utilization of High Sulfur Coals III] Eds., Markuszewski, R.; Wheelock, T D . ;
Elsevier Sei. Pub., 1990, 371-377.
13. Huggins, F.E.; Vaidya, S.V.; Shah, N.; Huffman, G.P. "Investigation of Sulfur Forms
Extracted from Coal by Perchloroethylene," Fuel Processing Technology, in press.
14. Brown, J.R.; Kasrai, M.; Bancroft, G.M.; Tan, K.H.; Chen, J.M. Fuel, 1992, 71, 649-
653.
15. White, C M . ; Collins, L.W.; Veloski, G.A.; Gray, R.J.; LaCount, R.B.; Kasrai, M.;
Bancroft, G.M.; Brown, J.R.; Huggins, F.E.; Shah, N.; Huffman, G.P. "A Study of
Mequinenza Lignite," submitted to Energy & Fuels.
16. Huggins, F.E.; Vaidya, S.V.; Huffman, G.P.; Mill, T ; Youtcheff, J.; Amer. Chem.
Soc. Div. of Fuel Chem. Preprints, 1992, 37(3), 1376-1382.
edited by B.K, Parekh and J.G. Groppo 15
1993 Elsevier Science Publishers B.V.
Release of organic, pyritic, elemental, and sulfate sulfur during

temperature-programmed pyrolysis of Illinois Basin coals
C.-C Chou, ICC. Hackley and J. Cao
Illinois State Geological Survey, 615 East Peabody Drive, Champaign, IL 61820, U S A
Sulfur release profiles (variation of sulfur dioxide in pyrolysis/combustion gases with

increasing temperature) for two Illinois Basin coals have been determined using a
temperature-programmed pyrolysis and gas-combustion apparatus in conjunction with
a quadrupole gas analyzer (QGA). For these determinations, a coal sample is heated
from ambient temperature to 800 <C at a rate of 20C/min in the pyrolysis chamber
under a nitrogen atmosphere. The volatile sulfur products are converted to sulfur
dioxide in the adjoining combustion chamber, which is maintained at 850>C under a
constant flow of oxygen. The abundance of sulfur dioxide in the combustion gases is
determined by the Q G A
Sulfur evolution profiles of a fresh sample (0.027% elemental sulfur) and a weathered
sample (0.10% elemental sulfur) were obtained for coal IBC-109 of the Illinois Basin
Coal Sample Program (IBCSP). The profile of the fresh sample shows two peaks, at
480 C and 610 C, that are interpreted to be a result of the release of organic sulfur
and the decomposition of pyrite, respectively. The profile of the weathered sample
shows three peaks at 350C, 475 *>C, and 600<>C. The low-temperature peak at 350C
appears to be related to elemental sulfur, which occurs in the weathered coal. Pyrolysis
of pure elemental sulfur indicates that it is released between 200 <>C and 360 <>C with a
peak at 320C. Pyrolysis of a mixture of 1.2 g of fresh sample of IBC-109 and 1.7 mg
of elemental sulfur produces a profile similar to the weathered sample of IBC-109.
Coal sample IBC-102 is known to be easily weathered. The sulfur release profile for
a weathered sample of IBC-102 (0.25% elemental sulfur and 0.12% pyritic sulfur) shows
two strong peaks at 340C and 450C, resulting from the release of elemental sulfur
and organic sulfur, respectively Pyrolysis of mixtures of coal IBC-102 plus ferric sulfate
shows a sulfur release peak at 5 2 5 ^ 0 The presence of sulfate minerals in weathered
coal causes a bulge at 525 C on the shoulder of the organic sulfur peak. Characteristic
sulfur evolution profiles obtained during coal pyrolysis/gas combustion can be
interpreted based on the abundance of various forms of sulfur in coal.
16
1. INTRODUCTION
Pyritic and organic sulfur are two major forms of sulfur in coal. In addition, sulfate
and elemental sulfur, which are derived from pyrite during weathering also occur in coaL
The amount of the latter two forms of sulfur is minute in fresh samples, but can be
significant in weathered samples [1].
A variety of temperature-programmed heating techniques have been used to
characterize sulfur evolution in relation to sulfur species in coal. For example,
temperature-programmed reduction (TPR) experiments were carried out by Attar to
determine the distribution of organic sulfur functional groups [2]. In the T P R method
each organic sulfur functional group was reduced by hydrogen to H2S at a rate that
corresponds to a peak temperature in the kinetic sulfur evolution diagranL A
controUed-atmosphere programmed-temperature oxidation method (CAPTO) was used
by LaCount et al. to determine the SO2 evolution profile [3]. A coal sample was heated
under an oxygen atmosphere, and the gases were flowed into a second furnace
maintained at 1050 **C and then transferred to a gas cell in a Fourier transform infrared
spectrometer (FTIR ) for determination. The SO2 evolution peaks were assumed to be
related to oxidation and volatilization of sulfur species in coal. Boudou studied the
temperature-programmed heating of coal in argon or air and monitored the gas
compositions using a quadrupole mass spectrometer [4]. Evolution profiles of volatile
sulfur species of hydrogen sulfide and sulfur dioxide were reported.
In the ISGS laboratory, a temperature-programmed pyrolysis-gas combustion
technique was developed, in which all sulfur species evolved during pyrolysis are
converted to SO2 and the gaseous species in the combustion gases are monitored with
a quadrupole gas analyzer [5]. In this paper, we report sulfur release profiles during
temperature-programmed pyrolysis for fresh and weathered coal samples and for
mixtures of coal with elemental sulfur or ferric sulfate. The SO2 evolution peaks
produced with this method can be interpreted in terms of the release of organic, pyritic,
elemental, and sulfate sulfur at different temperatures during coal pyrolysis.
2. EXPERIMENTAL PROCEDURES
2.1. Samples
Two coal samples from the Illinois Basin Coal Sample Program were used in the
experiments: IBC-102 and IBC-109. Sample IBC-102 is a Colchester seam coal collected
from a preparation plant in Fulton County, western Illinois [6]. Sample IBC-109 is a
Herrin seam coal collected from a preparation plant in Franklin County, southern
Illinois. Both samples are high-volatile bituminous coal, IBC-102 is a high sulfur coal
(3.30% total sulfur) and IBC-109 is a medium-sulfur coal (1.13% total sulfur).
Each pyrolysis experiment was conducted typically on 1 g of coal with a particle size
of -60 mesh. Three samples of coal IBC-102 were studied: a fresh sample, a slightly
weathered sample that had been exposed to air for 34 days to 66-days, and a weathered
sample that had been stored in a bottle in the laboratory for about 5 years. Three
samples of coal IBC-109 also were tested: fresh, slightly weathered, and weathered
samples.
17
2.2. Determination of forms of sulfur

The forms of sulfate, pyritic, and organic sulfur in the fresh and weathered samples
of coal were determined using methods similar to those described in Hackley et al. [7].
A sample of coal (1-2 g) was boiled with dilute HCl for 40 minutes to dissolve sulfate,
which was later determined gravimetrically by adding BaCl2 to the filtrate solution to
precipitate BaS04. Elemental sulfur was extracted from the acid-leached sample with
hot (120 <>C) perchloroethylene (PCE) for approximately 30 minutes. The elemental
sulfur dissolved in the P C E filtrate was converted to Ag2S using the lithium aluminum
hydride (LAH) method. The pyritic sulfur was extracted with reductive L A H and
determined gravimetrically as Ag2S. The remaining coal was combusted at 1350 *C
under pure oxygen to determine the organic sulfur content.
2 3 . Temperature-programmed pyrolysis-gas combustion technique

The temperature-programmed pyrolysis-gas combustion apparatus used in this study
is similar to that described by Hackley et al. [7]. Major components of the system
include a quartz tube reactor, a gas flow controller, two split-tube furnaces, a
programmable temperature controller, 75- capillary tubing connecting a quadrupole
gas analyzer (QGA) to the pyrolysis-combustion system, and a microcomputer (Figure
1). Approximately 0.5-1.0 gram of coal is heated (temperature programmed at
20C/min) under a controlled atmosphere in the quartz-tube reactor which consists of
two consecutive chambers. The coal is heated in the first (pyrolysis) chamber under a
nitrogen atmosphere, and the volatile products are carried with the nitrogen flow to the
second (combustion) chamber which is maintained at 850 **C under a constant flow of
oxygen, where they are combusted. The gaseous products are sampled through the
capillary tubing and monitored with a quadrupole mass spectrometer referred to in this
paper as a quadrupole gas analyzer (QGA). Gaseous species are ionized within the
Q G A and analyzed according to the mass-to-charge ratio produced for different gaseous
species. For example, SO2 is monitored using the mass-to-charge ratio (m/z) of 64. The
data from the Q G A and temperature controller are then transmitted to and stored on
a microcomputer. The experiments are designed specifically to relate sulfur evolution
peaks to sulfur forms in coal.
3. RESULTS OF PYROLYSIS-GAS COMBUSON EXPERIMENTS
3.1. Replicate determinations of sulfur evolution

The SO2 evolution profiles determined by the pyrolysis-gas combustion-QGA in four
replicate runs for coal IBC-109 are shown in Figure 2. The general shapes of the
profiles are reproducible and the sulfur evolution peaks occur at essentially the same
temperature for each replicate run. The profiles show three peaks: an initial peak at
approximately 350<*C, a major peak at approximately 475 *>C, formed by the evolution
of organic sulfur, and a third peak at approximately 600 <C derived from the
decomposition of pyrite. The two higher temperature peaks are similar to those
obtained for four other Illinois Basin coal (Figure 13 in [7]). The low-temperature peak
observed with coal IBC-109 probably represents the release of elemental sulfur as
explained below. Weathering of Illinois Basin coals is known to form elemental and
sulfate sulfur [e.g., 1, 8].
18
Figure 1. The experimental setup for temperature-programmed pyrolysis-gas combustion in conjunction with a quadrupole
gas analyzer (QGA).
19
100 200 300 400 500 600 700 800

Temperature { C)
Figure 2. Sulfur evolution profiles for four replicate pyrolysis experiments on a slightly
weathered sample of coal IBC-109 (run No. EL92012,13,14, and 15). Volatilized sulfur
species were converted to SO2 and monitored with a Q G A The shape of the profiles
is similar and reproducible. There are three peaks in the SO2 release profiles: an initial
peak at approximately 350 C, a major peak at approximately 475 C, and a third peak
at approximately 600 **C. These three peaks indicate that three kinds of sulfur forms are
released at successively higher temperatures: elemental, organic, and pyritic sulfur.
3.2. Pyrolysis of fresh samples of coal IBC-109

The SO2 profiles for fresh samples of coals IBC-109 and IBC-102 were obtained from
samples which had been stored under a nitrogen atmosphere before the experiments.
The profile for the fresh sample of IBC-109 shows two peaks at approximately 480 <>C
and 610 o C (Figure 3A, solid line). The profile for the fresh sample of coal IBC-102
also shows two peaks at approximately 480 <>C and 640 **C (Figure 3B, soHd line).
33. Weathered coal samples

Coal IBC-109. The profile for the weathered sample of IBC-109 shows a slight shift
of the two large peaks to lower temperatures of 475 *>C and 600 C, respectively (Figure
3A, dotted line). In addition, there is a low-temperature peak at approximately 350*>C.
To determine whether the 350 <*C peak is due to the release of elemental sulfur formed
20
2.8
2.6 Coal IBC-109
2.4 Fresh sample
2.2 Weathered sample
b 2
1.8
1.6
D
(0 1.4
V) 1.2
a
oi
CD 0.6
t 0.4
t 2
0.2
100 200 300 400 500 600 700 800
Temperature ( t )
Figure 3A. Sulfur evolution profiles of fresh and weathered samples of coal IBC-109.
CO
0)
I
D
C
0)O
CO
t

Q .
100 200 300 400 5 0 0 ^ 600 700 800
Temperature ( C)
Figure 3B. Sulfur evolution profiles of a fresh sample, a slightly weathered 66-day
sample, and a weathered sample of coal IBC-102.
21
from pyrite during coal weathering, pyrolysis experiments were conducted on elemental
sulfur (Aldrich Chemical Co., 99.999%). The results showed that elemental sulfur was
released between 200 C and 360 *C with a peak at 320 C. Thus, release of elemental
sulfur is the likely cause of the 350C peak in the sulfur evolution profile. This
interpretation is supported by elemental sulfur data of coal IBC-109 that the weathered
sample contains much more elemental sulfur (0.10%) than the fresh sample (0.027%)
(Table 1).
Coal IBC-102. The sulfur release profiles of a slightly weathered 66-days sample
(Figure 3B, dashed line) and a weathered sample of IBC-102 (Figure 3B, dotted line)
are compared with that of the fresh sample (Figure 3B, solid line). The 66-day sample
shows two prominent peaks at 475 <C and 600 C, corresponding to the release of
organic and pyritic sulfur, respectively. The 475 C peaks shows a significant broadening,
and the organic sulfur starts to evolve at about 270 C from this sample as compared to
about 400 C from the fresh sample of the coal. The pyritic sulfur peak of the 66-day
sample occurs at 600 *C, which is lower than that of the fresh sample of IBC-102
(640 o C), but is the same as that of the weathered sample of IBC-109 (600 >C).
The profile for the weathered sample of IBC-102 has two strong, but partially resolved
peaks at 340 C and 450 C. The positions of the peaks in terms of pyrolysis
temperature are rather different from those of the slightly weathered and fresh samples
of this coal. The 340 <*C peak results from the release of elemental sulfur, which will be
explained in the next section. The 450<>C peak of the weathered coal is significantly
lower than the release temperature of organic sulfur from the slightly weathered and
fresh samples at 475 C and 480 *C, respectively. The pyritic sulfur peak becomes a
minimum at 600C on the profile. A weak peale at approximately 525 <*C on the high-
temperature shoulder of the organic sulfur peak probably results from the
decomposition of sulfates in coal, which will be discussed later.
The three profiles shown in Figure 3B indicate the effects of weathering on the
abundances of sulfur forms in coal IBC-102 and their release temperature during
pyrolysis. Elemental and sulfate sulfur are formed from pyrite during its long-term
exposure in the air, and pyrite content decreases as elemental and sulfate sulfur
increase. This interpretation is supported by the analysis of sulfur forms in the fresh
and weathered samples. The fresh and weathered samples of coal IBC-102 contain
0.048% and 0.25% elemental sulfur, respectively, 0.14% and 1.28% sulfate sulfur,
respectively, and 1.85% and 0.12% pyritic sulfur, respectively (Table 1).
3.4. Pyrolysis of mixtures of coal plus elemental sulfur

To test whether the low-temperature peak (340C - 350C) in the sulfur release
profiles of weathered samples is due to the release of elemental sulfur, pyrolysis
experiments were conducted on fresh coal samples spiked with a small amount of
elemental sulfur. Figure 4A shows the sulfur evolution profile for a fresh sample of coal
IBC-109 (1.2 g) plus elemental sulfur (1.7 mg) as compared with that of a weathered
sample of IBC-109. The profile of the mixture (solid line) is similar to that of the
weathered coal (Figure 4A, dotted line), although the low-temperature peak of the
mixture, at 320<C, is slightly lower than the 350C peak of the weathered coal. The
relative intensity of the third peak (pyritic sulfur) versus the second peak (organic sulfur)
for the fresh coal-elemental sulfur mixture (Figure 4A, solid line) is stronger than that
22
Table 1
Forms of sulfur in fresh and weathered samples of coals IBC-109 and IBC-102 (in %)
Sample Sulfate Elemental S Pyritic S Organic S Sum Total S*
IBC-102
Fresh 0.14 0.048 1.85 0.96 3.00 3.29
Weathered 1.28 0.25 0.12 1.01 2.66 3.18
IBC-109
Fresh 0.033 0.027 0.41 0.60 1.07 1.12
Weathered 0.21 0.10 0.15 0.64 1.10 1.09
*Total sulfur was determined independently to check on the sum of sulfur forms.
Table 2
Percent sulfur volatilized during pyrolysis and collected in hydrogen peroxide solution,
% sulfur remained in char, and % char yield for fresh and weathered samples of coals
IBC-109 and IBC-1Q2
Sample % total sulfur % total sulfur % char

volatilized in char yield
IBC-102
Fresh 37. 63. 55.9
Weathered 45. 55. 62.7
IBC-109
Fresh 39. 61. 63.3
Weathered 42. 58. 68.2
for the fresh coal alone (Figure 3A, solid line), indicating additional sulfur release from
the mixture possibly due to the reaction between sulfides and elemental sulfur.
Figure 4B shows the sulfur evolution profile for a mixture of 1.1 gram of fresh sample
of coal IBC-102 and 4.7 mg of elemental sulfur (solid line) as compared with that of a
weathered sample of IBC-102 (dotted line). The profile of the mixture shows a low-
temperature peak at 310C resulting from the release of elemental sulfur. The
weathered coal shows a low temperature peak at 340 C. This peak is partially resolved
from the organic sulfur peak in the profile of the weathered sample; the true peak
temperature of the former would be lower if it were resolved as a single peak. It
appears that the 340 C peak in the sulfur release profile of the weathered sample of
coal IBC-102 results primarily from the release of elemental sulfur.
23
3.4
c 3.2 Coal IBC-109
Weathered sample
2.8 Fresh sample plus

2.6 1.7mg elemental
O 2.4 sulfur
2.^
<D
1.8
1.6
W 1.4

CO 0.8
t 8:S

0.2
Q .
So5 200 30 400 50 ^600 700 800
Temperature CC)
Figure 4A. Sulfur evolution profile of a mixture of fresh sample of coal IBC-109 (1.2 g)
plus 1.7 mg elememal sulfur as compared with that of a weathered sample of IBC-109.
_ 9 Coal IBC-102
Weathered sample
Fresh sample plus
4.7mg elemental
2 6H sulfur
2 5 -
4 -

3 -
CO 2-
t 1-
00 200 300 400 500 ^600 700 800

Tennperature ( t )
Figure 4B. Sulfur evolution profile of a mixture of fresh sample of coal IBC-102 (1.1 g)
plus 4.7 mg elemental sulfur as compared with that of a weathered sample of IBC-102.
24
3.5. Pyrolysis of a mixture of coal with ferric sulfate

Pyrolysis of pure ferric sulfate [Fe2(S04)3.xH20) alone showed a peak between 600 *C
and 750 *>C with a peak maximum at 705 C. However, the release of sulfur from ferric
sulfate in coal during pyrolysis is quite different from the release from the pure
compound alone. Figures 5A and 5B show pyrolysis sulfur release profiles for a slightly
weathered sample of coal IBC-102 (34 days since the sample was exposed to air) and
for a mixture of 0.94 g of the same sample of IBC-102 and 17 mg of ferric sulfate,
respectively. The sulfur release profile of the pure coal (Figure 5A) shows three peaks
at approximately 360C, 460C, and 590C, corresponding to the release of elemental,
organic, and pyritic sulfur, respectively. The sulfur release profile of the mixture of coal
plus ferric sulfate shows four peaks: 360C, 450C, 525 C, and 585 >C. The 525 C
peak is apparently due to the release of sulfur from the ferric sulfate. Reaction of the
ferric sulfate with the coal causes it to be decomposed at a lower temperature during
pyrolysis than that for pure ferric sulfate (705 <*C).
3.6. Mass balance

Mass balance data for the pyrolysis reactions are listed in Table 2. During pyrolysis
of the fresh and weathered samples of IBC-102, 37% and 45%, respectively, of the total
sulfur in the raw coal were volatilized. Similarly, 39% and 42% of the total sulfur in raw
coal were volatilized during pyrolysis of fresh and weathered samples of IBC-109. A
large portion of the sulfur remains in the pyrolysis char.
Two major reactions occurred during temperature-programmed coal pyrolysis to
800 C. First, a large proportion of the organic sulfur compounds is volatilized during
pyrolysis. However, various organic sulfur compounds have different thermal stabilities.
Calkins showed that model compounds of aliphatic sulfur are almost totally converted
to volatile H2S and CS2, but thiophenic compounds are little affected at a pyrolysis
temperature of 800 ^C [9]. It is likely that thiophenic organic sulfur largely remains in
the residues in our experiments. The second major pyrolysis reaction is the
decomposition of pyrite, which results in the formation of pyrrhotite and release of
sulfur. Pyrrhotite is stable at 800 C [10, 11] and remains in the residues.
4. CONCLUSIONS
Sulfur release profiles were determined for two Illinois Basin coals by temperature-
programmed pyrolysis-gas combustion technique in combination with a quadrupole gas
analyzer to measure SO2 in the combustion gases. The results show that 37-39% of the
sulfur was released from fresh samples of IBC-102 and IBC-109 and 42-45% of sulfur
was released from weathered samples of the same coals (Table 2) during pyrolysis to
8OO0C.
The peaks in the sulfur release profiles result from the volatilization and
decomposition of four sulfur forms in the coals. For the samples investigated in this
study, elemental sulfur is volatilized between 260 <C and 360 C peaking at
approximately 320*>-350C. Part of the organic sulfur is released between 380 C and
550 C with maximum volatilization occurring at approximately 450C-480C, and pyrite
(FeS2) decomposes to pyrrhotite (Fe^^S) plus sulfur between 550C and 700C with a
25
100 300 500 ^ 700

Temperature { C)
Figure 5A. Sulfur evolution profile of a slightly weathered sample of coal IBC-102 (34
days since being exposed to air).
100 300 500 700

Temperature { C)
Figure 5B. Sulfur evolution profile of a mixture of a slightly weathered sample of coal
IBC-102 (0.94 g) plus ferric sulfate (17 mg). The 525 " C peak apparently results from
the reaction of ferric sulfate with coal.
26
peak at approximately 600 C. The ferric sulfate sulfur has a peak of sulfur release at
525 **C as a result of its reaction with coal. The pyrolysis-gas combustion technique in
conjunction with quadrupole gas analysis is an effective method for characterizing four
sulfur forms in coal.
ACKNOWLEDGMENTS
This work was sponsored by the Illinois Department of Energy and Natural Resources
through its Coal Development Board and the Illinois Clean Coal Institute, and by the
U.S. Department of Energy. We thank Dr. J.H. Goodwin for constructive editorial
suggestions.
REFERENCES
1. C.-L. Chou, ACS Symposium Series 429 (1990) 30.

2. A Attar, Analytical Methods for Coal and Coal Products III (1979) 585.
3. R.B. LaCount, D.G. Kern, W.P. King, T.K. Trulli and D.K. Walker, ACS Div.
Fuel Chem. Preprints, 37 (1992) 1083.
4. J.-P. Boudou, ACS Symposium Series 429 (1990) 345.
5. K.C. Hackley and C.-L. Chou, ACS Div. Fuel Chem. Preprints, 37 (1992) 738.
6. R.D. Harvey and C.W. Kruse, J. Coal Quality, 7 (1988) 109.
7. K.C. Hackley, R.R. Frost, C.-L. Liu, S.J. Hawk, and D.D. Coleman, Illinois State
Geological Survey Circular 545 (1990) 33 p.
8. L.M. Stock and R. Wolny, ACS Symposium Series 429 (1990) 241.
9. W.H. Calkins, Energy Fuels, 1 (1987) 59.
10. A Attar, Fuel, 57 (1978) 201.
11. J.R. Craig and S.D. Scott, Sulfide Mineralogy (edited by P.H. Ribbe), Mineral.
Soc. Amer. Short Course Notes, 1 (1974) CS-1.
edited by B.K. Parekh and J.G. Groppo 27
The Petrological and Geochemical Characteristics of Permian High

Organosulfur Coal from Guidin , China
Lei Jiajin and Ren Deyi
Graduate School of China University of Mining and Technology
Beijing,100083, P.R.China
Abstract
Some high organosulfur coals occur in upper Permian coal-bearing sequence in
Guidin, southwest China . By electron microprobe analyses, the content of organosulfur
in desmocollinite is as high as 10.3%. Petrologically, the coal has following characteris
tics: l)Desmocollinite accounts for a great part of maceris; 2)Most of the
desmocollinite fluoresces brown - orange, although the coal rank is up to
V R o , m a x = 1.48% ; 3)There are many pyritized microbe bodies with the shapes of
coccoid , rod and curved rod , indicating that a large amount of microbes took part in
the peatification ; 4)Many authigenic calcite , dolomite and quartz crystals existed in the
c o a l ; 5)Some marine fossils are found in c o a l . XPS analysis has been made on the bulk
sample. The major organosulfur form is thiophenic , while a very small part is aliphatic .
Three series of thiophenic compounds and its derivatives were determined by G C M S
in extract, and no aliphatic sulfur was detected.
Introduction
There is a large quantity of high organosulfur coals ( H O S C ) among high sulfur
coals in China. This kind of fuel has caused serious environmental problems in some re
gions. U p to now no technology is in use for effective removal of organic sulfur. This is
due in part to insufficient information regarding the types of organic sulfur present in
coal. Characterization of organic sulfur forms is required for developing desulfurization
technologies.Origin of sulfur in coal was recently reviewed by Chou(1990). Two origins
of organosulfur in coal are known: indigenous sulfur which existed in coal - forming
plant and secondary sulfur which formed during diagenesis. The primary organosulfur
in H O S C is secondary, which were formed by a reaction of organic molecules with
28
inorganic sulfur species (HjS . H S " . S") which were produced by sulfate-reducing
bacteria (Chou, 1990) .Such reaction mainly occurred at double bonds or other active
functional groups (Sinninge Damste et al., 1990; Casagrande, 1987). However, to a large
extent the degree and speed of the reaction depend on depositional environments, stage
of diageneses and characteristics of coalforming materials, which would be reflected in
petrological features.The organosulfur content (OSC) of Guidin coal is as high as 10.
32%. Characterization of the organosulfur compounds in it is expected to attain infor
mation for desulfurization.
Geological setting
Guidin coal mine is located in the middle part of Guizhou province, China. The
coal-bearing sequence, the Changxin group, is upper Permian and is composed of
carbonates and a minor amount of siliceous rocks, carbonaceous shales, and coal
seams. The coal seams were accumulated on a tidal flat enviroment of restricted
carbonate platform. The principal seam. No,3 coal seam, was selected for study. At the
site where we collected samples the thickness of the coal seam is 1.10 m. There is a clay
parting of 5 cm thick in the middle. Its roof and floor are both carbonate rocks.
Petrological characteristics
Guidin coal is dull and brittle, and macroscopically shows finely banded, linear and
granular textures. The coal has a strong sulfur smell, but no pyrite grains is visible.The
coal seam was divided into 7 slices which represent different lithotypes ( G D - 1 to G D - 8
from top to bottom). The bright bands and dark bands alternate with each other in the
coal profile.
Under microscope desmocollinite whose surface is smooth is prevailing among
maceris (Table 1). It flouresces brown-orange under blue light excitation. The cell tex
tures of telinite were poorly preserved due to gelification. Among the inertinite group
many fusinites occur in the forms of lenes, short bands,and lumps which can be ob
served macroscopicly on polished surfaces. Their sizes are generaly 17 mm by 4 mm. The
cell walls of these fusinite are relatively thin and broken. Cell lumens are filled with clay
minerals or calcites. Most of the other kinds of fusinites and semifusinites which can be
observered only under microscope were dilated in different degrees also due to
gelification, and many of them have become macrinite. According to the anatomical
characteristics of some fusinites which were well-preserved, it is concluded that
29
Lepidodendrons, Psaroniuses and Gymnosperms account for a large amount of

coal-forming plants.
table 1 Composition of maceris in Guidin coal
^ organic components(%) inorganic components(%)
r oQ
o 2 g Maccral Maceral Carbonate
TO cc DC VD SF F Ma Fossil Cry Epi.
GD-1 15 87.5 0.6 0.6 0.6 84.5 1.2 12.5 1.2 10.2 ... 4.0 4.0 3.0 2.0 2.1 1.0
GD-2 10 80.8 0.8 1.4 0.5 75.4 2.7 19.2 4.1 14.1 1.0 5.0 14.0 5.0 3.0 -
GD-3 15 89.4 - 4.0 0.7 84.8 - 10.5 1.2 8.5 0.8 3.0 3.0 4.0 1.0 3.0
GD-4 10 85.0 0.9 5.3 0.1 64.6 12.9 16.2 5.6 9.4 1.2 4.3 17.7 9.5 0.2 1.4 0.9
GD-6 15 86.7 0.2 1.2 1.0 83.1 1.2 13.3 1.2 10.1 2.0 4.4 7.1 3.0 2.0 0.5
GD-7 20 83.9 1.1 2.3 4.6 75.9 - 16.1 3.5 12.4 0.2 3.4 2.6 3.0 0.1 4.0 -
GD-8 15 89.9 0.6 2.8 1.1 85.4 - 10.1 1.1 8.5 0.5 1.6 4.2 2.0 2.0 -
Vvitrinite ; Ttelinite ; TCtelocollinite ; CCcorpocollinite ;
DCdesmocollinite ; VDvitrodetrinite ; Iinertinite ; SFsemifusinite
Mamacrinite ; Ffusinite ; Qquartz ; Cry crystal; Epiepigenetic;
MCclay minerals
Carbonate, quartz, pyrite and clay minerals are the major mineral matter in the
coal. Some phosphates is observed.Many idiomorphic calcite and dolomite crystals in
the shapes of rhombus, rectangle and rod of variable sizes are shown under microscope.
A number of marine calcareous zoolites, calcispheres, calcareous algae and their frag
ments have also been observed embedded in matrix, especially in the upper slice. Most
of these fossils are broken with their long axis parallel to bedding indicating
transported. The quartz grains are all in the shapes of prism with sharp ends. The sizes
are usually 1 0 ^ 100/xm. Their irregular arrangement indicates that the crystals are
authigenic. F o u r forms of pyrite existed in Guidin coal: framboid, crystal, fine grain and
pyritized microbe body. Framboidal pyrites occur as aggregats, and scattered distribu
tion is the most common occurrence of finegrained pyrites. The shapes of euhedral
30
crystal pyrites are hexagonal and cubic under microscope with hexagonals most com
mon. Their sizes are generally 10-20/im. The pyritized microbe bodies ordinarily occur
as rods, coccoids and curved rods in the 0 . 5 ^ 2/xm size range, many of which may be
identified as Desulfurovibrio.
Illite and montmorillonite are the primary clay minerals which filled lumens of cells
or mixed with organic matter to form organomineral matrix. There are two types of
phosphate: pentagonal crystals and bands with laminae within them. Electron
microprobe analysis shows that their chemical composition is similar to apatite.
Using transmitted electron microscope, a large amount of small len, ellipse or
sphere bodies were discovered in desmocollinite of Guidin coal. They are brighter than
matrix and have distinct boundaries. Some reports (Taylor and
Lin,1987,1989;Wang,Shi and Lei,1993) are available about such materials. Here we
propose that they are remains of algae and bacteria.
Chemical characteristics
Data of chemical analyses of Guidin coal are listed in table 2. The coal is medium
bituminous coal by criteria of volatile matter content ( = 21.82%) and
VRomax(= 1.48%).Other characteristics about the coal which can been seen from table 2
are high ash and high sulfur content with organosulfur accounting for majority (more
than 83%) of total sulfur, placing it among the rare high organosulfur coals (HOSC) of
the world.
To study the distribution of organosufur in coal, desmocollinites in different slices
were analysed using EDX for OSC. The results were shown in table 3. Except the slice
directly under the parting, all others are over 10% in OSC.
To study the organosulfur compounds in mobile phase, Guidin coal was extracted
using trichloromethane. From the extract, '''aromatic'^ fraction was isolated using col
umn chromatography, from which then some sulfurcontaining compounds were ob
tained. G C - M S analysis shows that those compounds mainly occur in homologous se
ries, such as benzothiophene series, dibenzothiophene series, phenanthrothiophene se
ries, among which dibenzothiophene is most abundant. Similar to well-known Rasa
coal studied by White(1990),the major organosulfur molecular structure in extract of
Guidin coal are in the form of thiophene, while the other compounds, such as
sulfides,thiols are relatively minor.But unlike Rasa coal , no organosulfur compounds
contained 2 or 3 sulfur atoms per molecule are detected. Of course, these compounds
31
only represent the low molecular weight compounds(LMWC) of mobile phase . In order
to study macromolecular network phase, which is the main component of coal, solid
coal sample was analysed using XPS(Fig.l) as described elsewhere (Keleman,1991). The
peak at 164.1 ev of binding energy (B.E.), representing thiophenic sulfur, was highest
which accounts for 7 5 . 4 % by area, while the peak at 163.2 ev, representing sulfides, is
only 9. 8%, which may contain aryl and alkyl sulfides because of their difficulty of reso
lution.Another two peaks are weak. As mentioned above, we can see that both in mo
bile phase and in macromolecular network phase organosulfur is mainly in form of
thiophene. The only difference is that macromolecular network contains some sulfide,
while the compounds were not detected in L M W C up to now.It is our future work to
testify if there is sulfide in high molecular weight component (i.e. nonhydrocarbon frac
tion and asphaltene) of extract.
table 2 Proximate analysis and composition of sulfur forms (%)

Mad Ad Vdaf St,d Sp.d So.d Ss.d So.daf
1.64 31.00 21.82 8.50 1.39 7.31 0.10 10.20
M - m o i t u r e ; A - a s h ; V-volatile matter; St-total sulfur; Sp-pyrite sulfur;So-organ-

ic sulfur; Ss-sulfate sulfur; a d - a i r dry; d - d r y ; d a f - d r y ash free
PK E N E R G Y MAX AREA
I G 168.85 7.64 8.1
2G 160.00 8.75 6.4
3G 164.10 88.1 75.4
4G 163.20 17.0 9.8
B.E.
Fig. 1 XPS spectra of Guidin coal
32
table 3 Organosulfur content of Guidin coal determined by E D X

Slice GD-1 GD-2 GD-3 GD-4 GD-6 GD-7 GD-8
So(%)
11.23 10.06 10.35 10.41 9.47 10.27 11.2
By EDX
Discussion
Guidin coal of China, similar to Rasa coal of Istria peninsula, is a rare high
organosulfur coal. The main reason was its special depositional
environment.Coal-bearing sequence shows that Guidin coals were formed in tidal flat
swamp on restricted carbonate platform, which was subjected to marine and tidal influ
ences. The floor of coal is dark grey shell limestone which contains a lot of
Gymnocodium fossils and their fragments, indicating that Gymnocodiums throve on
tidal flat before peat accumulation. It was just the deposit of the algae that led to the
formation of peat swamp. The tidal flat peat swamp was different from other common
peat swamp in following aspects:
1) coal-forming material contained a large amount of algae and bacteria. Some
telalginites and lamalginites were found in thin-section, and supermicroexinites were
observed under T E M . At the same time desmocollinites of coal fluoresce b r o w n - or
ange color, despite of the higher rank of coal. These observations indicate that many
algae and bacteria and their metabolite contributed to the peat accumulation. The inter
esting point is that Gymnocodium is a kind of Rhodophyta whose sulfur content is
highest among algae (Wolfe et al., 1991), It might be an important source of
organosulfur in coal. 2) Peat swamp was strongly influenced by tidal water and often
covered by marine water. Dark layers with abundant minerals and bright layers with
rich vitrinite alternate with each other in the coal seam. M a n y calcareous fossils are em-
beded in the coal matrix arranged parallel to the bedding plane. Calcisphere fossils are
broken (calcisphere is a spore of Acetabularia that lived in the shollow zone of gulf), in
dicating that they were transported into peat swamp by tidal water. The desmocollinites
of Guidin coal are rich in Na(728 ppm), K(4310 ppm), Mg(4070 ppm), B(180 ppm),
Mo(160 ppm),Sr(140 ppm) by I N A A , whose contents are several times as high as that
of coals formed from alluvial peat. These are evidence for peat swamp being influenced
by sea water. 3) The peat swamp water were neutral to weakly alkaline and anaerobic.
A lot of syngenetic carbonates and quartzs are in the coal. The two kinds of minerals,
which differ in resistance to acidity, were formed almost in the same time.It means that
the peat swamp water must have been neutral to weakly alkaline. Microbes, especially
33
sulfate-reducing bacteria, were very active in the condition, reducing SOj"to HjS,
HS"(Chou,1990). Cohen (1984) reported a similar case in modern mangrove swamp de
veloped on carbonate platform in Florida. The strong activity of sulfate reducing bacte
ria in marine deposit could result in precipitation of quartzs and carbonates (Lalou,
1957). In Guidin coal, the occurrences of both syngenetic carbonate and quartz were re
lated to activity of sulfate-reducing bacteria.
The formation of Guidin high organosulfur coal is also related to low concentra
tion of ferrous iron of medium and types of coal-forming material. Generally speaking,
sulfur species, such as HjS, S " , HS", would react with ferrous iron prior to organic mat
ter. Only under condition of lacking supply of ferrous iron, could sulfur species be ad
ded to organic matter. As mentioned above, Guidin coal was accumulated on carbonate
platform where the supply of terrigenous detritus was limited. The concentration of fer
rous iron in swamp was also minor. To demonstrate this, samples were analysed by
INAA. The result was that the total Fe content in Guidin coal is only 8600ppm, while
that of Liuzhi coal, whose total sulfur is much lower ( = 4.3%), is as high as 16000 ppm,
with a lot of pyrite. According to Sinninghe Damste and De Leeuw (1990) the reaction
between sulfur species and organic matter easily take place at active functional groups
of organic materials. The coal-forming sources of Guidin coal were rich in algae and
bacteria which contained compounds with abundant active functional
groups.Additionally,an alkaline marine environment high in HjS and HS~is favorable
for incorporation of sulfur into organic matter(White,1990). These conditions exactly
favored the formation of organosulfur in coal.
The organosulfur compounds formed during early diagenesis are relatively rich in
sulfides, thiols and other aliphatic sulfur containing compounds. But during diageneses
a large part of them may be converted to thiophene and its derivatives. There are not
any aliphatic sulfur detected in L M W C of mobile phase(extract) of Guidin coal. It
means that the relatively small molecules are easily cyclized and aromatized during
diageneses,because of the mobility of chains as shown in Fig.2. But it is much difficult
to large molecules to undergo such change.Therefore,although the sulfurs in network
are mainly converted to thiophene,but many of them are also apt to become aryl
sulfides,which acted as '^bridges'^ bewteen structure units of network. Aryl sulfides
which are primary form of sulfides in network, are stabler than other sulfides.Similar
conclusion was attained in Rasa coal (Brown, 1992).However, it is also possible that
34
there are aryl sulfides in H M W C ( i. e. nonhydrocarbon fraction and asphaltene) of ex

tract, because of their condensation similar to network to some extent. This is why there
are less sulfides in L M W C than in network and H M W C (high molecular weight com
pounds ) of mobile phase.
Fig.2 Cyclization and aromatization of L M W C
Conclusions
1. Maceris in Guidin coal commonly underwent deep gelification leading to poor
preservation of cell structure.
2. The condition of medium of ancient peat swamp was neutral to weakly alkaline
and anaerobic resulting in thriving of bacteria, especially sulfate-reducing bacteria.
This condition also favored incorporation of inorganic sulfur into organic matter.
3. A large amount of algae, bacteria and their metabolites took part in coal forma
tion.
4. Geololgical setting was very important to the enrichment of organosulfur in
Guidin area. It provided suitable conditions for limiting Fe ions and supplying sulfur.
5. There are more aryl sulfides in network and H M W C than in L M W C in Guidin
coal due to diagenesis.
Acknowledgments
We thank National Natural Science Foundation of China for the support of our
project. We are also indebted to G u Yongda and Wang Xuzhen for their offering of
G C - M S data.
References
Brown,J.R.et al.(1992) Direct identification of organic sulfur species in Rasa coal
from sulfur L-edge absorption near-edge spectra.Fuel, 1992,Vol.71,June,pp.649-653.
Casagrande, D.J.,(1987) Sulfur in peat and coal. In Scott, A.C.(ed.), 1987, Coal
and coal-bearing strata: Recent Advances, Geological Society Special Publication
No.32. pp. 87-105.
35
Chou,C.-L.,(1990) Geochemistry of sulfur in coal. In Geochemistry of Sulfur in

Fossil Fuels(edited by W.L.Orr and C.M.White) ACS Symposium Series 429 ,Chapter
2,pp. 30-52. American Chemical Society, Washington,D.C.
Cohen, A.D. Spackman, W. and Dolsen, P.,(1984). Occurrence and distribution of
sulfur in peat-forming environments of southern Florida. International Journal of Coal
Geology, 4(1984) 73-96.
Kelemen, S.R.et al.,(1990) Direct determination and quantification ofsulfur forms
in heavy petroleum and coals. I.The x - r a y photoelectron spectrascopy (XPS) approach.
Fuel, 1990, vol. 69. August.
Lalon, C , (1957) Studies on bacterial precipitation of carbonates in sea water.
Journal of Sedimentary Petrology, vol.27. N o . 2, pp. 190-195.
Sinninghe Damste, J.S. and De Leeuw J.W., (1990) Analysis structure and
geochemical significance of organically-bound sulfur in the geosphere: state of the art
and future research. Org. Geochem. vol.16, N o s 4 - 6 pp.1077-1101,1990
Taylor,G.H.and Liu,S.Y., ( 1987) Biodegradation in coals and other organic-rich
rocks.Fuel,66:1269-1273.
Taylor,G.H., Liu,S.Y.and Diessel,C.F.K.(1989) The c o l d - climate origin of
inertinite-rich Gondwana coals.Int.J.Coal Geol.,11:1-22.
Wang,F.Y.,Shi,G.S.and Lei,J.J.,(1993) The detection and its significance of
supermicroexinite in coal.Science Bulletin(in Chinese) N o . 1,1993.
Wolfe et al., (1991). Climatic and environmental implications of biogas exchange at
the sea surface:modeling D M S and the marine biologic sulfur cycle. In Ocean margin
processes in global change (Edited by R.F.E. Maufoura et a l . ) , pp.383-400.
RESEARCH ON DIFFERENT PYRITES IN LATE PERMIAN

COAL OF SICHUAN PROVINCE, SOUTHWESTERN CHINA
Yuegang Tang and Deyi Ren
Beijing Graduate School,China University of Mining and Technology,Beijing
100083,P.R. China
ABSTRACT
A number of different pyrites in Late Permian sulfur-containing coals and some
associated rocks in Sichuan province of southwestern China have been studied system
atically by optical microscope,SEM and STM for crystal shape, distribution,
morphology and atomic structure. The chemical composition were analyzed using by
, techniques. The results indicated that there are different pyrite
paragenesis and desulfurization properties in the different types of sulfur-containing
coals formed on different depositional environments. Super microscopes reveal that
there is colloidal pyrite in coal. The microanalysis shows that the several types of pyrite
have difference in element composition and physical and technological property such as
susceptibility etc. The crystallization of pyrite plays an important role in concentration
of major elements.
INTRODUCTION
Investigation on the sulfur in coal may date back to the begining of this century
(Thissen,1919; White, 1913) in America, In recent twenty years, more and more articles,
reports and books about sulfur have been published. Key studies of sulfur in coal in
clude Casagrande(l); Berner; (2)Cohen(3) et al in America; Hunt(4) in Austrilia;
Kizilstein in Russia and so on.
T w o - t h i r d s of total sulfur in the high sulfur coals in China are dominated by
inorganic sulfur, at least 9 5 % of which consists of iron sulfide. Therefore, researches on
pyrite,a major carrier of sulfur which infiunces the quality of coal, have increasingly at
tracted coal technologists^ attention . Nantong of Sichuan province is one of the impor
tant coal production area in southwestern China, which is one of the high sulfur coal
regions in China.Our reseach objective is to study the character of pyrites in coal and
associated rock,such as their distributions, physical and physicchemical properties
etc.,and to supply fundamental data for coal desulfurization technology, coal processing
and utilizations .
SULFUR FORMS IN SICHUAN COAL

Objective coal seams of our investigated fields are Toulianzi coal of Wuyi coal mine
at Anxian county , # 5 and # 6 seams of Nantong coal field at Chongqing, C2 seam of
38
Muchuan county.Basically they represent for several types of coal containing different
sulfur forms in Sichuan province. Table 1 shows sulfur forms of coals at different sites.
Table 1. The Sulfur Forms in Different Coals of Sichuan Province,China
Sulfur Analysis % Coal

Reseach Coal So/St
Ash % - O rt / l oA
oOyOai /o
f Depositional
Site Scam %
St,d Sp,d Ss,d So,d Enviroment
Muchuan
C2 39.81 0.65 0.26 0.12 0.24 0.40 36,92 Alluvial Plain
Gouty
Nantong
#5 17.59 4.81 4.06 0.06 0,69 0.83 14.34 Tidal Flat
in Chongqing
Nantong
#6 21.56 2.73 1.53 0.12 1.08 1.38 39.56 Coastal Plain
in Chongqing
Wuyi Coal Mine
TLZ 13.81 11.13 3.56 0.08 7.58 8.70 67.39 Marine Platform
Anxian County
Generally, when total sulfur content(St.d) is less than 0.5% ,the main sulfur form in
coal is organic sulfur (Hunt,1987)(4). But C2 coal seam at Muchuan countuy mainly
contains inorganic sulfur which occupys 63. 0 8 % of total sulfur. From continental to
marine environment, total sulfur content in coal increases , the sulfur forms are
different. The sulfur form in Coal formed on tidal flat is mainly in the form of iron
sulfide (Sp.d). The Wuyi and Nantong # 6 coal seams is rich in organic
sulfur(So.d).Both of them are influenced by roof rock of l i m e - stone or m u d - l i m e stone
of marine facies. Moreover, there is a trend that organic sulfur content increases with
the increases of total sulfur,and pyritic sulfur is the main form of sulfur in many
Sichuan c o a l s .
THE DISTRIBUTION OF PYRITES IN COAL

Macroscopically there are rarely single crystal or film pyrite in low sulfur coal
formed in alluvial swamp at Muchuan. However, there are a lot of nodular, lenticular,
pisolitic, chrysantheman-like, massive, v e i n - like pyrites etc. in Nantong # 5 , # 6 coal
seam where sulfur is accumulated on transitional facies. At the lower part of Wuyi high
sulfur coal seam,there are a lot of fine disseminated pyrites showing lamellar
structure,but no pyrite can be seen by naked eye at the middle and upper p a r t . Nodular
pyrite occasionally contains marcasite and pyritized organism and biological relics.
Microscopically, there are single crystals and aggregates, framboid and its aggre-
gates,globular,nodular,pore-nodular, biological, massive, vein, r o d - like pyrites and
marcasites in coals.Table 2 shows the quantitative statistics of 300 iron sulfide particles .
Obviously, pyrites in Muchuan coal are mainly framboidal which are mostly associated
with clay ,and partly epigenetic vein-like pyrite. In Nantong coal, there are a lot of
nodular and cell- infilling pyrites. The pyrites in Wuyi coal are mainly euhedual crystal
and framboid and their aggregates (figure 1-a ).Euhedual crystals are mostly
octahedron. Wuyi coal contains more marchasites(figure l - b ) . I n general, framboidal
morphology is present in all salinites (5).Similarly,framboidal pyrites in Sichuan coal
are seen in all depositional facies.Using scanning electron microscope( SEM) , we have
observed pyritized Desulfovibrio,rod-chain bacteria,fme coccoides etc.There are also a
39
lot of pyritized algae such as Permocalculus Sinica,and Rhodophyceae.The crystal

shapes of pyrite such as cube, octahedron, pentagonal dodecahedron and their combi
nation can be easily observed by SEM.The cubic pyrite tends to distribute in continental
facies, while the others are mostly devoloped in marine sediment(6), e.g.octahedron
pyrite in Wuyi coal was formed in marine facies. The results are similar to that reported
by Anchun Li et al(1991)(7).Marcasite is usually lamellar. orever,crystal
imprint,crack, grow lamination,defect,erosion relic and other matter on crystal face
have been seen by SEM.Especially colloid like structure, which devoloped in nodular
pyrite, also has been observed. Coal pyrites, microscopically, contain a lot of pore
pyrites,pyritized organisms and marcasites.
Table 2: Microanalysis of iron sulfide in coal
Muchuan Nantong Nantong Wutyi

analysis item
C 2 coal # 5 coal # 6 coal ToHanzi
euhedral crystal pyrite 12.8 20.6 1.5 45.0

framboid pyrite 64.4 0.7 1.5 30.6
nodular pyrite 75..9 89.8
massive pyrite 2.1 2.7
vein-like pyrite 19.2 0.7 2.9 0.9
marcsite 1.6 4.4 20.7
<1 41.5 5.1 2.2 28.1

1-50 25.9 41.9 37.1 42.5
iron
5-10 17.0 23.5 25.3 24.2
sulfide
10-20 11.6 11.0 9.6 3.3
particle
20-50 2.0 13.2 13.6 0.7
size(/im)
50-100 1.4 2.9 3.9 0.7
>100 0.7 2.2 8.4 0.3
no liberated 59.9 37.9 24.4 69.9

- 2 0 mesh liber less liberated 17.7 14.6 16.2 22.8
ating analysis more liberated 4.8 9.0 15.4 1.4
Hberatcd 17.7 36.3 44.1 5.9
Table 2 shows that the pyrite particles in Muchuan coal are basically not liberated.
In N a n t o n g coal, 1-5 ^m pyrite particles are dominant.The quantities of +100 ^m
pyrite particles in Nantong # 6 coal are much more than those in other coals.The liber
ated pyrite in this size is as high as 44.1 % . In Wuyi coal, 7 0 % of pyrite particles are not
liberated in 1-5 m size fraction. It results in difficulty in desulfurization. Wuyi coal al
so contains high organic sulfur, therefore it is very important to study the properties of
pyrites.
40
STM ANALYSIS ON SURFACE OF COAL PYRITES

Scanning tunneling microscope (STM) is an effective tool for the analysis of mate
rial surface.lt directly reflects the image and structure of substance surface from 3m to
lA scale.Eggleston(8,9)(1990,1992) and Fan(10)( 1991) successefully studied pyrite from
other sources except in coal by using STM .In order to explain the difference in physical
properties such as magnetic and oxidation ones of different pyrites, we studied surface
properties of pyrites with STM. The followings are our results and explanations :
Seven coal pyrites and two ore pyrites have been examined by C S T M - 9 0 0 0 scan
ning tunneling microscope for topography in constantcurrent mode and for atomic
image in constant-hight mode.The scanning ranges are 2000X2000A to 33 for to
pography. The granular, pellet,framboid-like, rod,fibre,bandary, milk colloidal and
smooth, level,uneven etc. structure had been observed on the surface of pyrite crystal or
fracture by STM .On the crystal face,oxidative corrosion pit( relics) are often observed.
Generally, on fine granular surface of pyrite, fine grains are in order which is gradually
grown into laminalars,while large granular grains are at random on coarse, and uneven
surfurce of pyrite, which may be caused by surface corrosion. The STM images of frac
ture surface of pyrites in coal show that pyrite of good crystalization is granular grain
(figure l-c),while nodular pyrite of poor crystalization displays more smooth and
milk-colloid like face(figure l-d).The above results observed by SEM indicate that
there may be colloid pyrite in coal.
We have obtained some atomic images in constant-hight mode of STM(figure
1e), they are not very nice and distinct,this is because that the pyrite is covered by an
oxidational film. After the fresh surface of pyrite are covered with silicaoil, we clearly
observed the atomic structure of pyrite surface, and the zigzag chains in some parts. The
interatomic distances reveal that the observed surface is in (210} direction of pyrite crys
tal. Eggleston and Fan observed {100} and (110} direction of pyrite crystal surface.
In summary,STM is a new and effective technique for probing surface topography ,
structure ,crystal growing, atomic structure as well as surface oxidation and corrosion.
STM and SEM directly prove that colloid pyrite exists indeed.
F i g . l . M i c r o p h o t o g r a p h o f iron sulfides in coals and associated rocks.

a.Reficction light micrograph showing aggregate o f pyrite crystals, framboid o f pyrite in W u y i
coal. 2 5 6 X .
b . S E M micrograph of marcasite showing organism structure in Wuyi coal.
c . S T M topomicrograph of coarse granular texture on fracture face o f pyrite, S T M i m a g e - r a n g e
is 3 X 3 .
d . S T M topomicrograph o f s m o o t h , m i l k - c o l l o i d a l texture and r o d - l i k e structure o n fracture
face of nodular pyrite in N a n t o n g coal, S T M i m a g e - r a n g e is 1X1 .
e . S T M atomic micrograph o f pyrite showing less clear image o f a t o m i c arrange a n d oxidation
film o n crystal face , S T M i m a g e - r a n g e is 4 0 X 4 0 A .
f.The clear S T M atomic micrograph o f pyrite s h o w i n g F e or S atom in peak, on crystal face,
S T M i m a g e - r a n g e is 3 5 X 3 5 A .
41
42
ANALYSIS OF PYRITES IN COAL

Electron probe microscope analysis(EPMA)is a method for composition analysis.
The precision of is 1% to 0 . 1 % . In this study, 8 6 0 - E D X of Link
Coporation in U.K. and W D X - 2 A of Microspec Coporation in U.S.A were
used . The latter has a better precision. Some conclusions about analysis of
pyrite in coal are as following.
1.Ordinarily ,besides Fe and S,pyrite in coal often contains Si,Al,Ca, Mg,Ti,Zr,Nb.
The content of those elements in pyrite are proportional to those in matrix vitrinite .The
Co,Ni,Cu,Pb etc, which can constitute the crystal latitices of pyrite,are minor in concen
tration, but they occur none or little in matrix vitrinite. In general,as crystal is trans
formed to framboid and cell- infilling pyrite, associated elements increase gradually.
2.1n same coal seam, S content and S / F e atomic ratio: euhedren crystal >
cell-infilling > circular shape > framboidal increase in the order of pyrite. This indi
cates that crystalization plays a role in sulfur enrichment. Either S or Fe in nodular
pyrite is richer in centre than that at the edge. Apparently nucleation plays a major role
in nodular pyrite formation.The framboidal pyrite in Muchuan coal has very high of
S / F e atomic ratio ( > 5).It contains a large amount of Co, Ni e t c . , and Co / Fe atomic
rafio is near to 3 / 4. So some parts of framboids are not pyrite.Because framboid pyrite
particle is small , the determined value influenced by matrix substance is usually lower
than actual value. It is only considered as referential value.But S / F e ratio is less influ
enced.
3. High S / F e ratio of pyrite devoloped in matrix vitrinite was found to be 6 to 17.
The S / F e ratio of pyrite is proportional to the organic sulfur of desmocollinite. The Fe
content of the desmocollinite in high sulfur coal is relatively low.
INAA ANALYSIS OF PYRITES IN COAL AND ASSOCIATED ROCK

Instrumental Neutron Activation Analysis ( I N A A ) has the advantages of high
sensitivity,good accuracy,multielemental analysis and non-destruction.We used I N A A
to measure trace elements,and associated elements of pyrite for searching the
genesis,physical properties of pyrite.Nine coal pyrite and two ore pyrite samples are an
alysed by I N A A in Institute of High Energy Physics, Academia Sinica ( 1 1 ) . Table 3 is
part of the I N A A results,it reveals the following facts:
I.The elements in pyrites of different coals are different paragenetic types, e.g.in the
pyrite of Nantong # 6 coal, Y REE, ^ , 3 (sum of lithogenic element) are very low, while
Ni,Zn,Na are higher. There are a large amount of associated elements such as Mn,Cr ,
5^2, V,Ba,Ca, Mg etc. in the m a t r i x - like pyrite of Nantong .
2.1n the pyrite from coal and associated rock,macroscopically,from crystal to
chrysantheman,nodular,vein-like and m a t r i x - like pyrite, Fe content decreases gradual
ly, and Co,Mn, R E E and other assoociated elements increase as the crystalizafional
degree of pyrite becomes worses. The worse the pyrite crystal the higher the Y 3
lithogenic elements .
3. The difference between c o a l - and ore-pyrite is that Y 3 and Y R E E content is
low in ore-pyrite,and As and Y 1 is rich , especially for hydrothermal type of
pyrite(No.39),
4. Table 3 shows some relations between INAA results and susceptibility of pyrite.
Table 3. Part INAA Element Results and Susceptibility of Pyrites
Sample No. 52 No.8 No.3 No. 20 No.1 No. 26 No. 25 No. 53 No.2 No. 39 No.9
Pyrite Cube Cube-acta. Chrysan- Vein Vein Vein Matrix
Nodular Nodular are are
Types Crystal Crystal themum like like like like
Songzao Nantong Nanpeng Nantong Nantong Nantong Nantong Nantong Hunan Chengmen
Sites Nantong
M6 "# 6 coal "# 6 Coal "# 5 Coal "# 5 Coal "# 5 Coal "# 4 Coal "# 4 Coal Leiyang shan
~REE 3. 95 O. 39 2.26 19.27 4.84 32. 32 2. 60 72. 54 66.89 - O. 33
V 1. 65 3.02 8.27 2.04 1.48 0.97 67. 10 O. 67 10. 40
Ba 131. 0 165.0 196.0 49.9 50.5 38.9 35. 2 88. 8 196.0 131. 0 57.2
As 45. 3 97.0 120.0 51.8 38.2 45. 1 89.0 90. 4 20. 6 249.0 122.0
Cu 125.0 55. 6 67.4 131. 0 47.8 72. 5 85.9 51. 4 13600.0
~1 207. 1 173.6 532.2 254.0 138.6 226.5 184.2 296.6 24.6 306.7 13789.5
Fe 411000 400000 390000 374000 387000 363000 310000 355000 321000 401000 305000
Co 0.9 1.9 18.9 6.9 6.3 2.8 12. 6 55.2 48.7 73.7 37.0
Ni 86. 6 77. 9
Cr 5.46 6.44 8. 60 7.87 6.04 6.24 6.32 6.68 31. 6 8.42 20.3
Mn 6.3 61. 2 405.0 76.6 48.4 71. 8 11. 2 14.1 1350.0 10.7 14.7
~2 12.72 156.09 510. 4 91. 39 60.64 80.85 30. 12 75. 98 1430.30 92. 82 72. 00
Na 1950 3550 4020 711 1220 1410 119 1410 837 2860 662
Al 4480 1340 2120 1990 2110 12500 489 18600 12900 1120 2180
Ca 20200 18500 10900 4850 - 37400
Mg 500 955 4510 1410 1380 2300 697 54 12600 829
~3 6930 5845 30850 22711 15610 21060 1305 20064 63737 4809 2842
Suscep-
1. 26 1. 64 30.91 12.14 1. 11 1. 69 11. 22 1. 51 58.40 O. 56 0.92
tibility
Note: 1. INAA unit is ppm. Susceptibility unit is lO-1eum!g.
2. ~l=Cu+As+Se+Sb+Zn; ~2=Co+Ni+Cr+Mn; 2:3=Na+AI+Ca+Mg; ~REE=La+Ca+Nd+Sm+Eu+Tb+Yb+Lu.
3. - is that element hasn't been determined by INAA. ~
w
44
is closely proportional to susceptibility of pyrite.Mg,Co,Ca etc. in coalpyrite have

a relation with susceptibility,while ore-pyrites, which are rich in As,have low magnetic
property.^] 2 (Mn,Co, Ni,Cr) elements, ^ 3 elements have a relation with susceptibility
of pyrites.
Apparently,the susceptibility of coal pyrites are all higher than that of ore pyrites
.So High Gradient Magnet selection ( H G M S ) technology can remove coal pyrite better
than ore pyrite. The magnet analyses of coals indicate that susceptibilities of bituminous
coal are all negative value, while anthracitous coals are all positive value which are ap
proximate to those of coal pyrites, therefore H G M S is more suitable for the
desulfurization of coking coals. We are continuing to undertake study on those fields
.here is only the brief conclusion.
CONCLUSIONS
The following conclusions can be drawn from the above analysis:
I . T h e sulfur content in limnic coal is very poor which is the main property of
framboidal pyrite.The marine-continent transitional facies coal is rich in sulfur,
which is mainly in the form of inorganic sulfur. The nodular and cell-infilling
pyrite are main types of pyrite and pyrite particles are large.The marine facies
coal has high sulfur content, which is rich in high organic sulfur.Monocrystal,
framboid pyrite and marchasite particles are small. Nodular pyrite often con
tains more marcasite, pyritized organisms and relics.
2. Liberation analyses show that the pyrite in transitional facies coal contains more
librated particles,while marine coal has less amount of liberated pyrite. Nantong
coal contains more nodular pyrites, in which pyrite particles is larger and liber
ated . It is predicted that they possess good behavior for physical
desulfurization.But Wuyi coal contains more fine crystal,framboid and pyrites
are not liberated.Moreover it has very high organic sulfur, so its desulfurization
behavior must be very poor.
3. By STM,we clearly obtain atomic image on (210} surface of pyrite, this is anoth
er new result following the studies by Eggleston and Fan for {100} and {110} of
pyrite crystal surface respectively .Moreover,we have observed several pyrite
structures such as granular, bandary, milk colloid like pyrite, as well as
corrosoion pit and oxidational film . STM,SEM directly prove that colloid pyrite
exists in coal.STM is a very potential technique for the study of pyrite.
4. The composition analyses show: As the pyrite crystallinity become better,Fe, S
and S / F e in coal pyrite increase,the associated elements decrease.There are
Si,Al, Ca, Mg,Ti,Zr,Nb etc.in coal pyrite. The pyrite with high S / F e ratio
grows in desmocollinite which S / F e atomic ratio is 617. The S / F e ratio of
pyrite is proportional to the organic sulfur in desmocollinite.
5. The susceptibility of coal pyrites are much higher than that of ore pyrites. The
susceptibility of coal pyrite has a relation with Mn, Co, Mg, Ca etc. elements. Bi
tuminous coals have negative value of susceptibility,anthracite coals positive.
H G M S is more suitable for the desulfurization of bituminous coals.
45
ACKNOWLEDGMENTS
The authors express thanks to Institute of High Energy Physics of Academia
Sinica,the University of Science and Technoloy of Beijing ,Mr. Libing Liao, China Uni
versity of Geoscience for their help with the use of facilities. We also wish to acknow
ledge financial support from National Natural Science Foundation of China and
Genaral National Coal Cooperation of China.
REFFERENCES
I . D . J . Casagrande, In : Coal Bearing Strata: Recent Advances; Scott,Ed;Geological
Society : London, 1987, pp87-105 .
2. R.A. Berner, Geochimica et Cosmochimica Acta, 48 (1984), 605-615
3. A.D. Cohen,W. Spackman,P. Dolsen, International Journal of Coal Geology, 4
(1983), 73-96.
4. J.W. Hunt, Austrilia Coal Geology, 7 (1987), 11-32.
5. A.M. Bailey, J.F. Sherrill,J.H. Blackson and E.C.Kosters, In : Geochemistry of Sul
fur in Fossil Fuels,ACS symposium series 429; Orr et al Ed; American Chemical Soci
ety , Washington,DC. 1990 , 186-203.
6. Erqin Zhu and Qi Wang, In: Authigenic Mineralogy of Marine; Marine Press:
Beijing, 1988, 32-49.( in Chinese )
7. Anchun Li , Lirong Chen and Shunxi Shen, Science Belletin, 1991,928-930.( in
Chinese and in English).
8. C M . Eggleston and Jr M.F.Hochella, Geochimica et Cosmochimica Acta, 54 (1990),
1511-1517.
9. C M . Eggleston and M . F . Hochella,Jr, American Mineralogist, 77 (1992), 221-224.
10. F u - R e n Fan and Allen J. Bard. Journal of Phsical Chemistry; 95 (1991),1969-1976.
11. NA A Lab. , Institute of High Energy Physics , Academia Sinica, Ed. In : Applica
tions of Neutron Activation Analysis in Environmental Science , Biology and
Geoscience. Atomic Energy Press :Beijing, 1991 ,ppl 98266. ( i n Chinese ).
Electrochemical equilibria in coal flotation systems and their role in

determining the interfacial properties of pyrite and its separation from coal
D. Liu, P. Somasundaran and P. F, Duby
Henry Krumb School of Mines, Columbia University, New YorJc, NY 10027
ABSTRACT
Various chemical reactions occurring during grinding and conditioning of Pittsburgh

No. 8 coal prior to flotation were studied using electrochemical equilibrium method.
The effect of these reactions on the interfacial properties of coal and pyrite as well as
on the separation of pyrite from coal by flotation was investigated. Enhanced pyrite
rejection obtained by increasing the p H during flotation was attributed mainly to the
reduced pyrite hydrophobicity. Induction time measurements showed that pyrite
hydrophobicity decreases with increasing solution p H . Results of the solution electrode
potential measurements suggested that the conversion of pyrite surface from partially
hydrophobic FeS2 hydrophilic Fe(OH)3 around p H 6 may be the reason for decrease
of the pyrite hydrophobicity with increase in p H .
INTRODUCTION
Froth flotation is recognized as an efficient method for separation of pyrite and

other ash-forming minerals from coal; while flotation separation is based on the
differences between interfacial properties of coal and mineral impurities. The
supernatant of coals with high sulfur and high ash contents can contain significant levels
of dissolved mineral species which can adsorb on particles and reduce such differences
[1-2]. p H is an important variable in coal flotation, and when it is subjected to changes
chemical reactions can occur among dissolved mineral species, hydrogen/hydroxide ions
and mineral surface species leading to surface conversions or formation of precipitates
that can attach onto the surfaces and alter the interfacial properties.
The oxidation/reduction potential of a system governs the equilibrium of the
reactions involving proton a n d / o r electrons [3]. Eh of the solution has been used widely
for studying the stability of ions, metals and minerals present in aqueous solutions [4-6]
and it can also be used for monitoring chemical reactions that occur in coal flotation
systems.
In this study, chemical reactions occurring in a coal flotation system upon subjecting
it to p H changes have been investigated by monitoring solution electrode potential and
48
dissolved mineral species. The effect of these reactions on the hydrophobicity of coal
and pyrite as well as their separation by flotation has been studied.
EXPERIMENTAL
Materials
Coal used in this study is a Pittsburgh No. 8 seam sample supplied by R and F Coal
Co., Ohio. The as-received sample (2-4 in.) was crushed, under an argon atmosphere,
to 1/4 in. nominal size using a jaw crusher. The proximate, ultimate and sulfur forms
analyses of this sample are given in Table 1. Flotation feed was prepared by wet
grinding the 1/4 inch sample in a rod mill to 9 5 % passing 200 mesh.
Pyrite was concentrated from a sample of Pocahontas No. 3 coal refuse suppUed by
Island Creek Coal Company, Oakwood, VA. The coal refuse supplied had a high pyrite
content, and was concentrated further by washing, sieving, panning, and magnetic
separation. The final concentrate containing about 90 % by weight of pyrite was used
for induction time measurements.
Coal supernatant was obtained from the coal slurry ground in distilled water and
subjected to aging and conditioning (without reagents) under conditions similar to that
used for the preparation of the flotation feed. N a O H and HCl of ACS Fisher certified
grade were used as p H modifiers. Distilled water was used for preparing stock solutions.
Methods
Analysis of dissolved mineral species: The concentration of dissolved ions was
measured using a Perkin-Elmer ICP/6500 Inductively Coupled Plasma (ICP)
spectrophotometer.
Measurement of solution electrode potential: Eh of the coal slurry was measured
using a Pt electrode with silver/silver chloride as the reference electrode. For
comparison p u o s e s , the Eh of coal slurry was also measured by using a standard
Table 1
Analysis of the coal sample - dry basis
Proximate analvsis and

Ultimate analysis (%) sulfur-forms analysis (%)
C 69.87 Moisture 2.30

5.10 Volatile matter 35.55
1.45 Fixed Carbon 51.86
O 6.40 Ash 12.59
S 4.58 SulfaticS 0.28
Ash 12.60 Pyritic S 2.72
Heating value, Btu/lb Organic S 1.64
12,420 Total Sulfur 4.64
49
calomel electrode (SCE) as reference. The potentials are reported on the standard
hydrogen electrode (SHE) scale.
Induction time measurements: Induction times for coal and coal-pyrite samples
were measured using a APT-lOO type induction timer following the procedure
established earlier [7].
Flotation tests: Flotation tests were conducted using a Denver D-1 flotation
machine with a two-liter cell and provisions for continuous removal of froth. Air was
supplied externally using a blower and a rotameter was used to monitor and control the
air flow rate. Details of flotation machine parameters and other pertinent variables are
given elsewhere [2]. The p H of the coal slurry was varied using N a O H which was added
into the mill prior to grinding.
Rejection of pyrite and non-pyritic minerals from coal

Flotation separation of pyrite and non-pyritic minerals from coal was evaluated as
a function of p H and the results are illustrated in Figures 1 and 2 respectively. In these
figures the separation efficiency has been presented in the form of selectivity curves of
pyritic or non-pyritic minerals rejection versus coal recovery. Increase in coal recovery
along a selectivity curve was obtained by increasing the frother dosage in the range of
0.07 to 0.54 g/kg while
maintaining the other variables
90
such as the p H and the collector 1 1
dosage constant. A shift of the

curve towards the upper right . 85 - CU H ^ w -
hand corner indicates increased
O
selectivity.
80
Figure 1 shows that -
increase of pH, in the p H range
of 4 to 8, leads to enhanced Ol
75 "
separation of pyrite; between cu o pH 4.0
A pH 4.8
p H 8 and 9.2 there is no V pH 5.2 \
improvement of selectivity. In ZD 7 0 pH 7.5 \
\
the case of non-pyritic minerals, in pH 8.0 ^
p H is found to have no
significant effect on selectivity
o
S 65 -

pH 9.2
added in mill
0.90 g/kg dodecane
(Figure 2). Improved pyrite 0.07 to 0 . 5 4 g / k g MIBC
rejection obtained with p H 60 1
increase can be due to a) 40 50 60 70 80 90 100

increase of coal hydrophobicity; COAL RECOVERY, %
b) decrease of pyrite
hydrophobicity; and/or c) Figure 1. Effect of p H on the separation of pyrite
decrease of carry over by from Pittsburgh No. 8 coal; coal recovery along each
entrainment. Decrease in carry curve obtained by increasing MIBC from 0.07 to 0.54
over by entrainment should g/kg.
result in increased rejection also
50
of non-pyritic minerals. Since 85 -i
p H has no effect on the

rejection of non-pyritic minerals
80 h
it appears that improved pyrite O
rejection is due to an increase

of coal hydrophobicity and/or a 75
decrease of pyrite hydro
Ol
phobicity with p H increase in
the range of 4 to 8. 70
CO
<
o
Effect of pH on coal and pyrite
t 65
hydrophobicities a:
pH 8,0
>-
Induction time measure _ pH 9.2
I
ments were carried out to 60 a d d e d in m i l
determine the effect of p H on 0.90 g / k g dodecane
0.07 to 0 . 5 4 g / k g MIBC
coal and pyrite hydrophobicities
55
and the results obtained are
40 50 60 70 80 90 100
shown in Figure 3. In the case
of coal, the induction time COAL RECOVERY. %
(which is inversely related to
hydrophobicity) decreases Figure 2. Effect of p H on the separation of non-
slightly with p H increase in the pyritic ash from Pittsburgh No. 8 coal.
p H region of 4 to 7. Above p H
8, the trend is reversed with the
200
induction time increasing with
Condiiioned In Coal Supernatant
p H increase. Decrease in the 180 [- Decreasing pH
coal hydrophobicity above p H 8 O Coal
can be attributed to the o 160 Coal-Pyrite

ionization of its surface w 140
carboxylic and phenolic groups
[8]. 120
In the case of pyrite, the ^ 100

induction time increases with
p H throughout the entire p H 80
range tested (4 to 10) with the 60

steepest increase occurring O
between p H 6 and 8. Thus, the 40
Q
results of induction time
20
measurements (Figure 3)
suggest that the decrease in 0
7 10 11
pyrite hydrophobicity with p H
increase can contribute pH
significantly to the improved
pyrite rejection with increasing Figure 3. Effect of p H on induction times for coal and
p H from 4 to 10. pyrite particles measured in the supernatant of the
flotation feed.
51
Solution electrode potential of

coal flotation system
To understand the
mechanism by which p H affect
the interfacial properties of
pyrite, the solution electrode
potential of the coal slurry was
measured as a function of p H
under flotation ':onditions and
the results obtamed are shown
in Figure 4. It can be seen
that the Eh of the coal slurry
remains almost constant in the
alkaline p H range; in the
acidic p H range the Eh
increases with p H decrease.
Figure 4 also shows the
concentration dissolved ions in
the supernatant of the coal
slurry. T h e concentration of
dissolved F e species increases
steeply with p H decrease in Figure 4. Eh and concentration of dissolved F e species
the p H range in which the Eh in the supernatant of coal slurry measured under
of the coal slurry also shows a
flotation conditions as a function of p H .
sharp increase; no dissolved Fe
species is detected in the
alkaline p H range where the Eh remains constant. Therefore, the increase of Eh with
p H decrease in the acidic p H range can be attributed to the dissolution of soluble F e
species, because the dissociation of F e ( O H ) 3 to Fe^^ and (OH)" is known to be a
reductive reaction which can result in an increase in the Eh of the solution.
Role of electrochemical equilibria on the interfacial properties of pyrite

Figure 5 shows the Eh-pH equilibrium diagram for Fe-S-H20 system at 25C and
10"^ calculated based on the available thermodynamic data [5,9,10]. It can be seen
from this diagram that at acidic p H values, in the Eh range of flotation (Figure 4), the
surface of the pyrite particle will dissolve forming ferrous iron to maintain equilibrium.
This implies that as long as there is enough material, the surface will remain as pyrite.
However, on increasing the pH, the surface will be transformed into F e ( O H ) 3 . It should
be noted that the species shown in this phase diagram (Figure 5) are expected to exist
at the equilibrium states of the aqueous iron sulfide systems; while, the nature of the
pyrite-related species existing under the coal flotation conditions could be more complex
than that indicated by the equilibrium diagram.
Figure 6 shows the Eh-pH diagram of Fe-S-H20 system, constructed for a meta-
stable equilibrium condition which is more likely to exist under flotation conditions, for
dissolved Fe and S species concentration level measured in the supernatant of the
flotation feed of 10"^ M. The main assumption involved is that the reaction
52
FeS2 + 8 H2O = Fe,2+ 1.0
25042 + 16 + 14e (1)
is too slow to occur during the

time period (2 hrs.) employed
for the flotation tests [11-12].
Instead, an intermediate step
FeS2 = Fe'^ + 2 S + 2e ("^
is assumed for the construction

of the diagram. The solution
electrode potential of the coal
slurry measured under the
flotation conditions is also
presented in this diagram.
Examination of Figure 6
shows that the Eh of the coal
slurry is very close to the line on
which both FeS2 and F e ( O H ) 3
co-exist between p H 4.2 and 6 Figure 5. Eh-pH equilibrium diagram for Fe-S-H20
and elemental sulfur and system at 25C and 10"^ M.
F e ( O H ) 3 co-exist below p H 4.2.
Above p H 6, F e ( O H ) 3 will be
IÊh-pH f o r coal slurry
the most predominant species. ' ^ ' - a d d e d in mill
It is b e l i e v e d that 0"Pt,,vs. Ag/AgCI
Pt. v s > C a l . ( S C E )
elemental sulfur is covalently
bonded with homo-atom and
hence it is hydrophobic, while [ C ] = 1 0 "^M
FeS2 is o n l y partially
hydrophobic because it is
covalently bonded with hetero-
atoms. F e ( O H ) 3 , on the other L
hand, is hydrophilic since the O

bonding in it is entirely ionic.
Thus a s h a decrease in the
hydrophobicity of pyrite around
p H 6 is attributed to the
conversion of pyrite surface
from partially hydrophobic FeS2
to hydrophilic Fe(OH)3.
Figure 6. Eh-pH diagram for Fe-S-H20 system under

CONCLUSIONS meta-stable equilibrium at 25C and 10'^ M; and Eh-
pH curve for coal slurry measured under flotation
Increase of pH, from 4 to conditions.
8, resulted in enhanced rejection
53
of pyrite from coal, but had no effect on the rejection of the non-pyritic minerals.
Increased pyrite rejection with increasing p H was shown, by induction time
measurements, to be mainly due to the decrease of pyrite hydrophobicity.
Solution potential measurements showed that electrochemical reactions play a major
role in determining the interfacial properties of pyrite. The conversion of pyrite surface
from partially hydrophobic FeS2 to hydrophilic F e ( O H ) 3 around p H 6 is proposed to be
a reason for the sharp decrease of pyrite hydrophobicity with p H increase.
ACKNOWLEDGMENT
T h e authors wish to acknowledge the United States Department of Energy (Project

No. DE-AC22-88PC88878) for support of this work.
REFERENCES
1. M.S. Celik and P. Somasundaran, "Effect of Multivalent Ions on the Flotation of

Coal", Sep, Set Technol, 21 (1986) 393.
2. D . Liu, T.V. Vasudevan, P. Somasundaran and C.C. Harris, "Role of p H and
Dissolved Mineral Species in Pittsburgh No. 8 Coal Flotation System - I.
Floatability of Coal", Submitted for Publication on: Int. I Miner, Process. (1993).
3. L.G.M. Baas Becking, I.R. Kaplan and D. Moore, "Limits of the Natural
Environment in Terms of p H and Oxidation-Reduction Potentials", Jour. Geol., 68
(1960) 243.
4. M. Pourbaix, "Atlas of Electrochemical Equilibria in Aqueous Solutions", (J. A.
Franklin, trans.), Pergamon Press Ltd., New York, 1966.
5. R.M. Garrels and C.L. Christ, "Solutions, Minerals, and Equilibria", Harper and
Row, New York, 1961.
6. J.O'M Bockris and A.K.N. Reddy, "Modern Electrochemistry", Plenum Press, New
York, 1970.
7. D . Liu, T.V. Vasudevan, P. Somasundaran and C.C. Harris, "Role of p H and
Dissolved Mineral Species in Pittsburgh No. 8 Coal Flotation System - II.
Separation of Pyrite and Non-Pyritic Minerals from Coal", Submitted for Publication
on: Int. J. Miner. Process. (1993).
8. T. Hamich and B. Siffert, "Determination of Point of Z e r o Charge and Acid-Base
Superficial Coal Groups in Water", Colloids and Surfaces, 61 (1991) 83.
9. J. Barin and O. Knacke, "Thermochemical Properties of Inorganic Substances",
Springer-verlag Berlin, 1973.
10. W. Stumm and J.J. Morgan, "Aquatic Chemistry", John Wiley & Sons, New York,
1981.
11. S. Chander and A. Briceno, "Kinetics of pyrite oxidation", 116th AIME Annual Meet.,
Denver, Colo., SME Preprint No. 87-150, Feb. 24-27, 1987.
12. G.W. Walker, P.E. Richardson and A.N. Buckley, "Workshop on the Flotation-
Related Surface Chemistry of Sulfide Minerals", Int. /. Miner. Process., 25 (1989)
153.
1993 Elsevier Science Publishers B.V,
The interaction of thioglycolic acid and pyrite

S. Luo*, J. F. McClelland*, and T. D. Wheelock''
"Ames Laboratory, Iowa State University, Ames, Iowa 50011
''Chemical Engineering Department, Iowa State University, Ames, Iowa 50011
Thioglycolic acid (TGA) has been shown to depress the recovery of pyrite by either the
froth flotation or the oil agglomeration process. Hence, it can provide a means for
improving the separation of coal and pyrite by these methods. For a better understanding
of the interaction between TGA and pyrite, FTIR-PAS was used to study the adsorption of
TGA on freshly ground mineral pyrite, oxidized pyrite, sulfurized pyrite, elemental sulfur
and coal. Exposure of freshly ground pyrite to ambient air for a few hours produced a thin
layer of iron sulfate, and subsequent treatment of the material with an acidic solution seemed
to leave a lm or coating of sulfur. While freshly ground pyrite and coal were found to
adsorb TGA at pH 3, the adsorption of TGA by sulfur required a pH of 4.6 or higher.
Experimental evidence indicated that the adsorption of TGA by either pyrite or elemental
sulfur involved the formation of a metal thioglycolate, whereas the adsorption of TGA by
coal involved a different mechanism, probably hydrogen bonding of the C = 0 group of TGA
to an - O H group on the coal surface or hydrogen bonding between the carboxyl group of
TGA and a carboxyl group on the surface.
INTRODUCTION
The difculty of separating coal and pyrite by either froth flotation or oil agglomeration
has been recognized for a long time (refs. 1-4). The problem arises because under some
conditions the surface properties of coal and pyrite are similar so the materials respond
similarly to these processes. In a recent study Drzymala and Wheelock (ref. 5) showed that
the separation of coal and pyrite by the oil agglomeration method became increasingly
difficult as the surface of the coal became more heavily oxidized.
Neither coal nor pyrite is stable in the presence of oxygen. On exposure to air the
surfaces of both materials will oxidize. As a consequence coal will become less
hydrophobic and more difficult to float or agglomerate (refs. 6-10). On the other hand,
pyrite can become either more hydrophobic or more hydrophilic depending on the balance
of surface oxidation products (refs. 4, 11). In one study (ref 12) a fresh pyrite surface was
observed to oxidize very rapidly in water, even though the oxygen concentration was very
low, and the pyrite became coated with a hydrophobic, sulfur-like material. In another
study Yoon et al. (ref 11) observed both hydrophobic and hydrophilic oxidation products
56
on pyrite particles which had been oxidized in aqueous suspensions. The product species
responsible for increasing the hydrophobicity of the pyrite appeared to be iron polysulfides,
and the amount of this material increased with decreasing pH. The product species
responsible for making the pyrite more hydrophilic seemed to be iron oxides and hydroxides
which increased with increasing pH. The floatability of oxidized coal pyrite was lower than
that of oxidized mineral pyrite because of a larger concentration of iron oxides and
hydroxides on the coal pyrite.
One way to improve the separation of coal and pyrite by froth flotation or oil
agglomeration is to use a pyrite depressant. Previous studies (refs. 13-17) have identified
a number of potential depressants. One of the most promising depressants is thioglycolic
acid (TGA) which has the following structure: HSCH2COOH. This material has been used
industrially to depress copper and iron sulfides during the flotation of molybdenite (refs. 18-
21). In this application TGA has proved more effective and less toxic than other depressants
such as hydrosulfide or cyanide (ref. 19).
The potential for TGA as a pyrite depressant was confirmed in our work (refs. 15, 17).
High-grade mineral pyrite, which apparently was somewhat oxidized from exposure to the
atmosphere, was readily floated by using diesel oil as a collector. However, the flotation
of the pyrite was depressed markedly by suspending the material in a 0.001 TGA
solution. TGA was s o found to depress both the flotation and oil agglomeration of very
hydrophobic pyrite which had been coated with elemental sulfur. Moreover, the separation
of Illinois No. 6 coal and sulfurized mineral pyrite by selective agglomeration with heptane
was improved greatly by suspending the materials in 0.003 TGA.
The present study was undertaken to achieve a better understanding of the interaction
between TGA and pyrite so as to improve the effectiveness of TGA as a pyrite depressant
in coal flotation or agglomeration. Earlier studies had focused on the interaction between
TGA and copper sulfides. Raghaven and Unger (ref. 19) studied the interaction between
TGA and chalcocite (97.2% CU2S) and they observed that TGA was oxidized rapidly to
dithioglycolic acid (DTGA) in a water suspension of chalcocite particles. The mineral
appeared to catalyze the oxidation reaction through chemisorption of TGA. The following
electrochemical reaction model involving the reaction of TGA in solution with adsorbed
TGA fit experimental rate data well:
TGA,ds + TGA,q ^ DTGA^q -h 2H-^ -h 2e- (1)
This reaction took place in conjunction with the following reaction in the presence of
oxygen:
22 + 2H-^ + 2e- H2O (2)

Both TGA and DTGA were found to be effective depressants for xanthate-coated chalcocite
in microflotation tests carried out with a modified Hallimond tube. However, TGA was
slightly more effective than DTGA. Both materials tended to exert a greater depressing
action in acidic solutions than in basic solutions.
Poling and Liu (ref. 21) studied the interaction of TGA with a mineral sample consisting
largely of chalcopyrite (75 wt. %), pyrite (20 wt. %), and silica (3.3 wt. %). Microflotation
tests of xanthate-treated particles showed that the effectiveness of TGA as a depressant was
57
greater in the presence of air bubbles than in the presence of argon bubbles and that the
effectiveness of TGA increased with increasing pH. Since aeration converted TGA to
DTGA, the increase in effectiveness appeared due to the presence of DTGA. Experimental
evidence indicated that TGA molecules were bonded to the mineral surface through their
- S H and - C O O H groups. Of the two groups only the - S H group seemed capable of
displacing adsorbed potassium ethyl xanthate from the mineral surface, and, therefore, the
- S H group appeared to form a stronger bond with the surface than did the - C O O H group.
Infrared spectra indicated the presence of both copper thioglycolate and TGA on the treated
mineral surface. It appeared that an initial monolayer of TGA was adsorbed on the surface
followed by multilayers of TGA and DTGA held by hydrogen bonding.
For the present investigation, Fourier transform infrared photoacoustic spectroscopy
(FT-IR/PAS) was used to study the adsorption of TGA by freshly ground mineral pyrite,
oxidized pyrite, sulfurized pyrite, elemental sulfur, and coal. Sulfur coated pyrite and
elemental sulfur were utilized since sulfur seems to be a natural oxidation product of pyrite
under some conditions. FT-IR/PAS was used for this study because it is a surface specific
technique.
EXPERIMENTAL METHOD AND MATERIALS
The materials chosen for the investigation included high-grade mineral pyrite from
Huanzala, Peru, a very clean coal from New Zealand, and powdered elemental sulfur. The
Pyramid No. 2 coal came from the Reefton coal field on the South Island of New Zealand.
The pyrite contained very little foreign material, and the coal had an ash content of L 3 %
and a negligible pyrite content. For preliminary measurement of IR spectra, the coal and
pyrite were freshly ground in air to a fine particle size by using a Wig-L-Bug vibratory mill.
For subsequent measurements the pyrite was protected from oxidation during grinding.
Several small pieces of pyrite were placed in a grinding capsule which was cooled by liquid
nitrogen. The capsule filled with nitrogen gas was sealed and further cooled with liquid
nitrogen. While still cold, the capsule was placed in the vibratory mill and the pyrite was
ground for 1 min.
One portion of ground pyrite was sulfurized by the method used previously (ref 15).
This method involved suspending 2 g of pyrite in 20 ml of water and then adding 5 ml of
0.1 NajS solution. The mixture was acidified next with 1 ml of HCl (1:10) and then
diluted to 100 ml. After stirring the suspension for 30 min, the sulfurized pyrite was
recovered by filtration, washed three times with distilled water, and dried in air overnight.
To treat the pyrite or sulfur with TGA, 0.2 g of powder and 4 ml of TGA solution were
placed in a 15 ml polypropylene centrifuge tube and the mixture was shaken at room
temperature for 30 min. The liquid was then decanted, and the treated particles were spread
over filter paper and dried over silica gel in a desiccator overnight. The TGA (98%) was
obtained from Sigma Chemical Company.
Infrared spectra were determined with a Perkin-Elmer Model 1800 FT-IR spectrometer
and MTEC Photoacoustics Model 200 photoacoustic detector. The spectrometer was
operated at 8 cm"^ resolution, with an open aperture and a mirror velocity of 0.05 cm/s.
58
1723
1422
1750 1650 1550 1450

WAVENUMBERS (cm-^)
Figure 1. Spectra for pure TGA, untreated pyrite, and pyrite samples treated with different
concentrations of TGA solution.
resulting in a modulation frequency range of 20-200 Hz in the 400-4000 cm'^ wavenumber

range. The photoacoustic detector was purged with cryogenically dried helium. Each
sample spectrum consisted of 128 co-added spectra and was divided by a spectrum of
Cabot Mogul L carbon black to normalize for spectral vibrations due to the infrared source
and spectrometer. Spectra were plotted without spectral smoothing.
For an initial set of measurements, a sample of mineral pyrite was ground in air and then
subdivided into several portions. One portion was analyzed directly by the FT-IR/PAS
technique. Other portions were treated with TGA in different concentrations. The treated
portions were recovered and dried over silica gel at room temperature overnight. These
portions were also analyzed by the FT-IR/PAS technique. The measured spectra for the
treated and untreated pyrite are shown in Figure 1 together with the spectrum for pure TGA.
It can be seen that the spectrum for the untreated pyrite had a prominent peak at 1632 cm"^
and that the spectrum for TGA had major peaks at 1422 cm"^ and 1723 cm"^ The peak
at 1422 cm"^ is believed due to CH2 group bending, and the peak at 1723 cm"^ to stretching
of the C = 0 group (ref. 22). Since dimerized carboxylic acids are known to exhibit a strong
C = 0 band at 1740-1660 cm~\ the results suggest that pure TGA exists as a dimer. While
the spectrum of pyrite treated with 0.0002 TGA was similar to that of the untreated
59
material, the spectra of pyrite treated with higher concentrations of TGA exhibited a broad
absotion band from 1700 to 1500 cm~^ The intensity of this band increased with
increasing TGA concentration. The broad band appeared due to a combination of the pyrite
peak at 1632 cm"^ and another peak at 1560 cm"^ which is believed due to the formation
of a carboxylic acid salt. Acetate salts are known to have IR bands at 1600-1550 cm"^ (ref.
22). Also Poling and Liu (ref. 21) observed strong asymmetrical stretching of the carboxyl
group ( C 0 0 ~ ) at 1572 cm~^ for copper thioglycolate and 1531 cm~^ for lead thioglycolate,
respectively. Therefore, our results indicate that TGA reacted with a metal ion on the
surface of the pyrite to form a metal thioglycolate. In addition, the appearance of a peak
at 1422 cm"^ confirmed the presence of TGA on the pyrite surface.
For the next set of measurements different portions of ground New Zealand coal were
treated with TGA in different concentrations. After the coal had been treated and dried, it
was analyzed and the spectra presented in Figure 2 were obtained. Since coal absorbs
infrared energy strongly in the mid-IR range, it is difficult to observe the interaction of
other materials with coal by an infrared absorption technique. Nevertheless the spectra for
TGA-treated coal indicated adsorption of TGA on the surface because of the shoulder at
1723 cm"^ on one of the coal peaks. The interaction between TGA and coal was observed
more clearly by subtracting the spectrum for untreated coal from the spectrum for each of
the treated coal samples. The resulting difference spectra which are presented in Figure 3
display the strong C = 0 band at 1723 cm"^ due to the presence of TGA on the coal surface.
Moreover, the height of the band increases with increasing TGA concentration. This band
was probably due either to the hydrogen bonding of the carboxyl C = 0 of TGA to an - O H
group on the surface or to the hydrogen bonding of the carboxyl group of TGA to a
carboxyl group on the surface (ref 22). Hydrogen bonding between carboxyl groups was
proposed previously to account for the adsorption of humic substances on the surface of coal
(ref 23). The shift in peak wave numbers from 1723 cm"^ at high concentrations of TGA
to 1746 cm"^ at low concentrations indicates a definite interaction or bonding between TGA
and coal. With high concentrations of TGA the interaction could have been masked by the
presence of unbonded or free TGA on the surface but not at low concentrations.
The TGA peak at 1422 cm~^ is not observable in the coal difference spectra of Figure
3 whereas it is observable in the pyrite spectra of Figure 1. The loss of the 1422 cm~^
feature in the coal spectra is probably due to a combination of the strong infrared absorption
by coal and correspondingly weaker infrared absorption by TGA in this spectral region.
In preparation for an investigation of the effect of pyrite oxidation on the adsorption of
TGA, a preliminary experiment was conducted to see how rapidly the surface of pyrite is
oxidized by air at room temperature and to determine the principal oxidation products. A
sample of pyrite was ground under a blanket of nitrogen and then quickly transferred to the
helium atmosphere of a photoacoustic detector. The FT-IR/PAS spectrum was measured
promptly and the results are shown in Figure 4. The pyrite sample was then exposed to the
laboratory atmosphere for 2 hr and the FT-IR/PAS measurement was repeated with the
results also shown in Figure 4. Then the sample was exposed for another 2 hr and the
measurement was repeated again. A progressive change in the pyrite spectrum shows the
effect of oxidation. Since the greatest change occurred during the first 2 hr of treatment,
the surface oxidation appeared to approach a final state quickly.
60
4000 1600 ' ^1000 400

3400 2800 2200
WAVENUMBERS (cm-')
Figure 2. Spectra for New Zealand coal treated with different concentrations of TGA
solution: (A) 0 M, (B) 5 10"^ , (C) 7.5 10"^ , (D) 4 10"^ ,
() 3.5 10-2 .
1950 1850 ' 1750 1650 1550 1450 ^ 1350
WAVENUMBERS (cm-')
Figure 3. Difference spectra obtained by subtracting the spectrum for untreated coal from
the spectrum for TGA-treated coal for each case shown in Figure 2.
61
-i 1 1 1 -
1900 1750 1600 1450 1300 1150 1000 850

WAVENUMBERS {cm-')
Figure 4. FTIR-PAS spectra for freshly ground pyrite (A), pyrite exposed for 2 hr (B), and
pyrite exposed for 4 hr (C). The difference spectrum (C-A) shows the oxidation
induced sulfate band.
IIIIIIIIIiiiiiiiiiiiiii1~
1820 1720 1620 1520 1420 1320

WAVENUMBERS ( c m - ^ )
Figure 5. Spectra for TGA, freshly-ground pyrite and oxidized pyrite treated with 0.003
TGA solution.
62
Also shown in Figure 4 is the difference spectrum (C-A) which was obtained by
subtracting the spectrum for untreated pyrite from the spectrum for pyrite which had been
oxidized for 4 hr. The difference spectrum has a broad band centered at 1110 cm"^ due to
some product of oxidation. The most likely product is iron sulfate since sulfate is known
to exhibit a strong, broad band at 1130-1080 cm"^ (ref. 24). Furthermore, this product was
also observed by Huggins et al. (ref. 25) to be the initial product of coal pyrite weathering
in a laboratory atmosphere. These investigators used a combination of Mossbauer
spectroscopy and scanning electron microscopy to determine the products of oxidation of
pyrite in a coal matrix. While a variety of iron sulfates were formed initially, goethite was
the eventual product. Brion (ref. 26) found by using photoelectron spectroscopy that the
surface of freshly ground pyrite was oxidized by air to form iron hydroxide or oxyhydroxide
initially with basic iron sulfate appearing later as the major oxidation product.
To investigate the effect of surface oxidation on the interaction between pyrite and TGA,
a sample of pyrite was ground under a nitrogen blanket. One part of the freshly ground
material was treated directly with 0.003 TGA, dried, and analyzed by FT-IR/PAS
spectroscopy, while another part was first spread in a thin layer on a plate and exposed to
air at room temperature for 7 days to oxidize the surface. The oxidized pyrite was divided
into several portions for subsequent treatment with TGA. One portion was treated with
0.003 TGA, dried, and analyzed. The spectra for this material and for unoxidized pyrite
treated with TGA are shown in Figure 5. It can be seen that the spectrum for unoxidized
pyrite is similar to that shown in Figure 1 for freshly-ground pyrite which had been treated
with 0.003 TGA. In both cases major peaks were present at both 1560 cm"^ and
1422 cm"^ indicating the presence of TGA on the surface. On the other hand, the spectrum
for the oxidized pyrite had only a single major peak at 1632 cm"^ and no peaks or bands
suggestive of TGA adsorption. The peak at 1632 cm"^ seems characteristic of pyrite since
this peak is also present in the spectrum for freshly-ground pyrite shown in Figure 1.
Other portions of the oxidized pyrite were given a preliminary treatment with either
acidic, neutral, or basic solutions before being treated with a TGA solution. The
preliminary treatment was applied because previous work by Fan et al. (ref. 4) had indicated
that when oxidized pyrite was suspended in an aqueous solutions, the surface properties of
the pyrite were affected greatly by the pH of the solution. When the pyrite was suspended
in an acidic solution, the particles became highly oleophilic as though they were coated with
elemental sulfur. On the other hand, when they were suspended in a basic solution, the
particles became highly hydrophilic as though they were coated with iron hydroxides.
Furthermore, the electrokinetic properties of acid-treated particles were similar to those of
sulfur particles, whereas the electrokinetic properties of particles treated above pH 4 were
similar to those of colloidal particles of ferric hydroxide.
The preliminary treatment was applied by suspending 0.5 g of oxidized pyrite in 8 ml of
solution having a predetermined pH and stirring for 10 min. The pH of the suspension was
checked and readjusted to the initial value if necessary. The suspension was then stirred for
another 10 min. The particles were subsequently recovered and resuspended in 0.003
TGA at pH 3 for final treatment. After the particles were dried, they were analyzed to
obtain the spectra shown in Figure 6. The spectrum of particles which had been given a
preliminary treatment with dilute hydrochloric acid (pH 1.8) is similar to that of untreated,
oxidized pyrite indicating that no TGA was adsorbed. However, the spectra for particles
which had been given a preliminary treatment with either water (pH 7) or dilute sodium
63
1820 1720 1620 1520 1420 1320

WAVENUMBERS ( c m " * )
Figure 6. Spectra of pyrite after air-oxidation, treatment with solutions of different pH, and
subsequent treatment with 0.003 TGA solution.
1632
Washed with
HCl
IIIIII\IIIIIIIIIIIIIIIr
1820 1720 1620 1520 1420 1320
WAVENUMBERS (cm-')
Figure 7. Comparison of spectra of fresh pyrite, oxidized pyrite washed with HCl or
washed with HCl and then acetone. All samples were treated with 0.003
TGA solution.
64
hydroxide (pH 10.1) had major peaks at both 1560 cm"^ and 1422 cm"^ indicating
adsorption of TGA.
Since the acid-treated, oxidized pyrite could have been coated with elemental sulfur,
another experiment was conducted in which some of the acid-treated pyrite was washed with
acetone to remove the sulfur coating. The washed pyrite was then treated with 0.003
TGA, dried, and analyzed. The resulting spectrum for the acetone-washed pyrite is shown
in Figure 7 together with the spectra for unoxidized pyrite and acid-treated, oxidized pyrite
both of which had also been treated with 0.003 TGA. Interestingly, the spectrum for the
acetone-washed pyrite showed that some TGA had been adsorbed since there was a small
peak at 1422 cm"^ and a shoulder was present at 1560 cm"' on the major pyrite band at
1632 cm"^ These results indicate that the acid-treated, oxidized pyrite was indeed coated
with elemental sulfur which was removed by acetone enabling TGA to be adsorbed.
To obtain more information about the interaction of TGA with elemental sulfur, a series
of measurements was carried out on different samples of powdered sulfur which had been
treated with 0.003 TGA at different pH levels. Since a 0.003 TGA solution had a pH
of 3, sodium hydroxide had to be added to achieve higher pH levels. After applying the
treatment and drying, the treated sulfur was analyzed, and the spectra presented in Figure 8
were obtained. Also shown is the spectrum for untreated sulfur. Since the spectrum for
sulfur treated at pH 3 was essentially the same as that for untreated sulfur, it is apparent that
TGA was not adsorbed at pH 3. On the other hand, the spectra for sulfur treated at either
pH 4.6 or 9.3 displayed a strong peak at 1580 cm"' indicating the formation of a metal
thioglycolate. This result suggests that sodium ions were adsorbed on the surface of the
sulfur and that the sodium ions then reacted with the thioglycolate anions to form a salt.
Adsorption of sodium ions by sulfur seemed likely because it had been observed previously
that sulfur particles bear a negative electrical charge in an aqueous solution above pH 3 and,
therefore, would attract positively charged cations (ref. 4). Because pure sulfur was used,
no other metal ions were likely to have been present.
Since the presence of sulfur on the surface of pyrite seemed to have a major effect on the
interaction between the surface and TGA, an additional set of measurements was conducted
with sulfurized (sulfur-coated) pyrite. The sulfurized pyrite was treated with 0.003 TGA,
dried, and analyzed to obtain the spectrum shown in Figure 9. Also shown are the spectra
obtained previously for both oxidized and unoxidized pyrite after a similar treatment (see
Figure 5), It can be seen that the spectra are remarkably similar for both oxidized and
sulfurized pyrite treated with 0.003 TGA at pH 3. Neither spectrum reveals adsorption
of TGA, whereas the spectrum for unoxidized pyrite shows strong adsorption of TGA.
To see how strongly TGA is bonded to the surface of pyrite, several measurements were
made with freshly ground pyrite. One portion was analyzed directly while another portion
was first treated with 0.01 TGA. Part of the treated pyrite was dried and then analyzed
while another part was washed before being analyzed. Washing involved mixing 200 mg
of TGA-treated pyrite with 10 ml of deionized and distilled water and then decanting the
water. The washing was repeated three times. The washed material was subsequently dried
and analyzed. The spectra for the different pyrite samples are shown in Figure 10. The
spectrum for untreated pyrite contained the characteristic pyrite peak at 1632 cm"^ and two
additional peaks at 1550 cm"^ and 1575 cm"^ due to impurities. Although the pyrite spectra
suffered from baseline drift, it is still possible to discern several important features,
especially after subtracting the spectrum for untreated pyrite from the spectrum for each of
65
\IIIIIIIIIIIIIIIIIIIr
1820 1720 1620 1520 1420 1320
WAVENUMBERS (cm-M
Figure 8. Spectra for sulfur and sulfur treated with 0.003 TGA under different pH
conditions.
1560
1632
Sulurized pyrite
IIIIIIIIIIIIIIIIIIIIIIIII-
1820 1720 1620 1520 1420 1320
WAVENUMBERS (cm-')
Figure 9. Spectra for different forms of pyrite treated with 0.003 TGA.
66
I1!1\I!1IIIIIIIIIIIIIII1
1840 1740 1640 1540 1440 1340
WAVENUMBERS {cm-')
Figure 10. Spectra for pyrite (A), pyrite treated with 0.003 TGA (B), pyrite treated with
0.003 TGA and then washed (C), and TGA alone (D).
IIIIIr-
1840 1740 1640 1540 1440 1340
WAVENUMBERS {cm'')
Figure 11. Spectra include the difference spectra (B-A) and (C-A) based on Figure 10 and
the reference spectrum for TGA (D).
67
the treated pyrite samples (see Figure 11). The difference spectrum (B-A) shows clearly
a peak at 1562 cm"^ due to the formation of a metal thioglycolate. Furthermore, this peak
is not present in the difference spectrum (C-A) which indicates that the metal thioglycolate
was destroyed by washing the pyrite. This observation agrees with previous results of oil
agglomeration tests which showed that the depressing action of TGA was destroyed by
washing TGA-treated pyrite (ref. 17). Since TGA was easily removed from the pyrite
surface by washing, it was not bonded strongly to the surface.
CONCLUSIONS
The results of this study showed that TGA is adsorbed on the surface of both coal and
pyrite but not by the same mechanism. Evidence obtained by FT-IR/PAS indicated that
TGA adsorption on coal probably involves hydrogen bonding of the carboxyl C = 0 of TGA
to an - O H group on the coal surface or hydrogen bonding between the carboxyl group of
TGA and a carboxyl group on the surface. Similar evidence indicated that TGA adsorption
on pyrite involves the formation of a metal thioglycolate. The formation of a metal salt is
consistent with the ease with which the material is removed from the surface of pyrite by
washing with water.
The adsorption of TGA by pyrite was found to depend strongly on both the state of
oxidation of the pyrite and the pH of the solution in which the materials were suspended.
The surface of freshly ground pyrite was oxidized rapidly on exposure to air at room
temperature. Iron sulfate was identified as a product of oxidation by FT-IR/PAS. When
pyrite which had been oxidized superficially was suspended in an acidic solution, it behaved
as though it was coated with elemental sulfur because it would not adsorb TGA from an
acidic solution at pH 3. Such behavior was also typical of sulfurized pyrite and elemental
sulfur. On the other hand, freshly ground pyrite readily adsorbed TGA at pH 3. Elemental
sulfur adsorbed TGA at pH 4.6 and at higher pH levels. It seems likely that sodium ions
were adsorbed on the surface of sulfur which then reacted with TGA to form sodium
thioglycolate on the surface.
No evidence was obtained to indicate bonding of the sulfhydryl group ( - S H ) of TGA to
the pyrite surface. The absorption peak at 2567 cm"^ representing the stretching of the S-H
group was difficult to observe. It is also possible that TGA was partly converted to DTGA
through oxidation which would have left no free - S H for attachment to the surface.
ACKNOWLEDGMENT
Ames Laboratory is operated for the U.S. Department of Energy by Iowa State
University under Contract No. W-7405-ENG-82. This work was supported by the Assistant
Secretary for Fossil Energy through the Pittsburgh Energy Technology Center. Coal was
supplied by Trevor Matheson of the Coal Research Association of New Zealand, Inc.
68
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The Use of Mineral Matter Dispersants and Depressants

During the Flotation of Bituminous Coals
C. E. Raleigh, Jr. and F. F. Apian
M i n e r a l Processing Section, T h e P e n n s y l v a n i a S t a t e U n i v e r s i t y ,
115 M i n e r a l Sciences B u i l d i n g , U n i v e r s i t y P a r k , P e n n s y l v a n i a , 16802, U S A
ABSTRACT
W h i l e m u c h d a t a from t h e froth flotation of b i t u m i n o u s coals i n d i c a t e t h a t

l i b e r a t e d m i n e r a l m a t t e r e n t e r s t h e c l e a n coal froth b y w a y of w a t e r carry-over,
o t h e r r e s u l t s s h o w t h a t discrete s u l f u r - b e a r i n g a n d a s h - f o r m i n g m i n e r a l s c a n b e
collected b y e n t r a p m e n t i n t o t h e froth m a s s , b y a t t a c h m e n t t o coal surfaces a s
slime coatings, b y specific flotation, or b y t h e m u t u a l flocculation a n d flotation of
d i s s i m i l a r fine p a r t i c l e s . I n several of t h e s e cases, t h e u s e of m i n e r a l m a t t e r
d i s p e r s a n t a n d d e p r e s s a n t s y s t e m s d u r i n g flotation c a n e n h a n c e t h e selective
s e p a r a t i o n of fine coal a n d refuse m a t e r i a l s .
To a s c e r t a i n t h e r e l a t i v e effectiveness of a d d i n g d i s p e r s a n t s a n d d e p r e s s a n t s
d u r i n g coal froth flotation, l a b o r a t o r y flotation t e s t s w e r e c o m p l e t e d on s e v e r a l
m i n u s 0 . 1 5 - m m (100 m e s h ) r a w coal s a m p l e s . C a n d i d a t e r e a g e n t s w e r e selected
u s i n g a s i m p l e l a b o r a t o r y o b s e r v a t i o n t e c h n i q u e t h a t allowed macroscopic
e v a l u a t i o n of m i n e r a l m a t t e r d i s p e r s i o n b e h a v i o r . F o r t h e coals t e s t e d , t h e u s e of
d i s p e r s a n t s d u r i n g froth flotation often i m p r o v e d t h e rejection of s u l f u r - b e a r i n g
m i n e r a l m a t t e r from t h e froth p r o d u c t . J u d i c i o u s a d d i t i o n of t h e s e r e a g e n t s w a s
r e q u i r e d , however, i n o r d e r to a t t a i n m a x i m u m p y r i t e a n d m i n e r a l m a t t e r
rejection w h i l e p r e v e n t i n g coal depression. T h e u s e of j o i n t d i s p e r s a n t - d e p r e s s a n t
s y s t e m s also d e c r e a s e d t h e t o t a l sulfur a n d a s h c o n t e n t of s o m e of t h e c l e a n coal
froths m o r e t h a n did t h e u s e of d i s p e r s a n t s alone. T h i s i n d i c a t e s t h a t m i n e r a l
m a t t e r c o n t a m i n a t i o n in t h e s e coal froths is s o m e t i m e s c a u s e d b y a c c i d e n t a l
flotation of free p y r i t e or locked coal-pyrite p a r t i c l e s or b y e n t r a p m e n t of m i n e r a l
m a t t e r i n t o a froth m a s s t h a t h a s poor d r a i n a g e capabilities.
L INTRODUCTION
R e m o v i n g a s h - a n d s u l f u r - b e a r i n g m i n e r a l s from coal w h i l e m a i n t a i n i n g clean

coal yield c a n be a challenge, especially w h e n c l e a n i n g fine coals. Of t h e
n u m e r o u s m e t h o d s t h a t a r e u s e d to i m p r o v e t h e q u a l i t y of fine coals, froth
"Present A d d r e s s : C Q Inc., O n e Q u a l i t y C e n t e r , H o m e r City, P e n n s y l v a n i a , 1 5 7 4 8 - 0 2 8 0 , U S A .

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flotation is t h e only commercial-scale process t h a t c a n efficiently c l e a n coals finer

t h a n a b o u t 0.15 m m (100 m e s h ) . E v e n so, t h e selective r e m o v a l of m i n e r a l s s u c h
a s clays a n d p5nrite u s i n g flotation is often difficult. V a r i o u s r e s e a r c h e r s h a v e
s h o w n t h a t a s h a n d p y r i t e rejection d e c r e a s e s significantly d u r i n g fine coal
flotation i n t h e p r e s e n c e of excess a d d i t i o n s of frother, collector, or air,
n e c e s s i t a t i n g a careful u s e of r e a g e n t s a n d flotation conditions [1-6]. To
complicate m a t t e r s f u r t h e r , coal-source p y r i t e s o m e t i m e s e x h i b i t s a s m a l l d e g r e e of
natural floatability-even after e x h a u s t i v e efforts a r e completed to r e m o v e
hydrophobic, u l t r a f i n e coal c o n t a i n e d w i t h i n p a r t i c l e i n t e r s t i c e s [7].
L i b e r a t e d p y r i t e a n d a v a r i e t y of ash-forming m i n e r a l s m a y also e n t e r t h e coal
froth i n a d v e r t e n t l y i n a n y of several m a n n e r s : b y w a y of w a t e r carry-over, b y
accidental e n t r a p m e n t in t h e froth m a s s , by a t t a c h m e n t to coal surfaces a s slime
coatings, by specific flotation, or by flotation of finely-sized, d i s s i m i l a r species
h a v i n g flotation r a t e s s i m i l a r to t h a t of coarse coal [5,8-11]. I n a d d i t i o n to t h e s e
m e c h a n i s m s , froth c o n t a m i n a t i o n m a y occur b y t h e m u t u a l flocculation a n d
s u b s e q u e n t collection of d i s s i m i l a r coal a n d m i n e r a l m a t t e r p a r t i c l e s . I n all b u t
t h e case w h e r e differences in p a r t i c l e size affect t h e h i e r a r c h y of flotation r a t e ,
m i n e r a l m a t t e r d e p r e s s a n t s a n d d i s p e r s a n t s c a n b e u s e d t o d e c r e a s e t h e collection
of refuse p a r t i c l e s d u r i n g coal flotation a n d r e d u c e froth c o n t a m i n a t i o n .
N u m e r o u s coal-source p y r i t e d e p r e s s a n t s h a v e b e e n i n v e s t i g a t e d , w i t h v a r y i n g
d e g r e e s of success. L i m e a n d hydroxyl ion a d d i t i o n s s o m e t i m e s d e c r e a s e t h e t o t a l
sulfur c o n t e n t of coal froths, b u t acid a d d i t i o n s a r e frequently n e e d e d t o d e c r e a s e
t h e i r a s h c o n t e n t [12-16]. T h e u s e of polysaccharides, dyes, a n d o r g a n i c colloids
h a v e also b e e n s h o w n to improve coal-mineral m a t t e r selectivity d u r i n g flotation
[1,15-17]. I n l i m i t e d work, d i s p e r s i n g a g e n t s from v a r i o u s chemical classes s u c h
a s s o d i u m silicate (also k n o w n a s "water-glass"), s o d i u m h e x a m e t a p h o s p h a t e
(Calgon), s o d i u m di-octyl sulfosuccinate (Aerosol OT), q u e b r a c h o (a t a n n i c acid),
a n d lignin sulfonates (such a s t h o s e m a n u f a c t u r e d b y D a x a d a n d M a r a s p e r s e )
h a v e b e e n r e p o r t e d t o p r e v e n t m i n e r a l m a t t e r from e n t e r i n g coal froths a t l e a s t a s
well a s some d e p r e s s a n t s [9,15,18,19]. However, u s i n g m i n e r a l m a t t e r d i s p e r s a n t s
to d e c r e a s e t h e sulfur a n d a s h c o n t e n t of floated coal h a s b e e n s t u d i e d s p a r i n g l y .
To e v a l u a t e t h e p o t e n t i a l of u s i n g d i s p e r s a n t s or joint d i s p e r s a n t - d e p r e s s a n t
r e a g e n t s y s t e m s to improve t h e rejection of a s h a n d sulfur d u r i n g coal flotation, a
two-step i n v e s t i g a t i o n w a s completed. F i r s t , l a b o r a t o r y s t u d i e s of coal a n d p y r i t e
dispersion w e r e performed to observe t h e flocculation a n d d i s p e r s i o n b e h a v i o r of
coal-source p y r i t e a n d coal froths i n t h e p r e s e n c e of v a r i o u s r e a g e n t s . T h e second
s t e p w a s t o e s t i m a t e t h e effectiveness of u s i n g a n y of t h e r e a g e n t s identified a s
p r o m i s i n g d u r i n g a c t u a l coal flotation t e s t s a n d conduct flotation t e s t i n g to
d e t e r m i n e m e a s u r e d i m p r o v e m e n t s i n t h e rejection of a s h a n d sulfur. S e v e r a l
a d d i t i o n a l flotation s t u d i e s w e r e also d e s i g n e d t o c o m p a r e t h e i m p a c t of u s i n g
joint d i s p e r s a n t - d e p r e s s a n t s r e a g e n t s y s t e m s to t h a t of u s i n g d i s p e r s a n t s alone.
2. EXPERIMENTAL MATERIALS PROCEDURES
S e v e r a l coal a n d p y r i t e s a m p l e s w e r e u s e d t o t e s t t h e d i s p e r s i o n abilities of
v a r i o u s r e a g e n t s d u r i n g l a b o r a t o r y o b s e r v a t i o n s a n d bench-scale flotation t e s t s .
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2.L Coal a n d P y r i t e Samples

Two coal s a m p l e s a n d four p y r i t e s a m p l e s w e r e u s e d i n d i s p e r s i o n t e s t i n g . T h e
coal s a m p l e s w e r e a h i g h volatile A b i t u m i n o u s coal from t h e Lower K i t t a n n i n g
s e a m (C & Coal Co., C l a r i o n C o u n t y , P e n n s y l v a n i a ) a n d a m e d i u m volatile
b i t u m i n o u s coal from t h e U p p e r F r e e p o r t s e a m (Helen M i n i n g C o m p a n y , I n d i a n a
C o u n t y , P e n n s y l v a n i a ) . S u m m a r y a n a l y s e s of t h e s e coals a r e given i n T a b l e 1.
Highly-purified s a m p l e s of coal-source pjnrite from t h e U p p e r F r e e p o r t , P i t t s b u r g h ,
a n d Lower/Middle K i t t a n n i n g s e a m s a n d a n ore p y r i t e from P e r u w e r e also u s e d .
T h e i r source, m e t h o d s of purification, a n d associated a n a l y s e s h a v e b e e n d e t a i l e d
e l s e w h e r e [7]. T h e s a m p l e s w e r e h a n d - c r u s h e d to n o m i n a l m i n u s 0.15 m m u s i n g
a n a l u m i n a m o r t a l a n d p e s t l e j u s t prior to u s e to m i n i m i z e oxidation effects.
A t o t a l of four r a w coals w e r e u s e d for flotation t e s t i n g (see T a b l e 1). I n
a d d i t i o n to t h e t w o m e n t i o n e d above, a s a m p l e of a coal m i x c o n s i s t i n g of low a n d
m e d i u m volatile b i t u m i n o u s coal from t h e Lower K i t t a n n i n g a n d M i d d l e
K i t t a n n i n g s e a m s ( B e t h Energy-Slope 3 3 P r e p a r a t i o n P l a n t , C a m b r i a C o u n t y ,
P e n n s y l v a n i a ) a n d a s a m p l e of h i g h volatile A b i t u m i n o u s coal from t h e Lower
C l a r i o n s e a m (C & Coal Co., C l a r i o n C o u n t y , P e n n s y l v a n i a ) w e r e u s e d . T h e s e
s a m p l e s w e r e s t a g e - c r u s h e d to m i n u s 1.68 m m (10 m e s h ) , split i n t o 200-g (~0.5-lb)
c h a r g e s , a n d t h e n g r o u n d a t 5 0 % solids (by w e i g h t ) i n a l a b o r a t o r y r o d mill t o
n o m i n a l m i n u s 0.15 m m (100 m e s h ) . F l o t a t i o n t e s t s w e r e p e r f o r m e d i m m e d i a t e l y
after g r i n d i n g to m i n i m i z e coal oxidation.
2.2. Reagents
T h e r e a g e n t s t e s t e d a s p o t e n t i a l d i s p e r s a n t s a r e given i n T a b l e 2. T h e s e
r e a g e n t s r e p r e s e n t a b r o a d v a r i e t y of commonly u s e d d i s p e r s i n g a g e n t s .
Table 1
P r o x i m a t e A n a l y s e s of F l o t a t i o n T e s t i n g Coals
Proximate Slope 33 Mix C&K C&K Helen
Analyses L/M Kittanning Lower Kittanning Lower Clarion Upper Freeport
(Wt.%, Dry Basis) Cambria Co., PA Clarion Co., PA Clarion Co., PA Indiana Co., PA
Volatile Matter 16.75 38.32 36.98 24.68

Fixed Carbon 56.71 51.09 47.08 51.88
Ash 26.54 10.59 15.94 23.44
Total Sulfur 1.69 3.18 5.78 3.09
Pyritic Sulfur 1.13 2.35 4.36 2.53
Organic Sulfur 0.37 0.78 1.22 0.15
Sulfate Sulfur 0.19 0.05 0.20 0.41
Heating Value-kJAg 25,726 31,224 29,082 27,014
(Btu/lb) (11,060) (13,424) (12,503) (11,614)
ASTM Rank Iv/mv-b hvAb hvab mvb
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Table 2.
Reagents Investigated as Potential Mineral Matter Dispersants
Name Chemical Composition Manufacturer Class and Application
Aerosol MA-80 1,3-dimethyIbutyl American Cyanamid Co, Sulfosuccinate-based

sulfosuccinate wetting agent
Aerosol OT American Cyanamid Co. Sulfosuccinate-based

2-ethylhexyl-8ulfosuccinate wetting agent
Calgon Fisher Scientific, Inc. Inorganic salt and ion

Sodium hexametaphosphate
exchange water softener
Citric Acid 2-hydroxy-1,2,3-propane J. T. Baker Co. Short-chain organic acid

tricarboxylic acid
Daxad IIKLS Polymerized alkyl W. R Grace Co. Sulfonate-based dispersant

naphthalene sulfonate
Hexanoic Acid 2-ethyl hexanoic acid Eastman-Kodak Co. Short-chain organic acid
n-Hexyl Alcohol Hexanol Eastman-Kodak Co. Short-chain organic alcohol
Meu-asperse CB Sulfonated sodium Reed Lignin Sulfonate-based dispersant

lignin sulfonate
Marasperae Sodium lignin sulfonate Sulfonate-based dispersant
Metsosilicate Sodium silicate Philadelphia Quartz Co. 1.0 SiOj/NajO wt. ratio
silicate dispersant
Silicate 1.60 Sodium silicate Philadelphia Quartz Co. 1.6 SiOj / NajO wt. ratio
silicate dispersant
Silicate 2.40 Sodium silicate Philadelphia Quartz Co. 2.4 SiOa/NajO wt. ratio
silicate disperstmt
Silicate 3.75 Sodium silicate Philadelphia Quartz Co. 3.75 SiOa/NajOwt. ratio
silicate dispersant
Triphosphate Sodium tripolyphosphate Fisher Scientific, Inc. Inorganic salt and ion
exchange water softener
Polyvinylpyrrolidone Synthetic polymeric pyrrolidone Aldrich Chemical Co. Nonionic polymerized

alcohol surfactant
Hypochlorite Sodium hypochlorite Eastman-Kodak Co. Strong oxidant salt
Succinic Acid Butanedioic acid Fisher Scientific, Inc. Short-chain organic acid
Tannic Acid Gallotannic acid Aldrich Chemical Co. Short-chain inorganic acid
Tergitol NPX Nonylphenolethoxylated Union Carbide Co. Glycol-based wetting agent

polyglycol
2.3. Dispersion Test Procedures

F o r d i s p e r s i o n t e s t i n g of t h e p y r i t e s , t w o g r a m s of t h e freshly-ground, m i n u s
0.15-mm p y r i t e a n d 10 m l of distilled w a t e r w e r e placed i n 25-cc t e s t t u b e s ,
stoppered, a n d s h a k e n vigorously to i n s u r e complete w e t t i n g of t h e p y r i t e . T h e
t e s t t u b e s w e r e t h e n u n c a p p e d , a n d a p p r o p r i a t e a m o u n t s of d i s p e r s i n g a g e n t s a n d
a d d i t i o n a l distilled w a t e r w e r e a d d e d t o give a final v o l u m e of 2 0 m l . D u r i n g t h i s
t i m e , p H w a s a d j u s t e d to t h e desired level by a d d i n g s o d i u m h y d r o x i d e or
hydrochloric acid solution. T h e s a m p l e m i x t u r e s w e r e a g a i n s t o p p e r e d a n d
s h a k e n . T h e t e s t t u b e s w e r e placed i n a s t a n d i i r d t e s t t u b e r a c k a n d observed a t
30, 300, a n d 3000 seconds in o r d e r t o q u a l i t a t i v e l y record t h e d i s p e r s i o n a n d
flocculation r e s p o n s e a n d t h e s e t t l i n g b e h a v i o r of e a c h s u s p e n s i o n .
75
D i s p e r s i o n o b s e r v a t i o n s w e r e also m a d e o n s a m p l e s of t h e Lower K i t t a n n i n g
(C & K) a n d U p p e r F r e e p o r t s e a m coals u s i n g p r o c e d u r e s s i m i l a r t o t h o s e
described for p y r i t e d i s p e r s i o n t e s t i n g . However, since t h e c o a l - w a t e r - d i s p e r s a n t
m i x t u r e s w e r e very t u r b i d a n d m u r k y , t w o a d d i t i o n a l s t e p s w e r e r e q u i r e d to
p e r m i t clear v i s u a l o b s e r v a t i o n of d i s p e r s i o n a n d flocculation t e n d e n c i e s . F i r s t ,
t h e q u a s i - s t a b l e froths t h a t developed d u r i n g t h e s h a k i n g of t h e s e m i x t u r e s w e r e
collected b y g e n t l e a s p i r a t i o n , placed on a v a n n i n g p l a t e , a n d e x a m i n e d u s i n g a
low-magnification b i n o c u l a r microscope to d e t e r m i n e t h e d e g r e e of d i s p e r s i o n or
flocculation. Second, t o e n s u r e t h a t sufficient a m o u n t s of l i b e r a t e d p y r i t e w e r e
a v a i l a b l e to observe dispersion/flocculation behavior, 0.25 g of purified p5rrite
( U p p e r F r e e p o r t coal-source p y r i t e ) w a s a d d e d to t w o g r a m s of c r u s h e d U p p e r
F r e e p o r t s e a m coal p r i o r t o p r e p a r i n g t h e c o a l - w a t e r - d i s p e r s a n t m i x t u r e . T h i s
s t e p w a s n o t n e c e s s a r y w h e n t e s t i n g t h e d i s p e r s i o n b e h a v i o r of Lower K i t t a n n i n g
s e a m coal (C & K), however, b e c a u s e t h e r a w coal s a m p l e c o n t a i n e d e n o u g h "free"
p y r i t e t o clearly observe i t s dispersion. A d d i n g p y r i t e also p r o v i d e d a m e a n s
w h e r e b y h i g h levels of p y r i t e c o n t a m i n a t i o n i n a n y of t h e collected froths could b e
n o t e d . T h e r e s u l t s of t h e s e p y r i t e a n d coal froth d i s p e r s i o n t e s t s w e r e u s e d to
identify p r o m i s i n g r e a g e n t s for s u b s e q u e n t froth flotation t e s t i n g .
2.4. F r o t h F l o t a t i o n Procedures
Rod m i l l - g r o u n d coal w a s floated i n t h e older-style (baffled) W E M C O - F a g e r g r e n
l a b o r a t o r y m a c h i n e , w i t h t h e i m p e l l e r s p e e d s e t a t 1750 r p m a n d t h e a e r a t i o n r a t e
a t 7.1 1pm (0.25 scfm). A g l a s s flotation cell w i t h a n effective p u l p v o l u m e of - 2 . 3
liters (0.6 gal) w a s c h a r g e d w i t h 200 to 220 g of coal to p r o d u c e a flotation p u l p of
a b o u t 8.5% solids b y w e i g h t . T h e p u l p w a s conditioned for five m i n u t e s i n t a p
w a t e r , w h i l e t h e p H w a s recorded a n d a d j u s t e d to p H 7 ( u n l e s s o t h e r w i s e n o t e d ) .
When used, dispersants and depressants were t h e n added a n d t h e pulp was
conditioned for a n a d d i t i o n a l 2 a n d 3 m i n u t e s m o r e , respectively. Following t h i s ,
frother ( a n d collector w h e n u s e d ) w a s a d d e d a n d t h e p u l p w a s conditioned for a n
a d d i t i o n a l m i n u t e prior to t h e s t a r t of a e r a t i o n . Zero flotation t i m e w a s t a k e n a s
t h a t t i m e w h e n froth spilled n a t u r a l l y over t h e cell lip. F r o t h w a s collected i n t w o
successive o n e - m i n u t e d u r a t i o n s a m p l e s via a h a n d - s c r a p i n g t e c h n i q u e , w h i c h
gave r e s u l t s w h i c h w e r e reproducible to a b o u t 2% of t o t a l yield. T a p w a t e r w a s
a d d e d t h r o u g h o u t t h e t e s t to m a i n t a i n a c o n s t a n t p u l p level.
All flotation p r o d u c t s w e r e filtered, dried, weighed, a n d a n a l y z e d for t o t a l sulfur
a n d a s h c o n t e n t . T o t a l sulfur a n a l y s e s w e r e completed u s i n g t h e L E C O m e t h o d
(ASTM D-3673) a n d a s h a n a l y s e s w e r e completed u s i n g A S T M m e t h o d D - 2 7 1 . F o r
convenience, only t h e r e s u l t s for t h e 1-min flotation p r o d u c t s a r e p r e s e n t e d i n t h i s
p a p e r . T h e m a t e r i a l t h a t floated in t h e second m i n u t e of flotation w a s found to
i n c r e a s e t h e coal yield only a b o u t 5%, w h i l e c o n c o m i t a n t l y i n c r e a s i n g t h e t o t a l
sulfur a n d a s h c o n t e n t of t h e froths.
2.5. F l o t a t i o n Reagents
M I B C ( m e t h y l isobutyl carbinol or 4 - m e t h y l , 2 - p e n t a n o l ) a n d No. 2 fuel oil w e r e
employed a s frother a n d collector, respectively. TVpically, w h e n No. 2 fuel oil w a s
u s e d , it w a s first emulsified w i t h t a p w a t e r i n a h i g h - s p e e d W a r i n g b l e n d e r . T h e
76
p y r i t e d i s p e r s a n t a n d d e p r e s s a n t s y s t e m s u s e d a r e s h o w n in T a b l e 3 . M i n e r a l
m a t t e r d i s p e r s a n t s u s e d i n flotation t e s t i n g w e r e selected b a s e d u p o n t h e r e s u l t s
of t h e coal a n d p y r i t e d i s p e r s i o n o b s e r v a t i o n s r e p o r t e d h e r e i n , w h i l e p y r i t e
d e p r e s s a n t s w e r e selected b a s e d u p o n flotation r e s u l t s r e p o r t e d previously [18,19].
O n e coal p y r i t e d e p r e s s a n t , C P C 3 0 0 5 ( o r d i n a r y c o m s t a r c h ) , w a s x a n t h a t e d t o a
10% level for u s e d u r i n g flotation t e s t i n g . T h e p r o c e d u r e u s e d for x a n t h a t i n g
p o l y m e r s for u s e a s coal a n d coal p y r i t e d e p r e s s a n t s is p r e s e n t e d i n d e t a i l i n t h e
l i t e r a t u r e [15] a n d will n o t b e discussed h e r e .
3. LABORATORY OBSERVATIONS OF COAL AND PYRITE DISPERSION
W h e n l i b e r a t e d sulfur-bearing a n d ash-forming m i n e r a l s a r e e i t h e r specifically

collected or accidentallty floated, t h e i r floatability c a n often b e r e d u c e d b y a d d i n g
Table 3
D i s p e r s a n t s a n d D e p r e s s a n t s U s e d i n Coal F l o t a t i o n T e s t i n g
Reagent Reagent Category* Mechanism Dosage
Test Code Name (ke^)
Dispersante
1, 8, 9, 10 1.6 SiOj/NaaO Silicate dispersing agent Silicate anions adsorb onto 0.025-0.25
Sodium Silicate solid surfaces.
2 Sodium Inorganic salt; ion Polyphosphate anions 0.25

Tripol3hosphate exchang^water softener complex metal cations.
3 Marasperse CB Lignin sulfonate-based Sulfonate anions adsorb 0.05

dispersant to minerals.
4 Hexanol Short-chain organic alcohol Adsorbs onto coal. 0.01-0.015
5 2-Ethyl Hexanoic Acid Short-chain organic acid COOH* groups adsorb on coal. 0.1
6 Citric Acid Short-chain organic acid As above, plus complexes 0.05

with cations.
7 Aerosol MA-80 or OT Sulfosuccinate-based Wetting agents; adsorbs 0.01-0.015

wetting agent to minerals.
Depressants
A,L Lime, pH=7(A) or 9(L) Hydroxyl ions, lime, and Ca** Ca** hydroxy species attach to 1.0
pyrite surfaces.
Sodium Hydroxide Oxidizing agenl/Dispersant Probably oxidizes pjrrite and 0.5

disperses coal and mineral
matter.
C Hylon VII Natural organic polymer Hydrophilic compound 0.1

(high amylose starch) adsorbs on mineral matter
surfaces.
D CPC3005X Xanthated organic polymer Xanthate group attaches to 0.1

(Xanthated com starch) pyrite. OH' groups reject air
bubbles.
Nigrosine Dye and chelation compound Chelates with iron on mineral 0.05
matter surfaces.
77
one or m o r e of several effective m i n e r a l m a t t e r d e p r e s s a n t s [6,17-19]. However, if

g a n g u e p a r t i c l e s e n t e r t h e clean coal froth b y w a y of e n t r a p m e n t i n t o t h e froth
m a s s , a t t a c h m e n t to coal surfaces a s slime coatings, or m u t u a l flocculation a n d
collection of d i s s i m i l a r species, t h e a d d i t i o n of r e a g e n t s t h a t c a n d i s p e r s e coal a n d
m i n e r a l m a t t e r m a y h e l p r e d u c e accidental froth c o n t a m i n a t i o n . Mild d i s p e r s i o n
of coal h e l p s to p r e v e n t t h e f o r m a t i o n of a m a t t e d froth, t h e r e b y p e r m i t t i n g a n y
m i n e r a l m a t t e r collected i n t o t h e froth a c h a n c e to d r a i n m o r e easily. A d d i n g
d i s p e r s i n g a g e n t s also r e d u c e s t h e electrostatic a t t r a c t i o n b e t w e e n coal surfaces
a n d clay a n d p y r i t e slimes a n d t h u s s h o u l d r e d u c e t h e i r s u b s e q u e n t recovery i n t o
t h e c l e a n coal froth. It is therefore very i m p o r t a n t to identify w h e t h e r t h e
incorporation of m i n e r a l m a t t e r i n a froth is t h e r e s u l t of one or m o r e of t h e s e
m e c h a n i s m s , since by observing t h e d i s p e r s i o n or flocculation b e h a v i o r of fine coal,
p y r i t e , a n d m i n e r a l m a t t e r in t h e p r e s e n c e of v a r i o u s r e a g e n t s , p r o m i s i n g flotation
a g e n t s m a y t h e n b e quickly identified for s u b s e q u e n t flotation t e s t i n g .
3 . 1 Dispersion of P y r i t e
T a b l e s 4, 5, a n d 6 show t h e effectiveness of 18 c o m m o n d i s p e r s i n g a g e n t s t o
d i s p e r s e a n ore p y r i t e a n d P i t t s b u r g h , U p p e r F r e e p o r t , a n d Lower-Middle
K i t t a n n i n g s e a m coal-source p y r i t e s . I n i t i a l s t u d y of d i s p e r s i o n b e h a v i o r w a s
performed a t a 5 p p m dosage level (roughly e q u i v a l e n t to 0.05 to 0.06 kg/t). F o r
some of t h e r e a g e n t s , however, d i s p e r s i o n o b s e r v a t i o n s w e r e also m a d e a t 1 p p m
(0.01 kg/t) a n d a t 0.5 p p m . F r o m t h e s e s t u d i e s , M a r a s p e r s e C B (sulfonated
s o d i u m lignin sulfonate) a n d s o d i u m t r i p o l y p h o s p h a t e w e r e found t o b e good
d i s p e r s a n t s for p y r i t e i n all cases t e s t e d , a s w a s 1.6-sodium silicate except for one
case. Citric acid, 2-ethyl h e x a n o i c acid, t a n n i c acid, a n d polyvinylpyrrolidone w e r e
also u s u a l l y effective a s p y r i t e d i s p e r s a n t s , while m e t s o - a n d 3.75-sodium silicates,
s o d i u m hypochlorite, a n d Tergitol N P X all w o r k e d in a t l e a s t one case.
3.2. Dispersion of CoaVPyrite M i x t u r e s

As o u t l i n e d i n t h e E x p e r i m e n t a l P r o c e d u r e s section, coal d i s p e r s i o n t e s t s w e r e
d e s i g n e d to s t u d y t h e r e s p o n s e of coal dispersion, p e r se, i n t h e p r e s e n c e of v a r i o u s
r e a g e n t s a n d t h a t of p y r i t e while w i t h i n t h e p u l p a n d w i t h i n a froth, b o t h for a
coal/pyrite m i x t u r e a n d for a h i g h pyritic sulfur r a w coal.
T a b l e 5 s h o w s t h a t U p p e r F r e e p o r t s e a m coaj/pyrite m i x t u r e a t n a t u r a l p H
flocculates i n n e a r l y all cases a t dosages of 5 p p m , w i t h only Aerosol MA-80 (a
sulfosuccinate-based w e t t i n g a g e n t ) a n d M a r a s p e r s e C B p r o v i d i n g good d i s p e r s i o n
of t h e m i x t u r e . B a s e d on t h e fact t h a t froth a s p i r a t e d from t h i s m i x t u r e h a d a low
p y r i t e c o n t e n t , M a r a s p e r s e C B is expected to b e s u p e r i o r t o Aerosol MA-80 a s a
p y r i t e a n d m i n e r a l m a t t e r d i s p e r s a n t d u r i n g flotation. It s h o u l d f u r t h e r b e n o t e d
t h a t t w o of t h e o t h e r r e a g e n t s w h i c h s h o w e d excellent p r o m i s e for d i s p e r s i n g
p y r i t e , 1.6-sodium silicate a n d s o d i u m t r i p o l 5 h o s p h a t e , also p r o d u c e d froths
h a v i n g low p y r i t e c o n t e n t , while only m i l d l y flocculating t h e coal/pyrite m i x t u r e .
Moreover, r e a g e n t s allowing m o d e r a t e levels of p y r i t e c o n t a m i n a t i o n i n t h e froth.
Aerosol MA-80, Calgon (sodium h e x a m e t a p h o s p h a t e ) , 2-ethyl h e x a n o i c acid, 2.4-
a n d 3.75-sodium silicates, Tergitol NPX, a n d t a n n i c acid m a y still b e viable p y r i t e
a n d m i n e r a l m a t t e r d i s p e r s a n t s a t lower dosages or o t h e r p H levels.
-J
Table 4 00
Pittsburgh Seam Pyrite and Ore Pyrite Dispersion Observations
PITTSBURGH 8EAM PYRITE ORE PYRITE
5 ppm 1 ppm 5 ppm 1 ppm

pH=7 pH=7 pH=7 pH=7
REAGENT 30s 300s 3000s 30s 300s 3000s 30s 300s 3000s 30s 300s 3000s
Aerosol MA-80 F F/S 8 F 8 8 F F/S 8
AerosolOT F 8 8 F 8 8
Calgon F 8 8 F* F/S* 8* F 8 8
Citric Acid F F/S F/S F(D*) F,IS(LVS*) 8(8*) D n'S n'S

Daxad llKLS F 8 8 F 8 8
Hexanol F 8 8 F 8 8
2-Ethyl Hexanoic Acid D n'S 8 IW n'S 8
Marasperse CB D IW n'S D n'S n'S D n'S n'S D IW IW

Marasperse N F/S 8 8 F/S F/S 8 F 8 8
Polyvinylpyrrolidone F 8 8 F/S F/S 8 D n'S 8 D IW 8
Metsosilicate F/S 8 8 F/S F/S 8 D n'S n'S D IW IW
Sodium 8ilicate 1.60 D n-s n-s D n'S n'S D n'S n'S D IW IW
Sodium 8ilicate 2.40 F/S 8 8 F 8 8 F F/S 8
Sodium 8ilicate 3.75 F/S 8 8 F 8 8 F F/S 8
Sodium Hypochlorite F 8 8 F 8 8
Sodium Tripolyphosphate D n'S 8 D n'S 8 D n'S 8
Tannic Acid D n'S 8 F/S F/S 8 D n'S 8
Tergitol NPX F 8 8 F/S F/S 8 D n'S 8
8tandard (No Reagent) F/S 8 8 F/S 8 8 F/S 8 8 F/S 8 8
D = All Material Dispersed n'S = 8upernatant Disperse~arse Solids Settled 8 = All Material Settled
F = All Material Flocculated F/S = 8upernatant Flocculate<VCoarse Solids Settled = Includes Results at pH=5
Table 5
Upper Freeport Seam Pyrite and CoaVPyrite Mixture Dispersion Observations
PYRITE COAI/PYRITE MIXTIJRE
5 ppm 1 ppm 5 ppm Relative Froth

pH=6 (Natural) pH=6 pH=6 Characteristics
REAGENT 308 3008 30008 30& 300s 3000& 30& 3008 3000s Stability Pyrite Content
Aerosol MA-BO F F,tS S D O'S O'S Poor Moderate
Aerosol ar F S S Poor High
Calgon F S S F S S Fair Moderate

Citric Acid D S S
Dsxad l1KLS F F,tS S Poor High
Hexanol F F,tS S Excellent High
2-Ethyl Hexanoic Acid F F,tS S Good Moderate

Marasperse CB D O'S O'S D O'S O'S D O'S S Fair Low
Marasperse N
Polyvinylpyrrolidone D O'S S F S S
Metsosilicate F F,tS S D Q'S S
Sodium Silicate 1.60 F F,tS S D O'S O'S F S S Poor Low
Sodium Silicate 2.40 F F,tS S F F,tS S Poor Moderate

Sodium Silicate 3.75 D I)'S I)'S D Q'S Q'S F F,tS S Poor Moderate
Sodium Hypochlorite D I)'S I)'S F S S Poor High

Sodium Tripolyphosphate D I)'S S F F,tS S Fair Low
Tannic Acid D I)'S S F S S Poor Moderate

Tergitol NPX D O'S S F F,tS S Excellent Moderate
Standard (No Reagent) I)'S S S I)'S S S O'S S S Poor High
---
D = All Material Dispersed O'S = Supernatant Disperse~arse Sol ids Settled S = All Material Settled -.J
\0
F = All Material Flocculated F,tS = Supernatant Flocculate~oarse Solids Settled
Table 6
Lower-Middle Kittanning (Slope 33) Pyrite and Lower Kittanning (C&K) Raw Coal Dispersion Observations
SLOPE 33 PYRITE C &. K RAW COAL
5 ppm 1 ppm 5 ppm 1 ppm or lese
pH=7 (Natural) pH=7 pH=7 pH=5 pH=7 pH=9
REAGENT 308 3008 30008 308 3008 30008 308 3008 3000e 308 3008 3000e 308 3008 3000e 308 3008 3000e
AeJ"0801 MA-80 F F~ S 0 D [S 0 [S S D [S S D ~ D
AeJ"080lar 0 [S S D S S 0
Calgon F
Citric Acid F S S 0 ~ S D* [S* S* 0 S S 0
Dsxad llKLS 0 ~
Hexanol 0 ~ S 0 ~ S 0 S S D [S
2-Ethyl Hexanoic Acid F F~ S F F F~ F(D*) F(~*) F/S(S*) D
Maruperee CB 0 [S ~ 0 [S ~ 0 D D 0 D D 0 D 0 0 0 0
Marasperee N F~
Polyvinylpyrrolidone F F~ S 0 ~ S 0 D D 0 [S S D S S D [S
Met808i1icate F F~ S F F~ S 0 0 [S
Sodium Silicate 1.60 D [S ~ 0 [S ~ 0 D 0 0 D D 0 0 0 0 0 0
Sodium Silicate 2.40 F S S F
Sodium Silicate 3.75 F S S 0 ~
Sodium Hypochlorite D [S ~ 0 [S
Sodium Tripolyphoephate 0 [S S 0 [S S D [S
Tannic Acid F S S F F~ S 0 ~
Tergitol NPX F F~ S D [S S 0 [S S 0 ~
Standard (No Reagent) [S S S [S S S [S S S [S S S [S S S ~
D = AII Material Disperaed ~ = Supernatant Di8peree~08J"I!Ie Solids Sewed S = All Material Settled
0 F = All Material F10cculated F~ = Supernatant F1occulate~08J"I!Ie Solids Sewed = Includes Results at 0.5 ppm Dosage
00
81
Using these same reagents on a different coal ( C & K Lower Kittanning),

though, produced radically different patterns in that all of the reagents with the
exception of 2-ethyl hexanoic acid dispersed this high pyritic sulfur raw coal
effectively at dosages of 5 ppm and 1 ppm and at all pH levels tested (pH=5,7,9).
Note that when the dosage of 2-ethyl hexanoic acid was reduced to extremely low
levels (0.5 ppm), some pjni-ite dispersion was observed.
These data clearly reinforce the admonition that "the best pyrite depressant or
dispersant for one coal is not necessarily the best for another coal" [11]. In the
present case, it appears to be easier to disperse the Lower Kittanning seam coal
(C & K) than the Upper Freeport seam coal. Also, the dispersion or flocculation of
these coals with the use of several of these reagent systems is concentration
sensitive. In general, flocculation is more prevalent at the relatively higher
dosage of 5 ppm than at lower levels (< Ippm).
3.3. Action of Effective Dispersants

As discussed above, among the better system dispersants were lignin sulfonate,
sodium silicate, short-chain carboxylic acids (citric, 2-ethyl hexanoic, and tannic)
and sodium tripolyphosphate, with most of the other reagent systems tested
dispersing pjrrite under at least some of the conditions listed in Tables 4 through
6. The better dispersants were generally those found to produce a coal froth from
the Upper Freeport seam coal having low to moderate pyrite content (Table 5).
Two reagents were found to disperse both the coal and pyrite much better than
did the other reagents: 1.6 sodium silicate and Marasperse CB. This is likely due
to the fact that upon dissociation both of these reagents produce anionic species
which are highly electronegative [20-22]. These anions should electrostatically
adsorb to coal and mineral matter particles very strongly, thereby causing the
density of charge in the electrical double layer about the coal and mineral matter
particles to increase. This results in an increase in electrical repulsion, which
creates dispersion behavior.
A possible explanation for the superiority of the 1.6-sodium silicate dispersant
over others tested may relate to its polymerization in solution. As reported in the
literature [20-22], soluble silicates having SiOg-NagO ratios less than about 1.5
often have very unpredictable dissolution and depolymerization kinetics and
reactivity, and the effectiveness of these low-alkaline content compounds will
undoubtedly differ from case to case. Note, however, that high-alkaline silicates
did not appear to disperse any samples of coal and mineral matter very well
either. When not hydrated, very rapid dissolution of these highly alkaline
silicates in water is reported to cause formation of insoluble siliceous gels (believed
to be colloidal hemi-micelles) on the surface of the undissolved silicate, passivating
undissolved solids and preventing further dissociation [21]. Sodium silicate
solutions of 1.5 to 2.0 weight ratio may have dispersed coal and mineral matter
better than higher level soluble silicates because they produce comparable
concentrations of highly-charged poljnneric anions and easily-dissolved monomeric
silicate anions in solution [20-22]. Thus, silicates having mixtures of simple and
complex species will probably prove best for utilization as pyrite dispersants
during coal flotation.
82
The data of Onlin [23] and Onlin and Apian [24] demonstrate that carboxylic
acids adsorb readily onto coal and may significantly alter its zeta potential and
point of zero charge in solution. Pjnrite and other sulfides are also known to be
easily floated with a fatty acid [25,26]. Thus, like the 1.6-sodium silicate and
Marasperse CB, the adsorption of citric acid, 2-ethyl hexanoic acid and tannic acid
can lead to an increased surface charge and interparticle repulsion. In addition,
since carboxylic acids are also well known to complex with a wide range of metal
ions, the use of these types of reagents should reduce the concentration of
multivalent cations in solution, thereby allowing an increased density of negative
charges on particles that then facilitates their repulsion and dispersion.
Sodium tripolyphosphate also tended to disperse coal and mineral matter fairly
well. l i k e the soluble silicate and lignin sulfonate, this complex salt produces
multivalent anions upon dissolution which are highly electronegative. Unlike
these anions, though, polyphosphate (and other similar phosphate) anions are
capable of having both strong electrostatic and covalent attraction to alkali earth
and other cations [22,23,27]. The data of Campbell and Sun [27] indicate that
these anions can strongly adsorb to clay and coal surfaces, eventually leading to
an increase in the repulsion between coal and mineral matter slimes.
4. M I N E R A L M A T T E R D I S P E R S I O N A N D D E P R E S S I O N
D U R I N G COAL F R O T H FLOTATION
After identifying several promising dispersants, bench-scale froth flotation

testing was completed on four coal samples (Table 1) to determine the
effectiveness of using dispersants to decrease the pyrite and ash-forming mineral
content of clean coal froths.
4.L F r o t h F l o t a t i o n w i t h Dispersants Alone

Flotation of samples of nominal minus 0.15-mm (100 mesh) Lower Kittanning
seam coal ( C & K Coal Co.) was completed using 0.125 kg/t of frother and
0.125 k^t of collector in the absence or in the presence of the dispersants listed in
Table 3. A feed particle top size of nominal minus 0.15-mm raw coal was used for
flotation testing because previous work showed that flotation at this particle size
generally produced clean coal froths lower in total sulfur content than did flotation
of either minus 0.6-mm (28 mesh) or minus 0.037-mm (400 mesh) coal feeds, for
systems with comparable clean coal yields [18,19].
Figures 1 and 2 show the results from the current study for laboratory flotation
of Lower Kittanning seam coal. Baseline tests (flotation with frother and collector,
but no dispersant or depressant), shown graphically by the dotted line, were
completed periodically throughout the study to define a base grade-yield
relationship and to ensure the reproducibility of results and congruity of test
conditions. Coal yields for baseline tests ranged from 66 to 75%, with ash and
sulfur contents ranging from 5.5 to 6.9% and 2.0 to 2.25%, respectively. As shown
in Figure 1, the use of dispersants during froth flotation usually improved the
overall separation selectivity between coal and pjnrite or mineral matter. In
general, the addition of dispersants decreased the sulfur content of the clean coal
100 100 100 .....- - - - - - - - - - - - - - - - - - - - - - - - - 100
Indlcat. . .v....ge .... t..t Indlcat. . .v.,age b tt
95 - By.t.m ....... 95 95 95
- By.t.m ..,I..
90 6E,7,3l,8,10
(l-R) . 90 90 90
-
85 2+ 85 85 2+ 85
~ 80 9
6P~V
~ 10
~ 80
~
80 80
"0
"0
Q) 1. lB.JSC" ~ Q)
f
75 3~ .1l 3C
>= lA
75
>= 75 75
ea0 1.E 3 lC 2C ea0 3E
.
70 2A 70 70
70
U
65
:t*
30C 2 + Indica",. 011 addition In 65
U
65
3*
+ Indlcat 011 addition In 65
exta. of .tarvatlon doaage .xce of .tJJrvation dONg.
60 * IndlClt"" 011 not emul.ffled 60 60 * Indlcat 011 not emul.lfIed 60
55 o IndlClt'" dl.".,.."t do.age 55 o Indlcat. . dl.".,.."nt do.age
Inc,..aed by 100%. 55 Increa.ed by 100". 55
~ ~ ~ ~
1.8 1.9 2.0 2.1 2.2 2.3 2.4 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Total Sulfur Content (%) Ash Content (%)
Figure 1. The Effect of Dispersant and Depressant Additions on the Total Figure 2. The Effect of Dispersant and Depressant Additions on the Ash
Sulfur Content of Lower Kittanning seam Coal Froths (1 min. products). Content of Lower Kittanning Seam Coal Froths (1 min. products).
Codes for point labels shown Bre given in Table 3. Codes for point labels shown are given in Table 3.
100 100 100 100
95 95 95 95
90 90 90 90
85 85 85 85
~ 80 80 ~ 80 80
. .
"0
.
"0
Q) B888
Q)
>
75
~ lB ! 88ee 75
>= 75 18 7
1
75
ea0 70 .10 II 70 ea0 70 10 II 70
U lC lE U lC lE
65 65 65 65
60 60 60 60
55 55 55 55
50 50 ~ ~
0.7 0.8 0.9 1.0 1.1 1.2 1.3 9.8 10.0 10.2 10.4 10.6 10.8 11.0
Figure 3. The Effect of Dispersants and Depressants on the Sulfur Content Figure 4. The Effect of Dispersants and Depressants on the Ash Content
of Lower Kittanning-Middle Kittanning Mix Coal Froths (1 min. products). of Lower Kittanning-Middle Kittanning Mix Coal Froths (1 min. products).
Codes for point labels are given In Table 3. Codes for point labels are given in Table 3. 00
W
100 100 100 100 00
~
95 95 95 95
90 90 90 90
85 85 85 85
l 80 80 l
"0
80 80
"0
.. .
Q) Q)
>=
75 Bue 75
>= 75 1A Base 75
ca0 70 1!J
10
1L 70 ca0 70
10 1B 70
U U
65 ~ 65
!
.
65 65
1E 1E
60 1~ 60 60 60
1~
55 55 55 55
~ ~ ~ ~
1.5 1.55 1.6 1.65 1.7 1.75 1.80 8.5 9.0 9.5 10.0 10.5 11.0 11.5
Figure 5. The Effect of Dispersants and Depressants on the Sulfur Figure 6. The Effect of Dispersants and Depressants on the Ash
Content of Upper Freeport seam Coal Froths (1 min. products). Content of Upper Freeport Seam Coal Froths (1 min. products).
Codes for point labels are given in Table 3. Codes for point labels are given in Table 3.
100 100 100 100
95 95 95 95
90 90 90 90
85
. .
85 85 85
l
"0
80
1B
1 1L
Bu.
80 -i?
"0
Q)
80
~ 10
Base
18
. 80
.
.1L
>=
Q)
75 75 75 75
>= 10 1C
ca0 1E 1C
ca0 70 1E 70 70 70
U U
65 65 65 65
60 60 60 60
55 55 55 55
~ ~ ~ ~
3.4 3.5 3.6 3.7 3.8 3.9 4.0 8.5 9.0 9.5 10.0
Figure 7. The Effect of Dispersants and Depressants on the Sulfur Figure 8. The Effect of Dispersants and Depressants on the Ash
Content of Lower Clarion seam Coal Froths (1 min. products). Content of Lower Clarion seam Coal Froths (1 min. products).
Codes for point labels are given In Table 3. Codes for point labels are given in Table 3.
85
froths further than did baseline flotation for comparable coal yield. More
importantly, however, flotation of this hvA-bituminous coal in the presence of
several of the dispersants tested caused clean coal yields to be about 10 to 15%
higher than did flotation under baseline conditions, with equivalent or lower total
sulfur content. This result is somewhat surprising since most of the limited data
that are available regarding coal flotation in the presence of dispersing agents
indicate that moderate to high levels of coal depression may be expected [8-10,18].
However, more recent research has shown that when relatively low amounts of
dispersing agents are used, coal depression can be minimized while attaining
improved pyrite and mineral matter rejection [18].
For convenience. Table 7 shows the best of the flotation results given in
Figures 1 and 2. The best dispersants for pyrite rejection are Marasperse CB,
1.6-sodium silicate, and citric acid. The use of Marasperse CB during flotation of
this coal produces froths with total sulfur content as low as 1.9%. Further, related
work has shown that flotation of this Lower Kittanning seam coal in the presence
of 0.05 kg^t of 1.6-sodium silicate produced a 1.85% total sulfur concentrate from
feed that contained over 3.2% total sulfur [18,19]. Figures 1 and 2 also show that
more coal was depressed using the sodium tripolyphosphate dispersing agent than
with any other reagent. Unfortunately, if additional No.2 fuel oil is used to
improve coal yield, the sulfur and ash content of the floated coal increases
dramatically (compare tests 2 and 2+). Dispersing agents that did not
significantly reduce the sulfur level of floated coal were the ones that were
observed to either mildly flocculate or only slightly disperse pyrite.
Table 7
Superior Flotation Results for C & Lower Kittanning Seam Coal
(Based on Grade-Yield Criteria for One Minute Flotation Products)
Frother: 0.125 kg/t MIBC Criteria:

Collector: 0.125 k g / t No.2 Fuel Oil Sulfur <2.0%, Ash <6.0%, Yield > 60%
Test Reagent Yield Sulfur Content Ash Content

ID System OVt.%) (Wt. %) OVt.%)
3E Marasperse CB / Nigrosine 74.3 1.85 5.6

3 Marasperse CB 66.4 1.91 5.5
1 1.6-Sodium Silicate (0.05 kg/t) 75.9 1.94 6.0
9 1.6-Sodium Silicate (0.10 kg/t) 77.1 1.95 5.9
IE 1.6-Sodium Silicate / Nigrosine 70.1 1.95 5.8
30 Marasperse CB / Hylon VII 63.7 1.97 5.8
6B Citric Acid/NaClO 81.2 1.98 6.0
6E Citric Acid / Nigrosine 78.7 1.99 5.8
7 Aerosol MA-80 79.0 1.99 5.9
3L Marasperse CB / Lime pH=7 80.5 2.00 6.0
86
Table 7 and Figure 2 also show that flotation in the presence of dispersants
often gave coal yields higher than that obtained for this coal with only frother and
collector, without increasing the ash content of the froths. This illustrates the
positive impact of using appropriate amounts of dispersants during flotation.
As stated earlier, the major reasons why gangue particles float with the coal
may be summarized as follows [5,8-11]:
Water carry-over
Flotation of locked particles
Specific flotation
Accidental entrapment in the froth mass
Attachment to coal surfaces as slime coatings
Mutual flocculation and collection of dissimilar particles
Flotation of fine gangue having flotation rates similar to coarser coal
It is not expected that the use of a dispersant during flotation will alter the
capture of gangue should the first three mechanisms be predominant. If, however,
the latter four mechanisms are the primary cause of pyrite and mineral matter
contamination in coal froths, using a dispersant should improve the separation of
the gangue from coal. Adding dispersants can help to reduce mutual flocculation,
release slime coatings, and increase the fluidity of the froth mass, which then
promotes effective drainage of entrapped gangue from the froth.
The effectiveness of some dispersant-containing systems to increase yield while
at the same time reducing the sulfur and ash content of the floated coal suggests
that in addition to water carry-over, one of the latter four mechanisms does
contribute to flotation selectivity problems. An increase in yield without
concomitant increases in the sulfur and ash content of the clean coal froth might
also be caused if the dispersant (or dispersanl/gangue depressant) encourages the
flotation of some essentially clean, but difficult to float coal particles (e.g., coarse,
surface-oxidized, slime coated, etc.), while at the same time helping to reject
locked coal-gangue or free gangue particles.
4.2. F r o t h F l o t a t i o n w i t h J o i n t Dispersanl/Depressant Systems

If the reason for froth contamination is the flotation of locked coal-gangue
particles or their failure to stay rejected once released from their attachment to
coal particles, then a specific pyrite or mineral matter depressant is needed. To
test this premise. Lower Kittanning seam (C & K) coal was floated using various
joint dispersant-depressant reagent systems. Depressants used in this
investigation were selected from those previously found effective on this and other
coals [5,6,9,11,14-19]. Figures 1 and 2 show the results of flotation in the
presence of these dispersant/depressant systems-a listing of the reagents and
identification codes for the tests shown in these figures is given in Table 3. To
simplify the assimilation of some 35 tests, those systems producing the best
results based on a grade-yield criterion are also shown in Table 7.
In general, the best dispersani/depressant systems are those that couple
Marasperse CB, 1.6-sodium silicate, or citric acid dispersant with Nigrosine (an
87
anionic water-soluble dye), Hylon VII (a high amylose starch), sodium

hypochlorite, or lime. The use of the joint Marasperse CB-Nigrosine reagent
system (Test 3E) produced a froth lower in sulfur than when Marasperse CB
dispersant was used alone. In fact, the use of this reagent combination produced
a froth with the lowest sulfur content (and nearly the lowest ash content) obtained
with this coal (Reference 18 may be consulted for details on flotation results with
depressant alone). Though Nigrosine, as with many dyes, is usually very
depressive to coal yield [16], it is believed that the use of a low dosage (0.05 kg^t)
mitigated coal depression. The use of citric acid in combination with depressants
also proved more effective in reducing the sulfur and ash contents of froth
products than when the dispersant was used alone. Note, however, that with the
exception of the 1.6-sodium silicate/Nigrosine reagent system, combining sodium
silicate with a pyrite depressant did not appear to improve the coal-ash or coal-
sulfur flotation selectivity over that attained when using the dispersant alone.
The reason for this may be that since the dispersants were added prior to adding
pyrite depressants and sodium silicates are reported to be reactive with metal
ions, the attachment of all but the most adsorptive depressants for the pyrite and
ash-forming minerals may have been prevented.
It should be noted here that caution must be exercised when dispersants and
depressants are used, either alone or in combination. When the dosage of
dispersant was doubled in the joint Marasperse CB-Hylon VII reagent system
(Test 3C and 3C-circle), coal flotation was depressed markedly. Furthermore, coal
yield and mineral matter rejection can be adversely affected if reagent dosages are
not carefully controlled [5,8,9,11,15,18]. Note that the optimal dosage of
1.6 sodium silicate needed to produce concentrates containing minimum amounts
of sulfur and ash content is about 0.05 to 0.1 kg/t (Compare the results shown in
Figures 1 and 2 for the systems 1, 8, 9, and 10).
Since the use of dispersants alone and in combination with pyrite depressants
reduced the levels of sulfur, and to a lesser degree the levels of ash, for the Lower
Kittanning seam (C & K) coal, several flotation tests using various joint
dispersant-depressant reagent systems were performed on samples of three other
bituminous coals: Lower-Middle Kittanning Mix, Lower Clarion, and Upper
Freeport seams. For most of these tests, the 1.6-sodium silicate or joint
silicate/Nigrosine reagent systems were used. However, based on the results from
the flotation of Lower Kittanning seam coal, the use of a Marasperse CB-
depressant system would likely prove to be very effective in rejecting pyrite and
ash from these coals.
For the Lower-Middle Kittanning coal (Slope 33), the only reagent required to
attain coal yields slightly above 70% was 0.125 kg^t of MIBC. Figures 3 and 4 (see
identification codes in Table 3) show that flotation in the presence and absence of
1.6-sodium silicate dispersant and several depressants did not appreciably reduce
clean coal yield from this level. While flotation with 1.6-sodium silicate alone
(Test Code 1) did not reduce the sulfur or ash content of the floated coal very
much, flotation with Aerosol OT (Code 7) proved effective in decreasing the sulfur
content of the clean coal. In addition, the joint use of 1.6-sodium silicate with
Hylon VII, CPC3005X (typical com starch that was xanthated), and Nigrosine
reduced the sulfur content 10% more than flotation with only MIBC (Figure 3),
while the use of 1.6-sodium silicate in combination with Hylon VII (Code C),
CPC3005X (Code D), sodium hypochlorite (Code B), and Nigrosine (Code E)
reduced the ash content from 11.0% to about 10,0% without decreasing coal yield.
Like the Lower-Middle Kittanning coal mix, tests with mvb Upper Freeport
seam coal only required the use of MIBC frother (0.10 kg/t) to achieve 70% coal
yield. Reference to Figures 5 and 6 shows a somewhat different response to a
similar set of dispersani/depressant reagent systems. The use of the gangue
depressants Hylon VII or Nigrosine with 1.6-sodium silicate dispersant results in
a substantial decrease in coal yield (-10%). For this coal, the lowest sulfur and
ash values were achieved with the use of 1.6-sodium silicate alone.
In the flotation of Lower Clarion seam coal, both 0.125 kg^t MIBC and
0.125 kg/t No.2 fuel oil were needed to achieve 75% coal yield (Figures 7 and 8).
None of the reagent systems were very effective in reducing the sulfur content of
this coal, probably because coal-gangue locking is severe [19,28]. However, the
trend evident from these results is that the use of 1.6-sodium silicate alone or in
combination with sodium hypochlorite, Hylon VII, CPC3005X, and Nigrosine (if
coal depression can be minimized through dosage control) may prove effective in
decreasing the sulfur content of the clean coal froth. In addition, the use of 1.6-
sodium silicate alone or with Nigrosine should also decrease the ash content. In
the present case, the ash content was decreased from 9.5% to about 9.0%. The use
of lime at pH=7, though, does not exhibit much promise.
In summary, Figures 1 through 8 show that the use of some dispersant-
depressant systems can be very effective in rejecting pyrite and mineral matter.
However, these data also reinforce the adages that the best gangue dispersant and
depressant for one coal is not necessarily the best for another coal and careful
control of the dosage of the reagents is paramount to their successful use.
5. CONCLUSIONS
The following conclusions may be drawn from this study:
1. A simple laboratory test for the dispersion of coal, pyrite, and ash-forming
minerals can be used to identify and select reagents which may be effective in
reducing the total sulfur and ash contents of clean coal froths.
2. The use of dispersants alone or in combination with pyrite or ash mineral
depressants provides an attractive means of reducing the sulfur and ash
content of clean coal froths.
3. Testing will likely be required to determine the optimum dosage of dispersants
and depressants. Too little is ineffective and too much can retard coal flotation
and actually increase the sulfur and ash content of a coal froth. Further,
excessive addition may deleteriously affect a blackwater flocculation circuit.
4. Test results indicate that judicious addition of dispersants and depressants
mitigates coal depression and, in some cases, actually increases coal yield
without increasing the sulfur and ash content of the froth.
89
5. For the coals and pyrites tested, 1.6 weight ratio sodium silicate, a sulfonated
lignin sulfonate (Marasperse CB), citric acid, and sulfosuccinate-based wetting
agents (Aerosol MA-80 and OT) were identified as promising dispersants for
flotation testing. Dosages between 1 and 5 ppm (0.02 to 0.06 kg^t) were
sufficient to obtain high levels of coal and pyrite dispersion in the laboratory.
6. The results of this study suggest that in addition to water carry-over, gangue
mineral contamination of the floated coal can be caused by mutual flocculation
and collection of dissimilar particles. Using dispersants can prevent this
phenomenon, while also reducing slime coatings on coal particles and increasing
the fluidity (and drainage capability) of the froth, thereby reducing accidental
mineral entrapment.
7. The use of a gangue depressant in conjunction with mineral matter dispersants
allows for the improved rejection of partially locked or free coal-gangue particles
that have been accidentally entrapped or collected in the froth mass.
8. While several promising dispersants and dispersani/depressant reagent systems
have been identified for use in flotation including Marasperse CB, 1.6-sodium
silicate, and citric acid alone and in combination with Nigrosine and Hylon VII,
these and other reagent systems should be studied more thoroughly, especially
with regards to the effect of the influence of reagent concentration on the trade
off between coal yield and gangue mineral rejection.
9. This study serves to illustrate the influence that the nature of the raw coal may
play in its flotation. The best dispersant or depressant for one coal is not
necessarily the best for another coal.
ACKNOWLEDGMENTS
The authors wish to thank the Penn State Cooperative Program in Coal
Research, Dr. Alan Davis - Director, and the U.S. Department of Energy (Grant
No. DE-GF22-85PC80523) for providing financial assistance for this work. Thanks
are also due to American Cyanamid Company, CPC International, Eastman-Kodak
Company, Philadelphia Quartz Corporation, Reed Lignin, W. R. Grace Company,
and Union Carbide Company for supplying reagents for this work and to Beth
Energy-Slope 33 Mine, C & K Coal Company, and Valley Camp Coal Company-
Helen Mine (formerly Helen Mining Company) for providing the coal samples used
in this study.
REFERENCES
1. J.T. Crawford, Trans. AIME, 189 (1936) 150-162.

2. D.J. Brown, Chapter 20 in Froth Flotation - 50^^ Anniversary Volume,
D.W. Fuerstenau, ed., AIME, Littleton, CO (1976) 518-538.
3. T.J. Olson and F.F. Apian, Proc. 2'''^ Inter. Cong. Applied Mineralogy in the
Minerals Industry, W.C. Park, D.M. Hausen, and R.D. Hagni, eds., TMS,
Warrendale, PA (1984) 367-393.
4. T.J. Olson and F.F. Apian, Proc. Util. High-Sulfur Coals II, Y.P Chugh and
R.D. Caudle, eds., Elsevier, Amsterdam (1987) 71-82.
90
5. R.J. Purcell and F.F. Aplan, Proc. Util. of High-Sulfur Coals IV, P.R. Dugan,
D.R. Quigley, and Y.A. Attia, eds., Elsevier, Amsterdam (1991) 279-294.
6. F.F. Apian and B.J. Arnold, Flotation, Coal Preparation 5th Ed., J.W. Leonard
and B.C. Hardinge, eds., SME, Littleton, CO (1991) 450-485.
7. M.C. Esposito, S. Chander, and F.F. Apian, Proc. Min. VII, A.H. Vassiliou,
D.M. Hausen, and D.J.T. Carson, eds., TMS, Warrendale, PA (1987) 475-493.
8. B.J. Arnold and F.F. Apian, Inter. Jour. Min. Proc, 17 (1986) 225-260.
9. B.J. Arnold and F.F. Apian, Proc. Util. High-Sulfur Coals III, R. Markuszewski
and T.D. Wheelock, eds., Elsevier, Amsterdam (1990) 171-185.
10. B.J. Arnold and F.F. Apian, Trans. AIME, 288 (1990) 1347-1351.
11. F.F. Apian, Trans. AIME, 294 (1993) 83-96.
12. H.F. Yancey and J.A. Taylor, USBM RI 2363, U.S. Bureau of Mines (1935).
13. R.E. Zimmerman, Trans. AIME, 177 (1948) 338-355.
14. F.G. Miller, Trans. AIME, 229 (1964) 7-15.
15. V. Choudhry and F.F. Apian, Min. Metal. Proc, 9 (1992) 51-56.
16. V. Choudhry, "The Use of Pyrite Depressants in Coal Flotation," M.S. Thesis,
The Pennsylvania State University (1979). Thesis supervised by F.F. Apian.
17. R.W. Perry and F.F. Apian, Proc. Util. of High-Sulfur Coals I, Y.A. Attia, ed.,
Elsevier, Amsterdam (1985) 367-393.
18. C.E. Raleigh, Jr. and F.F. Apian, Min. Metal. Proc, 8 (1991) 82-90.
19. C.E. Raleigh, Jr., M.S. Thesis (In Preparation), The Pennsylvania State
University (1993). Thesis supervised by F.F. Apian.
20. J. Leja, Surface Chemistry of Froth Flotation, Plenum Press,
New York/London (1982) 614-619.
21. J.H. Wills, Encyclopedia of Chem. Tech., 18, 2nd Ed., John Wiley & Sons, Inc.,
New York (1968) 134-166.
22. The Philadelphia Quartz Corporation, "Multi-functional Characteristics of
Soluble Silica," Information Bulletin 17-101^0 (1980).
23. T. Onlin, "Evaluation of Collectors for Low Rank and Oxidized Coal,"
M.S. Thesis, The Pennsylvania State University (1984). Thesis supervised by
F.F. Apian.
24. T. Onlin and F.F. Apian, Proc. Annual Tech. Conf. Filtration and Separation,
S.H. Chiang, ed., American Filtration Society, Kingwood, TX, (1989) 37-44.
25. A.F. Taggart, Handbook of Mineral Dressing, John Wiley & Sons, Inc., (1945)
New York.
26. F.F. Apian and D.W. Fuerstenau, Chapter 7 in Froth Flotation - 50'^
Anniversary Volume, D.W. Fuerstenau, ed., AIME, New York (1962) 170-214.
27. J.A.L. Campbell and S.C. Sun, Trans. AIME, 247 (1970) 111-114 and 120-122.
28. T.S. White, "A Study of the Distribution of Pyrite in the Upper and Lower
Clarion Coal Seams and its Preparation Plant Products, M.S. Thesis, The
Pennsylvania State University (1989). Thesis supervised by A.S. Davis.
Dry Electrostatic Separation of Fine Coal
by
Dennis Finseth, Terri Newby and Robert Elstrodt
The Pittsburgh Energy Technology Center

U.S. Department of Energy
P.O. Box 10940
Pittsburgh, PA 15236
A current research project in the PETC Coal Preparation Division focuses the
beneficiation of fine dry coal powders after triboelectric charging. In this process, the fine
coal powder is entrained in a gas stream and made to impact on a metal surface under
turbulent flow conditions. This forceful turbulent contact causes differential charging of the
organic and inorganic phases in the coal. The particles of organic matter acquire a
positive static charge, and the mineral matter, both silicate and sulfide, acquire a negative
charge. When this gas-entrained, charged cloud of particles is directed into a high voltage
field, the positive and negative particles deposit on oppositely charged plates. This paper
will discuss some of the technical aspects of the triboelectrostatic separation and the
results of applying this technique to the beneficiation of a number of coals. The motivation
for this work is to explore the possibility of developing an effective dry separation
technique which could circumvent the problems associated with water removal following
classical fine-coal cleaning. Related dry separations have been the subject of several
recent reviews (1,2,3,4).
Background
Electrostatic separation of particles from gas streams is a well-developed commercial

technology and is practiced on a large scale in electrostatic precipitators used on electric
utility boilers. A number of other well-documented industrial separations are based on
related technology for the beneficiation of minerals (5), food products, and recycling
wastes. Most of these separations utilize induction or corona charging, and the separation
is based on differences in the charging or discharging characteristics of particles of
different composition. Methods utilizing induction or corona charging have also been
applied to the separation of coal from its mineral impurities but, for the most part, these
methods have met with limited success (6). Recent efforts to use electrostatic methods
for the cleaning of coal have focused on the use of triboelectric charging of the coal
92
particles followed by separation of the dry charged material in a static high-voltage field
(7,8). These studies have demonstrated the feasibility of triboelectric charging to achieve
high separation efficiency, but the application of this technique at a commercial scale has
yet to be demonstrated for coal. Further, the fundamental mechanism of differential
charging and the behavior or dense clouds of oppositely charged particles is not well-
understood. Even though the fundamental understanding is not complete in the coal
system, it has been demonstrated that triboelectrostatic charging has deifinite advantages
over inductive or corona charging because the mineral and the organic phases assume
opposite charges and surface conductivities are low.
The conceptual design of a triboelectrostatic separator for coal consists of a charger, a

separator, and some means of collecting the separated streams. Such a design for a
system operating on air entrained dry coal is indicated in Figure 1 below.
(^^^^Refs^^
Flow
Splitter
Tribocharging
Surface
^ ^ o a T ^
Coal Separator
Pyrite Plates
Silicate
Figure 1. Schematic of Triboelectrostatic Coal Separation
In this schematic, only the two product streams are collected. However, evaluating the
process performance is easier by collecting the separated fractions on the separator
plates and determining the composition as a function of distance. This composition as
a function of distance is a convenient measure of the separation efficiency, as illustrated
in Figure 2.
Triboelectrostatic research at PETC has focused on development of a totally pneumatic

system without mechanical charging devices (9). The coal is first entrained in a gas
stream via a venturi injector and then passed through a copper in-line mixer, which
introduces high turbulence, forcing the particles to contact the metal surface and become
93
charged. This charged particle cloud is then immediately expanded through an injection
nozzle and directed between two charged plates which separate the positively charged
coal from the negatively charged mineral matter. These two fractions then collect on the
respective plates. The analytical separator shown in Fig. 2 has plates which are 12" wide,
48" long, and are spaced 4" apart. The normal operating conditions for coal involve a
charge of + or - 25,000 volts on the respective separator plates. The injector nozzle has
a cross section of about 1/8" by 4" and is located equidistant between the two plates. The
entire unit is attached to a vacuum system at the downstream end of the separator which
provides controlled, low-turbulence, sweep air flow through the separator and eliminates
dust emissions. The quality of this separation depends on the charging efficiency, the
charge lifetime, and the efficiency of particle transport and separation in the electrostatic
field. The degree of turbulence in the separator is a very important limiting factor
determining particle transport efficiency, which in turn determines the minimum separator
volume. Data on collection efficiency and deposition profiles indicate that the very simple
entrained flow charger described above is capable of efficiently charging a variety of coals
and maintaining this charge through an appropriately designed injector into the separation
chamber. Early work at PETC focused on small sizes (-400 mesh) to maximize both
liberation of fine mineral matter and the charge to mass ratio of the injected particles (9),
but more recent research has been successful in separating larger size fractions.
Deposition
Injector Profiles in
Clean Coal The Separator
Coal
Refuse
Refuse
Ash Content of
Separator Deposits
SEPARATOR LENGTH
Figure 2. Analytical Separator and Representative Data

94
Results and Discussion
The separation of a 23.2% ash Illinois #6 coal indicated that this coal could be efficiently
beneficiated via triboelectrostatic nnethods. When the -400 mesh size fraction of this coal
is separated the deposition profiles indicate that the separation is essentially complete
within the first 8 to 10 inches for both clean coal and refuse components. The quality of
this separation can be determined by measuring the cumulative recovery of combustible
matter, sulfur, and ash as a function of position on the clean coal plate. Shown in Figure
3.
O
L c
o
CL
O
LU
GC o

i "
S ^
=> S
6 8 10
POSITION, Inches
Figure 3. The Recovery of Combustible Matter, Sulfur, and Ash on the Clean Coal Plate
for -400 mesh Illinois #6 Coal
This data indicates that 70% of the combustible matter in the feed is recovered on the
first 10 inches of the clean coal (negative) plate. While this clean coal contains 70% of
the combustible matter, it contains only 12% of the ash in the feed. These figures
indicate high selectivity for this process. With this coal, the triboelectric separation is
particularly effective in removing ash but, as Figure 3 indicates, the total sulfur removal
is not as impressive. The technique is effective at rejecting inorganic (pyritic) sulfur but
95
the organic sulfur, as in any physical separation, reports to the combustible matter. The
data used to generate Figure 3 above, at 12 inches of separator length indicate a 75%
rejection of pyritic sulfur even though the total sulfur rejection is only 55%. Although this
technique appears to be widely applicable to different coals, they do respond differently
to triboelectrostatic separatio:). The high ash Illinois #6 coal separated above at a very
small particle size can be compared with the separation of a low ash Pittsburgh #8 coal
at a particle size of -200 mesh. In this case, the ash content of the feed is low at 5.06%
and the sulfur content is also much lower (1.6%) than that of the Illinois #6. The response
of the Pittsburgh #8 coal to triboelectrostatic cleaning is presented in Figure 4. This data
is presented in a grade recovery format to emphasize the response of the pyritic sulfur
in this sample to the triboelectrostatic separation. The data indicate that with this coal it
is possible to reject 88% of the pyritic sulfur while collecting neariy 80% of the
jcombustible matter on the clean coal plate.
>
O

liJ
QC

m
t

Si
m
5 o
O )
O
UJ
> m
CUMULATIVE PYRITIC SULFUR RECOVERY

AS % OF FEED PYRITE
Figure 4. Grade Recovery Curve for Triboelectrostatic Separation of Pyrite from -200
mesh Pittsburgh #8 Coal
This separation on the -200 mesh Pittsburgh #8 coal indicates that, on this carefully
selected low-ash sample the separation is very effective in removing pyritic sulfur.
However, interest also exists in determining the performance of this technique on typical
feed to a pulverized coal combustion system. To investigate this, a PC combustion feed
(80% through 200 mesh) generated from a high ash (16%) run of mine eastern
bituminous coal (Pittsburgh No. 8, Blacksville mine) was obtained. This coal was being
used in the PETC combustion facilities and was not ground to specifications. Prior to
96
separation in the triboelectrostatic system, the coal was submitted for washability analysis.
The results of the triboelectrostatic separation are compared with this analysis in Figure
5.
The data indicates that the mineral matter is efficiently liberated for this coal and that
the triboelectrostatic clean coal composition parallels the density curve obtained from the
washability analysis. The points on the triboelectrostatic curve are obtained by analyzing
material collected on the clean coal plate at different separator distances. The triangular
symbol in the triboelectrostatic data is obtained from analysis of the clean coal fraction
generated in a continuous separator. These results indicate significant room for
improvement in the performance of the electrostatic separation, but they do indicate that
it performance on a continuous separator comparable to that on a simple analytical unit
pan be obtained. This dry separation, although not optimized, compares favorably with
other classical beneficiations for these fine-size fractions.
Washability - - y -. c\Bn coot an! clean
100
80
60
w 40
Z3

20
16 24 32 40
Cumulative Ash, Wt.%
Figure 5. Comparison of Washability Analysis and Triboelectrostatic Separation of PC

Grind Blacksville Coal
These evaluations of the potential for triboelectrostatic separation indicate that a number
of different coals respond favorably to the triboelectrostatic technique. Simple
demonstration of the feasibility of a separation is the first step in developing an improved
beneficiation process, but it must then be followed by development of a practical
separator. Recent work at PETC has focused on the operation of a separator which can
be used to evaluate solutions to the problems of fraction collection, recycle operation, air
97
flow control, and separator geometry. A schematic of this separator is shown in Figure
6.
This separator uses rectangular separator geometry, as in the analytical separator, but
a splitter is added to separate clean coal from refuse. Provision is made for continuous
collection of the two particle product streams using small high efficiency dust collection
cyclones. During continuous operation, the refuse and clean coal can be allowed to build
up on the plate surfaces to be dislodged by periodic mechanical rapping. This mode of
operation permits continuous operation to determine the dependence of operating
conditions on perfomiance. Current work focuses on determining the influence of feed
rate, feed particle size, moisture content, separator geometry, and sweep air velocity on
the separator performance.
Figure 6. Schematic Design of a Continuous Triboelectric Separator for Coal Beneficiation

98
Conclusions
Current results using research on triboelectrostatic beneficiation of fine coal indicate that
the principle can be applied to a variety of different feeds, and, under the appropriate
conditions, triboelectrostatic separation can be very effective for removal of both pyrite
and silicate minerals from fine coals. The performance of this separation can be
comparable with other advanced fine coal cleaning processes without the need to remove
water from the product. The focus of research is in the area of continuous operation to
determine the optimum design of a practical separator and to determine the influence of
important processing parameters, such as particulate feed loading, on performance.
References:
1. Lochhart, N.C. et al.. Dry Beneficiation of Coal, Powder Technology, 40 17-42, 1984.
2. Ralston, O.C., Electrostatic Separation of Mixed Granular Solids, Elsevier, Amsterdam,

1961.
3. Kelly, E.G. and Spottiswood, D.J., The Theory of Electrostatic Separations, A Review:
Parts 1,2, and 3, Minerals Engineering, 2, no 1, pp 33-46, no 2, pp 193-205, and no 3,
pp 337-349, (1989).
4. Butcher, S.G. and Symonds, D.F., A Review of Dry Cleaning Processes, Alberta Coal
Mining Research Centre Report CMRC 81/21-T, 1981.
5. Ciccu, R. et al.. Experimental Study On Triboelectric Charging of Mineral Particles, J.

Electrostatics, 23, p. 157-168. (1989).
6. Inculet, I.I. et al.. Electrostatic Beneficiation of Hat Creek Coal in the Fluidized State,
CIM Bulletin, 73, 51-61, (1980).
7. Zhou,G. and Brown, J.D., Coal Surface Conditioning for Electrostatic Separation, Can.
J. of Chem. Eng., 66, 858-863, (1988).
8. Alfano, G, et al.. Application of Static Electricity in Coal and Ore Beneficiation, J.

Electrostatics, 16, 315-328, (1985).
9. Link, T. et al., Initial Study of Dry Ultrafine Coal Beneficiation Utilizing Triboelectric
Charging with Subsequent Electrostatic Separation, DOE/PETC/TR-90/11,19 pp, (1990).
COAL BENEFICIATION USING METHANOL

A. Perkson, S. Meffe and O. Trass*
Dept. of Chem. Eng. and Applied Chemistry
University of Toronto, Toronto, Ontario M5S 1A4
ABSTRACT
A study of total sulfur removal from Illinois coals with methanol as the solvent,
combining extraction and reaction, has been conducted. The coals have total sulfur
contents of 4.32 and 2.63 wt% of which 70 and 85%, respectively, is organic sulfur.
Preliminary experiments were carried out in tubing-bomb reactors, followed by a
systematic autoclave study along with subsequent work in a semi-continuous reactor, with
solvent flowing through a fixed bed of coal.
Temperature, pressure, solvent-to-coal ratio and reaction time were the main
variables in the batch experiment. For the flow reactor, methanol flow rate was added
and temperatures from 375 to 500C were covered. The percentage of total sulfur was
typically reduced from feed to product by 40 to 50%.
Subsequent work involved rapid decompression of the reactor products after

different time periods. Some reincorporation of sulfur was observed at a short operating
time in the semi-continuous reactor and after decompression from batch reaction
conditions.
When the extracted sulfur had been removed prior to decompression, total sulfur
removal increased to 62 percent compared to 42 percent under the same conditions
without decompression. Thus, rapid decompression allowed significantly enhanced sulfur
removal.
INTRODUCTION
Coal beneficiation has lately received considerable attention. With the Clean Air
Act Amendment of 1990 adopted in the U.S.A. and with similar stringent environmental
constraints in place elsewhere in the developed western world, removal of sulfur from coal
has become even more critically important than before. Sulfur, one of the most
undesirable elements in coal, is normally present as inorganic (mainly pyrite), organic and
elemental sulfur. During combustion, most of the sulfur is oxidized to sulfur dioxide which
contributes to the formation of acid rain. Thus, environmental considerations rather than
economic incentives are providing the impetus for the beneficiation efforts, particularly for
sulfur removal. Compared to flue gas scrubbing, removal at the source is preferable
under most scenarios due to the reduced corrosion and, hence, lower maintenance costs
100
of boilers. Waste disposal costs will also be reduced. This will be especially important
in urban areas.
Along with a growing interest in environmental protection, the effort to develop

methods of coal cleaning prior to combustion have increased. Using physical
demineralization processes, e.g. flotation or selective oil agglomeration, it is possible to
remove the major part of the pyritic sulfur. However, to remove mineral sulfur completely,
and also substantial amounts of the organic sulfur, the use of chemical coal cleaning
methods becomes necessary.
The feasibility of organic sulfur removal using methanol has been investigated.
Some initial work by Muchmore and coworkers [1,2] on supercritical extraction with
alcohols and a patent by Keller [3] on various 'Methacoal' fuel technologies were the
starting point. The ability of methanol to penetrate the coal structure and wet all surfaces,
both internal and external, is well known. Two concurrent processes are involved. First,
the methanol, above its critical temperature of 239C, solubilizes various components of
the coal. Some organic sulfur is removed by this solvent action. Secondly, the methanol
begins decomposing at 400C. It is expected that the nascent hydrogen and other
radicals from the methanol decomposition would preferentially attack the organic sulfur
within the coal matrix.
Some of the results of this research project, from the batch reactor study have
been presented previously [4,5] and will be summarized only briefly.
BATCH REACTOR STUDY
The two coals used in this study were supplied by the Illinois State Geological
Survey, from the Illinois Basin Coal Sample Program. One. the IBC-101 contained 10.5%
ash and 4.3% sulfur, 3.0% organic. All percentages used here are weight percent. The
other coal, IBC-108, was a physically cleaned, micronized coal with a total sulfur content
of 2.63%, 2.25% organic.
In the initial phase of this project, total sulfur removal was the dependent variable.
The effects of temperature, solvent density (equivalent to pressure), time and solvent-to-
coal ratio were studied in a series of experiments using 40 and 11 cc tubing bomb
reactors.
Total sulfur in the feed coal and the resultant product char was determined using
a LECO instrument. It uses an induction furnace to bum the sample and an automatic
titrator to determine the total sulfur. Using a calibration curve obtained with standards,
the analysis error is 2%.
Results indicated that going from 350 to 400C gave an improved sulfur removal,
but there was no difference going from 400 to 450C. The sulfur removal proved to be
insensitive to solvent density, with a pressure range of 4 to 16 MPa being covered at
400C. After a period of 30 minutes, run time was also not important, with only a slight
101
further increase in going from 30 to 60 minutes. Finally, the solvent-to-coal ratio indicated
no clear trend [4]. The IBC-101 coal gave slightly higher sulfur removal values compared
to the IBC-108 coal.
Those early experiments were followed by a more systematic study carried out
using the IBC 101 coal, in a 300cc reactor equipped with a thermocouple, pressure
transducer and vent valve. The effects of time, temperature and solvent density were
investigated in this batch reactor [5].
A three level, three factor incomplete factorial design was used. A total of fifteen
experiments were conducted, three of which were replicates at the origin. The three
levels of time were 0, 15 and 30 minutes, where zero minutes was taken as the time
when the system reached the operating temperature for a given experiment. The
temperatures used were 400, 425 and 450C and solvent densities 0.01, 0.02 and 0.04
g/ml. These solvent densities correspond to 1.6,3.3 and 6.3 MPa, respectively, at 400C.
The actual pressure range covered by the experiments was 3.4 to 13.7 MPa. These
higher pressures were due to gas production. The solvent-to-coal weight ratio was fixed
at one for all experiments.
A regression analysis was performed on sulfur removal, weight loss of coal and
weight loss of liquid. All experimental details and analysis results are given in Reference
[6].
Emphasizing here the sulfur removal results, calculated as the difference between
the initial percent sulfur in the feed coal and the percent sulfur in the resultant char, the
following was observed:
During the heat-up time (about 30+ minutes) i.e. time zero in the study, a great
deal of sulfur was removed. The removals were highest at 15 minutes, varying from 39
to 53%, and dropped slightly thereafter. It seems likely that the negative effect of the
longer time is accounted for by reincorporation of sulfur in the coal. Initially, the most
easily removed sulfur comes off, after which the rate of removal is relatively slow and the
concentration of sulfur in the surroundings relatively high, thus favouring reincorporation.
The highest sulfur removal was achieved at a temperature of 450''C. This is

expected since the higher temperatures not only promote the decomposition of methanol
but also increase the reactivity of the coal and the solvent action of methanol. The higher
the solvent density, however, hence pressure, the lower the sulfur removal. This does
suggest that of the two concurrent processes, reaction is more important than extraction.
If extraction were more important, the effect of solvent density would have been the
opposite, with higher densities giving higher sulfur removal.
The weight loss of coal, or coal conversion, was typically 25%, with all the
experiments falling between 21 and 28%. If weight loss of coal is allowed for, the
highest, 5 3 % feed-to-product sulfur removal corresponds to 66% actual removal of the
total original sulfur. About 45% of the pyrite, FeSg, is changed to troilite, FeS, and about
75% of the organic sulfur is removed [5].
102
SEMI-CONTINUOUS REACTOR STUDY
Several series of experiments were conducted using semi-continuous reactors.

In these reactors, there is a fixed bed of coal with continuous flow of preheated methanol
passing through the coal bed.
Initially, when the experiments were started, the emphasis was on supercritical
extraction. A small 20 cm^ tubing reactor was used at relatively high pressures. It was
soon apparent that supercritical extraction was not as significant a factor in desulfurization
as had initially been expected. The switch was, therefore, made to a larger semi-
continuous flow reactor which operated at lower pressures and higher temperatures so
as to emphasize the conditions important for chemical reactions. Finally, a reactor for
rapid decompression was designed to investigate the impact of the rate of pressure
letdown and removal of voltiles prior to decompression
Experimental
A horizontal, stainless steel 316 tube reactor, 25 cm long and 2 cm ID was used
for most of the work. It was heated using temperature-controlled band heaters. The inlet
part of the reactor was connected to the feed line for pre-heated methanol. The methanol
tank was equipped with a check valve and a metering valve. The outlet port of the
reactor was connected to a pressure control valve, condenser and to a sample collection
flask. The non-condensibles were collected in a wet gas trap.
Figure 1 shows the reactor assembly. The first version ends at the ball valve. For
later experiments, the ball valve and the decompression chamber were added.
An experiment was started by packing the coal in the middle of the reactor
between two wire mesh screens. The methanol flow rate was adjusted. A measured
amount of methanol was then transferred to the methanol tank and the connections
made. The preheating system was then started, followed by the band heaters. The
methanol tank was pressurized, and, when the reactor temperature reached 300C, to
prevent clogging of the reactor, the methanol flow was started. At the operational
temperature, pressure was adjusted to the desired value. Gas and liquid samples were
taken at selected time inten/als and the gas flow rate was also recorded at regular
intervals by measuring displaced water from the gas trap.
At the end of a run, methanol flow was terminated, the reactor was cooled,
disconnected and dried ovemight at 107C in a vacuum oven. Gas and liquid samples
were analyzed using the Varian 3400 gas Chromatograph equipped with TOD (thermal
conductivity detector) and FID (flame ionization detector) detectors, 3m Porapak QS and
30 m DB-1 Megabore capillary columns. The solid product, following drying, was weighed
and divided longitudinally, usually into six equal portions. Each portion was analyzed for
total sulfur content using the LEGO apparatus. Atomic Absotion Spectroscopy was also
preformed to determine the residue of inorganic sulfur in some of the post-reaction coals.
Further experimental details are available in Reference [7].
103
Methonol
Fron ^ Preheater
Methonot
reed
Tonk
To Salbung Port
ond Gos Collector
Figure 1 Rapid Decompression, Semi-continuous Reactor Assembly
Rapid Decompression Runs
After the outlet port of the reactor had been connected via a 2-cm ID ball valve to
a 25 litre decompression chamber, rapid decompression experiments were performed.
In the first set of these experiments, the reactor was used in the batch mode, charged
with coal and methanol and then heated to 400C with the flow lines closed. At the
end of a run. the ball valve was opened, as rapidly as possible. A gas sample was
withdrawn and analyzed immediately. After the equipment had cooled down, the
decompression chamber was opened and coal collected from it for subsequent analysis.
In the final set of experiments, the reactor was again used in the semi-continuous
mode, as described earlier. At the end of a run, however, the pressure control valve was
closed and methanol flow terminated. Following that, the ball valve was opened as
rapidly as possible and the heaters tumed off. After cooling, the decompression chamber
was opened, and post-reaction solids collected, and. following drying, analyzed for total
sulfur content.
104
The experiments using the IBC-101 coal in the semi-continuous reactor covered
the following conditions: 5 to 60 minutes reaction time, 375 and 400C temperatures, 120
c m % methanol flow-rate and 2.1 to 6.9 MPa pressures. In one experiment, a 35%
aquatic HCl solution was added in methanol as a promoter in an amount stoichiometric
to residual troilite.
The experiments using the IBC-108 coal covered the following conditions: 30 to 60
minutes reaction time, 40 to 120 cm^/h methanol flow-rate, 400 to 500C temperatures
and 0.35 to 4.2 MPa pressures. Conditions and results are tabulated in Reference [7].
IBC-101 Series
After the initial experiments, it was found that, at the highest pressure of 6.9 MPa,
the tarry extraction products plugged the reactor after some 5 to 10 minutes of reaction
while the low pressures were not sufficient to penetrate the packed coal bed after it
reached glass transition temperature. Results at the intermediate pressure of 4.2 MPa
only are reported here.
At the temperature 375'*C, only 27% of the total sulfur was removed from the coal.
Methanol decomposition was minimal at that temperature and, as the coal glass transition
point was not reached, methanol likely did not penetrate well into the coal matrix.
Therefore, sulfur removal was mainly due to extraction, particularty from coal particle
surface layers.
For the tests utilizing a temperature of 400C, the extent of sulfur removal was
evaluated by obtaining the total sulfur level in coal at various points in time by terminating
the reaction at those times. Figure 2 gives the effect of time on sulfur removal. The sulfur
removal at 20 minutes is lower than expected, 24%. According to the bomb reactor
series [6], sulfur removal reached 30% in 15 minutes. After 60 minutes, a sulfur removal
of 38.6% was reached, in good agreement with Meffe's results of 39.4% removal.
The profiles of the total sulfur content in the coal for the same sequence of
experiments, 5, 20 and 60 minutes reaction time, are plotted in Figure 3. The data were
obtained by the longitudinal sectioning of the coal bed in the semi-continuous reactor.
It is obsen/ed that sulfur reincooration occurred for the 5 minute mn (open

triangles) as the sulfur level in the last two sections exceeded the value in the feed coal
(hollow circles). However, after 20 minutes, (filled triangles) the concentration of sulfur
starts to level off, and after 60 minutes a constant sulfur level has been achieved along
the coal bed, with a total sulfur removal of 38.6%
105
Pressure: 4.2 MPo

Cool: IBC-101
Temperoture: AOCPc
0 5 10 15 20 25 30 35 40 45 50 55 60 65
TIME (min)
Figure 2 Effect of Time on Sulfur Removal

*
C
(/)
Temperoture: 400*C
5 2 O - feed cool IBC-101

V - 5 minutes run
- 20 minutes run
1 h - 6 0 minutes run
^ MeOH flow direction
2 3 4 5
Section Number
Figure 3 Profiles of Total Sulfur Content in Char as a

Function of Reaction Time
106
Considering the hydrogen-rich environment presented by the decomposing

methanol and the coal matrix, hydrogen sulfide should be formed and begin to diffuse
away through the pores of the coal matrix. However, active carbon sites that are being
generated by the devolatilization of the coal matrix react with the H, hereby trapping
the sulfur as newly formed organic sulfur, which may eventually be removed.
To confirm this scenario, the sulfur content of individual sections is reported

cumulatively for the different types of sulfur in Figure 4. These data were obtained by
analyzing longitudinal sections of the coal for pyritic and troilite sulfur content of the coal
bed for the 5 minute run using an Atomic Absorption Spectrophotometer. The standard
test for sulfur forms in coal, the ASTM D2492-84 procedure was followed. The organic
sulfur content is calculated by difference.
5h
Originol TotoK
4h
Organic Sulfur
2h
Originol Pyrite
Troilite
Figure 4 Sulfur Forms Profiles for Coal Bed in the

Semi-continuous Reactor for 5 min. Run
It is clearly seen in Figure 4 that the HgS formed from pyrite and the coal matrix
decomposition upstream in the reactor is reincorporated downstream as organic sulfur.
It is also apparent that the lack of hydrogen in the downstream section of the reactor left
the pyritic sulfur virtually untouched. The pyritic sulfur upstream is reduced 90% from the
original, whereas the organic sulfur content is substantially unchanged upstream and
exceeds the original value of 3% in the downstream section of the reactor.
Atomic Absotion Spectroscopy also revealed that the pyritic sulfur is reduced to
the FeS (troilite) form, which does not react with the methanol or, to be more precise, with
the methanol decomposition products, carbon monoxide and hydrogen. The pyrite
reduction to FeS, during 60 minutes of reaction time, was 89-92%, averaging 90%.
107
Table 1: Sulfur Forms in Feed Coal and Char for the 60-minute Run at 400''C and
4.2 MPa: removal percentaaes.
Initial Char Removed

/'
Organic f.9 35
Pyrite 1.27 0.127 45
Troilite 0.57
The organic sulfur removal value of 35% (Table 1) might be higher. It is yet unknown
how much of the sulfur from pyrite becomes reincoorated as an organic sulfur form.
Raymond and Hagan [8] who studied sulfur transfer in coals during pyrolysis, using ^ S -
doped pyrite have shown that 38% of overall sulfur liberated in the decomposition of
pyrite as hydrogen sulfide became fixed as organic sulfur. Similar behaviour of inorganic
and organic sulfur was noted by Sugawara et al. [9].
Gas Chromatographic analysis was used to identify and monitor the reaction
products in the gas phase. It showed that the main sulfur form in the gas was hydrogen
sulfide with some methyl mercaptan also present. Figure 5 is a plot of HgS concentration
leaving the reactor as a function of time during the reaction. Initially,
Figure 5 Hydrogen Sulfide Concentration in Leaving Gas

versus Time; various conditions
the measurements were obtained to establish the time of reaction. Thus, samples were
not taken frequently enough to allow more continuous curves to be drawn.
108
Curve #1 on the figure represents HgS emission at a reaction temperature of 375C.

Curves #2 and 3 are for reactions at 400C. Curve #3 is for the run where hydrochloric
acid was used as a promoter. Hydrogen sulfide emission was much more rapid than for
#2. Also, besides HgS and MeSH, COS, EtSH and CSg were present in trace amounts
in the gas. As total sulfur removal was 60 percent, the peak may well have been higher
and occurred earlier than shown despite the fact that the coal sample size for Curve #3
was one-half as large as the others, 10 vs. 20 g [7].
The concentration of sulfur in the gas was between 10-12% of the total removed
sulfur for runs at 400C without the promoter. In the case of HCl, most of the removed
sulfur (93%) was found in the gaseous form. The liquid analysis was prefomried on the
gas Chromatograph using a Flame Photoelectric Detector (FPD), and on GC-MS. A
typical chromatogram for liquid is given in Figure 6a. For comparison, the chromatogram
obtained from Meffe's [6] batch reactor studies is given as Figure 6b. The data from GC-
MS are not reported due to their great volume and because most sulfur compounds were
not identified. The data from the FPD indicate that more than 30 different sulfur forms
were present in the liquids from the semi-continuous series, while only five sulfur forms
were present in the post reaction liquids from the batch reactor.
Based on these analyses, it was concluded that most of the sulfur was removed
by extraction with methanol rather than reaction. Addition of HCl to methanol apparently
promotes the decomposition of methanol; hence, more reactions occur.
Following these results, a new direction was taken. Rather than pursuing the
identification of each sulfur species, an oxygen bomb method (ASTM D129-64) was used
to determine the total sulfur content of the liquid.
109
1
if '-
6.7 13.3 20 26.7 33.3 AO 46.7 53.3 60 66.7 73.3 80 86.7 93.3
Figure 6a FPD Chromatogram of a Liquid Sample from

the Semi-continuous Reactor

20 40 60 80
Figure 6b FPD Chromatogram of a Liquid Sample from

the Batch Reactor
110
IBC-108 Serles
At this point of the research project, it was decided to use the IBC-108 coal to
eliminate problems caused by the pyrite, since most of the pyrite had been removed by
physical cleaning. The median particle size of this coal is <10 m (compared to 380 for
the IBC-101 coal).
The results at different pressures are shown in Figure 7 and indicate that there was
some improvement in sulfur removal going from a pressure of 4.2 to 2.1 MPa which then
levelled off going from 2.1 to 0.69 MPa. Actual sulfur removal could be higher for the
pressure of 0.69 MPa since, according to the longitudinal analyses of the char, some
sections had sulfur removals as high as 52.4% (extreme points marked with diamonds).
Observing post-reaction solids, removed as a rod from the reactor, channels were
appearing and disappearing on the surface (at lower pressures), suggesting uneven
exposure of the coal. The results also show that reaction compared to extraction is more
significant at lower pressures and, as the sulfur-containing gases are removed faster due
to shorter residence times at low pressure, higher sulfur removal occurs since less sulfur
reincorporation takes place.
30 -
25 -
20 -
- lowest and highest values of sulfur J
15 -
removal of individual sections
10 - - ovoroge value of sections
Temperature: 400C
5 -
Cool: IBC-108
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

Pressure (MPa)
Figure 7 Effect of Pressure on Sulfur Removal
The effect of temperature is shown in Figure 8 at a pressure of 0.69 MPa. The

results are significantly better at 500C than at the lower temperatures; the results at
450C were expected to have been better to agree with the batch results of Meffe [6]
summarized earlier. The similar results for 400 and 450C may be caused by the
channeling in the coal bed, to be discussed next.
Ill
55
50
45
40'i
I 35
1 30
I 25
I'
15
Coal: IBC'IOS
10 Pressure: 0.69 MPo
-
5
400 410 420 430 440 450 460 470 480 490 500
Temperoture ( ^ )
Figure 8 Effect of Temperature on Sulfur Removal
Analysis of the longitudinal sections of the coal bed for total sulfur content showed
large variation with position (Figure 9). Putting various pieces of evidence together [7],
what emerges is the conclusion that the large differences in sulfur content of the residue
were, indeed, caused by channeling. As the methanol vapour flowing through the coal
bed searches the path of least resistance, some more tightly packed portions of any
section may be substantially bypassed; exposure to a slow rate of renewal of the
methanol vapour in those portions would correspond to a slower rate of sulfur removal.
The effect of channeling is reduced with the higher pressures and longer run durations;
see the curves marked with hollow symbols in Figure 9.
At the pressure 4.2 MPa, channeling occurs to a minimal extent. The problem
starts at the pressure 2.1 MPa and becomes more severe at lower pressures, directly
related to volumetric gas flow, and coal particle size. Channeling was not a problem with
the IBC-101 coal due to is large particle size. If channeling would not have occurred with
the IBC 108 coal, sulfur removal could be over 50%, in the range of the highest individual
section values recorded.
112
55
50
I 40
^ 35 Cool: IBC-108
O - 5 0 0 C. 0.69 MPo. 60 minutes
V - 500* C. 0.69 MPo, 80 minutes
30 - 5 0 0 C. 0.35 MPo. 60 minutes
- 4 5 0 C. 0.69 MPo, 60 minutes
^ MeOH flow direction
25 - J-
3 4
Section Number
Figure 9 Total Sulphur Removal Profiles for Coal Bed

in the Semi-continuous Reactor
Gas analyses, for hydrogen sulfide, and gas flow-rate measurements were made
during the reaction period, since it had been noted from previous experiments that the
gas flow escaping the reactor was fluctuating throughout the reaction period. Figure 10
gives the calculated volumetric flow-rate of HgS per gram of coal in the reactor [7].
The results for temperatures 450 and 500C and pressures 0.35 and 0.69 MPa
show that all the maxima of hydrogen sulfide emission occur in 9-12 minutes. While there
is no real difference in time of the maximum for hydrogen emission between 450 and 500
C, the rate is considerably lower at 450C. After the maximum, hydrogen sulfide
emission decreases rapidly and levels out after around 20 minutes and then stays
substantially constant, even up to 80 minutes. Duplicate experiments (one followed by
rapid decompression) at 500C and 0.35 MPa indicated goor agreement.
Most likely, the scheme of decomposition of sulfur forms is as follows; the thiolic
group decomposes first, followed by the aryl sulfides and eventually the aliphatic sulfides.
Khan [10] has shown that the decomposition of these three functional groups is complete
at about 450C in 25 minutes or less, which is in good agreement with this study.
However, Kelemen et al. [11] demonstrated that aliphatic sulfides initially present in coal
can be converted to aromatic sulfur forms. Further decomposition of aromatic sulfur
forms such as thiophenes is difficult and takes place to a lesser extent. It can explain the
long tail of hydrogen sulfide emission even after 80 minutes.
113
8
U
O

c
mm
CM
I
30 40 50
TIME (min)
Figure 10 Hydrogen Sulfide Volumetric Flow-rate versus Time

(at ambient temperature and pressure)
Rapid Decompression, Batch Mode
A series of experiments was carried out to test the hypothesis of the impact of rapid
decompression sulfur removal patented by Keller [3]. This system involves two
concun-ent processes. Firstly, the methanol, above its critical temperature of 239C and
pressure of 8.08 MPa, solubilizes various components of coal. Some organic sulfur may
be removed by this action. Secondly, the methanol begins decomposing at 400C. It is
114
expected that, by rapid pressure letdown, methanol entrapped in the pores of the coal
matrix not only breaks down the coal particles, thus creating new surfaces and radicals,
but also decomposes to nascent hydrogen and other radicals; these would preferentially
attack the organic sulfur.
Three experiments were carried out at 400C, a solvent-to-coal ratio of 2 and a

pressure of 6.3 MPa (0.04 g/cm^ solvent density) with the IBC-101 coal. The pressure
letdown was done after 15, 30 and 60 minutes at 400C. Sulfur removal was much lower
than expected, well below the results obtained by Meffe [6] for comparable temperature
and initial pressure conditions but without the rapid decompression. Those results were
in the range of 33 to 4 1 % of sulfur removal, all after a reaction time of 60 minutes,
compared to the highest value of only 23% sulfur removal here, also after 60 minutes.
Analysis of the gas sample for sulfur compounds withdrawn from the
decompression chamber did not show any sulfur gases, although these were detected
by smell. The coal in the decompression chamber was deposited in a very fine powdery
form on the walls of the chamber. The limited results do not allow final conclusions to
be drawn, but an explanation for the low sulfur removal results could well be the
adsotion and/or back-reaction of sulfur in the gas with highly active coal particles
suspended in the gas.
Rapid Decompression, Semi-continuous iUlode
Two experiments were carried out at 500C and a pressure of 0.35 MPa using the
IBC 108 coal in the semi-continuous reactor. The previously described procedure was
used with the addition of rapid decompression after 60 minutes of methanol flow.
Results for these two experiments were more encouraging. Relating the results
back to similar conditions (temperature, pressure, time) except for the rapid
decompression, the sulfur removal improved from 42 to 62% for both experiments.
One conclusion which can be drawn from these encouraging results is that
removing voltiles and more reactive sulfur forms prior to the decompression can improve
sulfur removal. With virtually very little sulfur in the gas space, reincorporation is virtually
eliminated.
Much work remains to be done on the impact of conditions for the removal of both
volatile and sulfur compounds before rapid pressure letdown. Similarly, the effects of
pressure and temperature and the rate of pressure decrease should be investigated.
Coai Weight Loss
In coal cleaning processes, the weight loss of coal is an important factor. The
objective is to minimize coal weight loss while maximizing sulfur removal.
115
For the IBC-101 series, typical weight loss was 20%, with the exception of the run
where HCl was used as a promoter. The weight loss for that particular run was
surprisingly low, 8.3%. One probable explanation for this is that the HCl added to the
methanol was a 35% aqueous solution. Water suppresses somehow the decomposition
of the coal matrix, or HCl catalyses the alkylation and halogenation reactions of the coal
matrix, hence, compensating the coal weight loss induced by pyrolysis.
For the IBC-108 series, values fell between 14 and 25%. Pressure and channeling
in the coal bed both had significant effects on weight loss. The higher the pressure, the
more extraction of volatile and bituminous products occurs; hence, coal weight loss
increases. On the other hand, channeling reduces weight loss because less extraction
occurs. This is opposite to the results observed in the batch study [6] where losses
increased slightly as pressure was reduced. Again, in the batch reactor, alkylation may
reduce weight loss. In general, increasing temperature increased the weight loss of coal.
SUMMARY COMMENTS
While there are many questions yet unanswered regarding desulfurization and the
chemistry of sulfur-methanol reactions, some statements can be made reliably, particularly
when observations agree with literature information.
Pyrite and marcasite, FeSg are readily attacked by hydrogen and about 90% is
converted to troilite, FeS, for a 45% removal of pyritic sulfur. This applies to both the IBC
101 and 108 coals for 60-minute reaction times.
Organic sulfur exists in different forms. The mercaptans or thiols (RSH). the
sulfides or thio-ethers (RSR') and the disulfides {RSSR') react fairly readily and would all
be broken done below about 400C [12]. The aromatic thiophenes are, however, much
more stable, fomning a major part of the residual organic sulfur [13] and, likely,
contributing to the slow liberation of hydrogen sulfide even after long reaction times.
The reincorporation of sulfur from the gas or vapour phase into the coal matrix has
been observed here and by a number of other authors [9,10,14]. It obviously makes
sulfur removal that much more difficult.
In a batch reactor, after a reasonable time, some equilibration will likely have
occurred, with whatever sulfur reincorporation already having taken place. The number
of sulfur-containing compounds in the vapour is small, about five, limited to the stable
ones. Yet, the batch reaction plus rapid decompression tests showed large, additional
reincorporation, apparently during decompression, into the fine adsorbing/reactive coal
dust.
At lower temperatures and higher pressures, extraction of sulfur by methanol

appears to predominate. A large number of sulfur compounds, more than thirty, is found
in the extract. If the pressure is above critical, this will be truly supercritical extraction.
In this work, pressures were mostly lower. With temperature at and above 400^C, lower
116
pressures enhanced sulfur removal, suggesting that chemical reactions predominate.

Thus, dual desulfurization mechanisms are at work, each, independently, being a complex
process with many variables.
The work of Hippo and coworkers [14,15] on the desulfurization of individual coal
maceris, while giving some contradictory results, certainly helps to elucidate the total
picture by offering information on the behaviour of important subcomponents. Reconciling
observations made with individual macerate and global results, such as those reported
here, should help make meaningful progress and, hopefully, provide a framework for
eventual modelling of the desulfurization processes.
The experimental data in the semi-continuous reactor are influenced by channeling

caused by fluid flow, thus, making the methanol-coal contact worse. Some re-design of
the reactor geometry may be necessary to eliminate thte problem which is more serious
for very fine coal.
Short contact times between the sulfur-containing vapours and coal, i.e., rapid
removal of the vapour phase, would reduce sulfur reincorporation. This is substantially
being done with the semi-continuous reactor. The added rapid reaction during the
decompression step obviously improved the results considerably, despite some
reincorporation which would be expected to have occurred also in those experiments.
Many other questions regarding optimal starting conditions, rate of pressure release, etc.
must be addressed.
In general, increased temperature results in increased sulfur removal. The same

applies to reaction time, but with the proviso that the positive trend levels off after 30-60
minutes, and, in the batch reactor, there may indeed be a reduction in sulfur removal.
Regarding the possible catalytic effect of pyrite or troilite in the coal, the evidence
in this work, just as in Reference [14] and [15], is contradictory. In the early experiments,
the tBC-101 coal appeared to give better desulfurization results, suggesting that there is
a beneficial effect. The later results, some not reported here, indicated the opposite,
however.
All results confirm that use of promoters such as potassium hydroxide or

hydrochloric acid improve desulfurization, but at a considerable penalty.
It is quite obvious that coal is a very difficult subject to study and sometimes
contradictory conclusions can be drawn.
Looking at the best IBC-108 result at 62% total sulfur removal, and assuming that
coal weight loss is comparable to other measured weight losses at about 20%, brings the
total sulfur rejection to 70%. Assuming, for simplicity, that all pyrite has been reacted to
troilite, all of which stays with the coal, gives the percentage organic sulfur actually
rejected from the coal as 73%, about the same as found from the best IBC-101 results
in the batch reactor. Unless, fortuitously, the best results were obtained in the first
117
experiments, a rather unlikely case, considerable improvement in these results is still

possible, hopefully to the level where they may have some practical value.
ACKNOWLEDGEMENT
Financial support from Hatch Associates Ltd. (Toronto), the Natural Sciences and
Engineering Research Council of Canada and the Ontario Universities Research
Incentives Fund is gratefully acknowledged.
REFERENCES
1. Chen. J.W.. Muchmore, C.B., Lin, T.C. and Tempelmeyer, K.E., "Supercritical
Extraction and Desulfurization of Coal with Alcohols". Fuel Processing technology.
,.289-295. 1985.
2. Muchmore. C.B., Chen. J.W., Kent, A.C. and Liszka, M., "Removal of Organic Sulfur
from Coal by Sequential Treatment with Alcohols", in Int. Conf. on Coal Science,
Moulijn, J.A., Nater, K.A. and Chermin, H.A.G., Eds., Elsevier Science Rubi.,
Amsterdam, pp. 439-442, 1987.
3. Keller, L T . , "Method of Producing Pulverulent Carbonaceous Fuel", U.S. Patent

#4,192,651, 1980.
4. Meffe, S., Perkson, ., Vasquez, E. and Trass, O., "Coal Beneficiation for Slurry Fuel
Preparation" in 'Processing and Utilization of Higti Sulfur Coals IV\ Dugan. D.R.
Quigley and Y.A. Attia, Editors, Elsevier Science Publ., Amsterdam, pp. 461-489,
1991.
5. Meffe, S., Perkson, A. and Trass, O., "Coal Beneficiation and Organic Sulfur
Removal". Proc. 17th Intl. Conf. on Coal and Slurry Technology, Cleanvater, FL, pp.
245-256, 1992.
6. Meffe, S., "Coal Beneficiation Using Methanol: A Batch Reactor Study", M.S.Sc.
Thesis, University of Toronto, 1992.
7. Perkson, ., "Coal Beneficiation Using Methanol: A Semicontinuous Reactor Study",

M.A.SC. Thesis, University of Toronto, 1993.
8. Raymond, R.Jr. and Haga, R.C., "Relationship Between Pyrite Formation and
Organic Sufur Content of Coals as Revealed by Electron Microscopy," Scanning
Electron Microscopy II, 619-627, 1982.
9. Sugavara, T., Sugawara, K., and the late Ohashi, H., "Dynamic Behaviour of Sulfur
Forms in Hydropyrolysis of Coal, Fuel, 67(9), 1263-1268. 1988.
10. Khan. Rashid M.. "Prediction of Sulfur Distribution in Products during Low
118
temperature Coal Pyrolysis and Gasification, Fuel, 68(11) 1439-1449, 1989.
11. Kelemen. S.R., Gorbaty. M.L, George, G.N., Kwiatek. P.J. and Sansone. M.,
"Thermal Reactivity of sulfur Forms in Coal" Fuel, 70(3), 396-402, 1991.
12. Boudou, . J.P., Boulgue, J., Malchaux, L , Nip, M.. de Leew, J.W. and Boon, J.J.
"Identification of Some Sulfur Species in High Organic Sulfur Coal", Fuel, 66(11),
1558-1569, 1987.
13. Damst, Jaap S. Sinninghe and de Leeuw, Jan W., "Organically Bound Sulfur in
Coal: A Molecular Approach, Fuel Processing Technolog/, 30(2), 109-178, 1992.
14. Hippo, E.J. and Crelling, J.C., "Desulfurization of Single Coal Maceris, Fuel
Processing Technology, 27(5), 287-305, 1991.
15. Hippo, E.J., Crelling, J.C., Sarvela, D.P. and Mukerjee, J., "Organic Sulfur
Distribution and Desulfurization of Coal Maceral Fractions, in: Processing and
Utilizing of High Sulfur Coals II, Yoginder P.C. and R.D. Caudle. Elsevier,
Amsterdam, pp. 13-22, 1987.
Characterization and fioccuiation of coal preparation plant blaclcwater
P.A. Rey" and F.F. Aplan^
"Calgon Corporation, P.O. Box 1346, Pittsburgh, PA 15230
^Mineral Processing Section, Penn State University,

University Park, PA 16802
ABSTRACT
S a m p l e s of the fine refuse slurry from several coal preparation plants were
characterized a s to their mineralogical content and the ionic content of their associated
water. Sample filtrates showed them to contain largely S04"^ (1500 p p m mean) and Ca"^^
(150 p p m mean), with lesser amounts of Cr, Mg"^^. Mn"^^, Fe"^^ and Zn"^^. The Al"^^
content w a s nil. The surface properties of the blackwater solids were studied by u s e of
zeta potential m e a s u r e m e n t s , both in the p r e s e n c e and a b s e n c e of Ca"^^ and S04'^.
These ions were found to affect the coal and the mineral matter constituents of the
blackwater differently. The flocculation of the blackwater and its coal and mineral matter
constituents by nonionic, anionic and cationic flocculants w a s evaluated, a s a function of
pH, by u s e of settling rate, sludge volume and supernatant turbidity. Flocculation w a s
found to b e improved in the p r e s e n c e of S04"^ and, especially, Ca"^^ or Al"^^.
1. INTRODUCTION
Blackwater is the n a m e applied to the fine refuse/water slurry exiting a coal preparation
plant. In a typical preparation plant, this is usually the flotation tailings and contains about
2-5% solids. The solid fraction is about half each of unrecovered coal and fine ash
minerals, mostly clays and quartz. In past times the blackwater w a s often sent to a slurry
pond from which the water w a s d e c a n t e d and the settled solids were impounded.
Modern practice m a k e s u s e of a thickener to remove the bulk of the water for recycle
while the thickener underflow, at about 30% solids, is d i s p o s e d of in a bore hole or slurry
pond or dewatered by, e.g., a belt p r e s s and incorporated with the c o a r s e refuse from
the plant for disposal.
An effective blackwater treatment system requires the u s e of a flocculant to produce
both rapid settling of the solids and a relatively clean water effluent. To design a system
properly, it is necessary to know the particle size and mineralogy of the solid particles,
their surface chemistry, the water chemistry, and the action of a polymer on both the coal
120
and mineral matter fractions of the solids to be flocculated. It is the goal of this study to
quantify these variables.
2. EXPERIMENTAL MATERIALS AND METHODS
2.1. Materials
2.1.1. Plant survey. Samples were collected from the ten preparation plants listed in
Table 1. These represented the thickener overflow, underflow and feed streams. In some
cases more than one feed stream was sampled. The slurry samples were filtered, the
solids dried and saved for further evaluation. The filtrate samples were divided into two
parts. One portion was immediately analyzed for water quality, while the other fraction
was acidified to pH 2 with HCl to prevent precipitation and subsequently analyzed for
cations by atomic adsorption. Sample J was used but sparingly.
The dried filtrate was treated by low temperature ashing and the ash mineralogy
quantified by x-ray diffraction using the procedures of Bradley (1).
Table 1
Preparation Plants Studied
Plant Seam County/State
A Upper/Lower Kittanning Cambria, PA

Upper/Lower Kittanning Cambria, PA
C Lower Freeport Cambria, PA
D Lower Freeport Cambria, PA
Lower Kittanning
Pittsburgh Greene, PA
F Elkhorn # 2 Pike, KY
Hazard # 4
G Elkhorn # 2 Pike, KY
Pittsburgh Washington, PA
1 Pittsburgh Washington, PA
J Lower Kittanning Cambria, PA
121
2.1.2. Synthetic blackwater. A synthetic blackwater was used for testing because
aging of the sample between its collection and testing proved to be a serious problem,
affecting both the surface property measurements and reproducibility of flocculation
experiments. The synthetic blackwater mineralogy, given in Table 2, will hereafter be
referred to as 'blackwater'. Its composition was based on the average blackwater
composition from 11 Eastern U.S. plants as determined by Bradley et al. (1) and on 9
plants from this study. For convenience the coal content was set at 50% using clean
Pittsburgh seam coal whose analysis is given elsewhere (2). The size analysis of the coal
was 100% minus 150 Mm, 4 1 % minus 41 Mm and 3% minus 1 Mm, while the mineral matter
was set at 100% minus 150 vn 83% minus 44 and 23% minus 1 . The size
structure of the coal and mineral matter components were taken from the average data
of Eastern U.S. plant blackwater as determined by Bradley, et al. (3).
Table 2
Composition of Actual and Synthetic Eastern U.S. Blackwater Solids
Mineral This Study Bradley et al. (1) Synthetic
(9 samples) (11 samples) Blackwater
Carbonaceous 56 59 50.0
Illite 22 22 28.1
Kaolinite 5 5 5.3
Quartz 6 6 8.5
Calcite 5 5 6.0
Chlorite tr 2 2.0
Dolomite tr - 0.1
Other ~6 ~1 -
2.1.3. Flocculants. The polymers used in this study were commercial types
representing nonionic, anionic and cationic forms. The nonionic flocculant was a
Polyacrylamide (PAM), with an approximate molecular weight (MW) of 13-15 million. The
anionic samples were NaOH hydrolyzed Polyacrylamides (HPAM) 15, 25 and 35%
hydrolyzed. They are considered, here, to have relative changes of - 1 , -2 and -3,
respectively. They have MW values of 5-10 million. The cationic polymer was a DMDAAC
(Dimethyl diallyl dimethyl ammonium chloride) polymer of 600,000 MW and was
assigned a relative charge of +4.
2.2. Methods
2.2.1. Surface studies. Because the samples represented a plethora of minerals with
different surface response to a change in pH, the average zeta potential was measured
122
in a relatively thick slurry (20%) using a Micrometrics mass transport analyzer. However,
a few experiments were done using the Zeta Meter and these will be so identified.
2.2.2. Flocculation studies. A procedure was developed to insure that the synthetic
blackwater sample was thoroughly wetted. This was achieved by placing 3 g in 50 ml
distilled water in a 150 ml beaker in an ultrasonic bath and agitating for three minutes.
Flocculation tests were conducted on the coal and mineral matter fractions, separately,
and on their blackwater mixture. After the solids were well wetted, the pH was adjusted
and the suspension again treated in the ultrasonic bath for 2-5 min. The suspension was
then stirred by a Phipps and Bird stirrer at 100 rpm with an additional 50 ml of polymer
solution (0.01%) and/or water added over a period of 80 sec. The stirring was stopped
and the beaker contents transferred to 100 ml graduate cylinder and inverted three times
to ensure slurry uniformity. The settling rate was measured as was the turbidity of the
supernatant liquid at 60 and 1440 min. The sludge volume was also measured after 1440
min.
3. EXPERIMENTAL RESULTS AND DISCUSSION
3.1. Composition of solids

These data have previously been given in Table 2. As with the study of Bradley et al.
(1), coal makes up over 50% of these 20 preparation plant samples. Incidentally, this
indicates the need for improved attention to the flotation processing of the plants
sampled. Also note from Table 2 that illite clay is the most important mineral present, with
kaolinite clay, quartz and calcite making up most of the rest of the blackwater solids. As
previously noted (1,4), the ash mineralogy differs strikingly from that of the coal measure,
per se, where kaolinite is the principal clay and gypsum is more important than is calcite
(5). The greater illite content of the actual blackwater has been attributed to overbreak
of the adjacent Pennsylvanian shales during mining (1).
3.2. Water chemistry

The water chemistry is given in Table 3 for the nine plants surveyed here. Included
in this study is additional data by Rey (6) on 22 more plants. It is apparent that 504"^ and
Ca"^^ are the two most important ions in solution. The pH averages "^7.8 and the
conductivity and alkalinity of the water is substantial. The low and high values of pH from
the Rey study were atypical (6). Because of an average pH of 8, essentially all of the
heavy metals have been precipitated as their hydroxides. One small thickener feed
stream in the present study came from a wet scrubber at pH 4.2. It had a very high Zn
content, but at pH 7.5 the thickener overflow ran only 0.03% Zn.
The data are comparable with those of Miller and Deurbrouck (7) who found 0.1-120
ppm Ca"^^ and 60-800 ppm SO^'^ from four plants. The data are also in general
agreement with that of Meerman (8) for German preparation plant waters, while the cation
contents are similar to those reported by Randolph et al. (9).
3.3 Surface properties of blackwater

The electrophoretic mobilities and zeta potentials of the blackwater solids from seven
preparation plants are given in Figure 1. With one exception, these samples are negative
under all conditions between pH 2-10.5. This is not surprising since the clays and quartz
are generally negative over this range (10), and coal is generally negative below pH 7 or
123
Table 3
Analysis of Coal Preparation Plant Thickener Water
Susp. Alkalinity Hardness
Conduct, Solids, methyl Bicarb., CaCOa CI SO4
Values pH mg/l orange mg/l mg/l ppm ppm
This studv (filtrates)
mean 7.9 1700 120 - 490 110 1500
low 7.3 600 10 - 70 40 60
high 8.2 4250 690 - 1460 530 4400
Rev (makedown water) (6)
mean 7.8 2477 117 29 180 431 111 882
low 3.6 410 5 0 4 0 6 5
high 11.9 2000 2500 178 516 2770 1000 12000
Ca Mg Mn Zn Fe AI Ca Na
Values ppm ppm ppm ppm ppm ppm ppm ppm ppm
This studv (filtrates)
mean 150 27 0.16 0.06 0.04 <0.1 - - -
low 20 4 <0.01 <0.01 <0.02 <0.1 - - -
high 470 72 0.34 0.25 1.10 <0.1 - - -
Rev (makedown water) (6)

mean 138 22 1.7 0.2 2.2 4.6 0.01 374 7
low 5 0.1 0.1 0.1 0.1 0.1 0.05 29 2
high 1100 220 55 18 650 80.0 0.45 6000 120
124
8, increasingly so as its surface becomes oxidized (11). Some of the samples are
strongly negative at pH >9. Miller and Deubrouck (7) found zeta potential patterns very
similar to those of Figure 1 for the four coal slurries they studied. A study of the aging
phenomena for blackwater indicated that a fresh plant sample showed a zeta potential
of about -10 mv for the range pH 2-10. This became -20 to -30 mv over a similar pH
range when the sample was aged for three years.
The zeta potential of the Pittsburgh coal, the mineral matter and the synthetic
blackwater is shown in Figure 2 as a function of pH. The Pittsburgh seam coal sample
used here shows a PZC (Point of Zero Charge) at pH '"4.7, while the mineral matter and
the coal/mineral matter mixture (synthetic blackwater) are strongly negative. Note in the
range pH 4.8-7.5 that the mixture is more negative than either parent indicating a strong
synergistic effect.
Because Ca"^^ and S04"^ are major ions found in preparation plant water, the effect of
'average' (150 ppm Ca"^^ and 1500 ppm S04"^) and 'high' (400 ppm Ca""^ and 4000 ppm
S04"^) values of these ions were compared to the response of the bare solids in water.
Figure 3 demonstrates that the influence of Ca"^^ on the coal is not great below its PZC,
but, as might be expected, Ca"^^ at the 150-400 ppm level sharply decreases the surface
charge of coal above its PZC of pH 4.7. Ca"^^ reduces the negative zeta potential of the
mineral matter constituent at all pH values studied. Figure 4 shows the effect of S 0 4 ' ^ .
Note that it makes the Pittsburgh seam coal less negative above its PZC (possibly due
to compression of the electrical double layer at these rather high concentrations, ^ 10"
^M/L). On the other hand, the mineral matter fraction becomes more strongly negative
in the presence of 1500-4000 ppm S04"^.
A reduction in the zeta potential at particle surfaces should make them easier to
flocculate. This is in accord with the long-time use of lime as a flocculant. Arnold and
Apian (12) have shown that Ca"^^ can also interact with clay minerals present to alter their
surface charge, inhibit the deleterious effect of slime coatings on coal, and improve coal
flotation.
3.4. Flocculation
Organic polymeric flocculants have been used for many years to flocculate blackwater.
While several general studies and the elucidation of principles are available in the literature
(see, e.g., refs. 6,7,13-15), most in-plant work has been done on a pragmatic basis or
based on proprietary information available only to the supplier's representative. Closely
allied to this process is the use of a higher concentration of a high MW polymeric
flocculant to produce pea-sized agglomerates, called "cattermoles" (16,17). They can
facilitate both rapid settling and enhance further dewatering steps, as, for example with
a belt press.
The flocculation of synethetic blackwater as a function of pH regulation using only the
inorganic compounds NaOH or C a ( 0 H ) 2 is shown in Figure 5. When NaOH alone is
used, flocculation is effective only at pH < 7 and at pH 13. As shown by the turbidities,
(), settling rates (S.R), and settled sludge volume ( S . V . ) , the blackwater is completely
dispersed in the range pH 8-12.5. Separate experiments showed this phenomenon to be
due largely to the mineral matter constituent, though coal alone was found to have a very
low settling rate. The use of lime decreases the long time (t^^^q) turbidity, but its biggest
advantage is to improve turbidities, settling rate and sludge volumes in the pH 9-12.5
Figure 2. Surface electrical properties of the
solid constituents in synthetic blackwater.
O mineral matter; Pittsburgh seam coal;
synthetic blackwater
pn
Figure 1. Surface electrical properties of unflocculated
125
thickener feed samples. Plant designations given in Table 1.
126
Figure 3. The effect of [Ca+2) on the surface Figure 4. The effect of [S04"2] in the surface
properties of blackwater constituents properties of blackwater constituents
(Zeta Meter). (Zeta Meter).
O none; 150 ppm; A 400 ppm O none; 1500 ppm; 4000 ppm
127
0.1, IIIII -II i20
0.05
in
lOOOc-
2 100
O

er
10
I440
J l__J L J L
7 9 II 13
pH
Figure 5. The effect of pH control on the settling characteristics of

synthetic blackwater.
NaOH; CaiOHlj
128
region. Flocculation and rapid settling occurs at pH 13 because of compression of the

electrical double layer at this high ionic strength.
3.4.1. Nonionic flocculant. The use of polymeric flocculants to flocculate the coal and
mineral matter parents and the synthetic blackwater mixture as a function of pH is shown
in Figure 6 for a nonionic RAM flocculant. It is immediately apparent in comparing the
three types of solids treated, that there is a synergistic effect that can be attributed to the
mixture of coal and mineral matter. The turbidity of the synthetic blackwater mixture is
similar to that of the mineral matter parent, while the settling rate at pH < 8 is even more
rapid than is that of the coal alone. For the blackwater and the mineral matter
constituents, the problem of essentially complete dispersion is apparent in the region pH
9-12.5, not unlike that in the absence of a polymeric flocculant seen in Figure 5. This is
due to the presence of many fine particles which remain in suspension even after 24
hours. If flocculation is to be achieved in this pH region, some method of surface charge
control might be used to incorporate the fines into the settling mass since bridging by a
polymer seems insufficient.
By way of contrast, coal is readily flocculated by this nonionic polymer. Mirville and
Hogg (13) have shown this polymer to be very strongly absorbed onto the coal. As a
consequence, the coal is readily flocculated, producing rapid settling rates and low
supernatant turbidities.
3.4.2. Anionic flocculant. The polymer used in this case is a 15% hydrolyzed RAM.
Titration with NaOH has resulted in the formation of some carboxyeate (COOH) groups
in the polymer. The coal (Figure 7C) acts much the same as it did when a nonionic
polymer was used, except the settling rate is inferior at pH 3. When using an anionic
flocculant, the mineral matter acts as it did in the presence of a nonionic flocculant in
terms of S.R. and S.V., except that settling rate with the anionic form is superior in the
region pH 6-8.
For the synthetic blackwater (Figure 7A) the influence of the carboxyl groups is
apparent. Roor flocculation and settling occur at pH < 5 because the neutral RCOOH
species predominates rather than the anionic RCOO' species found at higher pH (10).
As the pH is increased, the settling rate increases markedly from pH 5 to 9. Carboxylates
are known to attach strongly to coal, probably through a mechanism of surface reaction
between surface hydroxyls and the reagent (18). The increase in turbidity in the region
pH 8-12 may be attributed to poor flocculation of the fine clay particles in the blackwater.
An anionic functional group would not be expected to attach readily to the highly negative
clay and quartz constituents of the blackwater (see Figures 1-4).
The interplay of the coal and mineral matter constituents of the blackwater again
manifests itself. Turbidities and sludge volumes of the blackwater are similar to the
mineral matter parent, while settling rates more closely resemble the coal constituent.
3.4.3. Cationic flocculant. The use of a DMDAAC homopolymer as a flocculant is

shown in Figure 8. Turbidities of the blackwater and the mineral matter constituent are
much reduced, ostensibly due to the interaction of cationic reagent and a highly negative
surface. With the exception of short term (TQQ) coal turbidity, the results, especially that
of the setting rate, are much less sensitive to changes in pH than were found with the
nonionic and anionic flocculants. The presence of both fine mineral matter and fine coal
Figure 6. Settling criteria of suspensions flocculated with 5 ppm nonionic polymer.
A. Blackwater; B. Mineral matter; C. Pittsburgh seam coal
129
130
Figure 7. Settling criteria of suspensions flocculated with 5 ppm anionic polymer
(15% hydrolyzed).
Figure 8. Settling criteria of suspensions flocculated with 5 ppm cationic polymer.
131
132
have resulted in low turbidities of the blackwater mixture, however. The very low S.R. with
this flocculant may be due to its comparative low MW 600,000).
3.4.4. Polymer hydrolysis. Accumulated experience has shown the preference of an

anionic over a nonionic polymer as a coal preparation plant flocculant. Tests were made
using a series of PAM flocculants of 0, 10, 15, 25 and 35% hydrolyzation. A higher
degree of hydrolyzation would give the polymer a higher negative charge. Tests were
made to determine the polymer dosage necessary to achieve various settling rates (0.5,
1.0 and 1.0 cm/sec). Reference to the previous data indicate all of these to be relatively
rapid settling rates.
Tests with the synthetic blackwater (Figure 9A) indicate that the minimum dosage
requirement for rapid settling is achieved at pH 7 when using a polymer hydrolyzed to
about 25%. The mineral matter constituent, alone, however, works best at about 10%
hydrolyzation. Apparently, for the flocculation of clays a slight charge is desirable,
Michaels and Morelos (19) have noted that clays have a tendency to absorb anionic
polyelectrolytes. The flocculation of coal by itself is difficult to portray. As polymer
hydrolysis exceeds 15%, the floes become large pellets or 'cattermoles' (refs. 16 and 17).
These bridge across the cylinder wall making an accurate measurement of the settling
rate impossible, but it is known to be relatively large ( ' " I cm/sec). Very large floes are
formed at dosages of only a few ppm of flocculant. As a consequence, excellent
blackwater flocculation seems to occur at 25% hydrolysis and good settling rates are
achieved at 3-5 ppm of the HPAM flocculant.
3.4.5. Addition of multiple flocculants and their sequence of addition. Previous data
have shown that both nonionic and anionic flocculants are good for general flocculation,
except for their inability to flocculate fine mineral matter, especially in the range pH 8-12.5.
Since cationic flocculants work well in this region, a mixture of an ionic and a cationic
flocculant seems appropriate. Much commercial practice makes joint use of these two
flocculant types. This procedure should provide the advantages of using the charge
neutralizing ability of the cationic polymer and the effective bridging capabilities (and,
hence, high setting rates) of the high molecular weight anionic polymer.
Figure 10 gives the results of synthetic blackwater flocculation at pH 7 using 3 ppm
of a 15% hydrolyzed PAM. The designation A/C means the initial addition of the anionic
flocculation followed by the cationic flocculant, and C/A represents the reverse. It is
immediately apparent that the low MW cationic flocculant alone cannot produce a
reasonable settling rate. It can, however, achieve a very low supernatant turbidity.
Conversely, the 15% HPAM anionic polymer can achieve a 0.42 cm/sec settling rate, but
its use also results in a very turbid solution. When added together, the advantages of
both are achieved. However, it is also apparent that the order of addition is important,
with the prior addition of the cationic polymer (C/A) being superior to the reverse
sequence. While excellent settling rates are achieved in the C/A mode by the addition of
2-20 ppm cationic polymer, maximum settling rate is achieved at ""5 ppm. Note from
Figure 10 that the A/C mode is inferior to the C/A mode in the terms of settling rates, but
that both methods achieve relatively low turbidities ( " NTU).
When the reverse experiment of using 5 ppm cationic and a variable amount of anionic
polymer was done (Figure 11), the C/A sequence gave slightly superior settling rates to
the A/C sequence. In terms of rapid settling, the concentration of anionic polymer
Figure 9. Polyacrylamide polymer concentration required to achieve specified
settling rate.
133
134
ANIONIC POLYMER CONCENTRATION (ppm)
Figure 10. Effect of cationic polymer concen
tration and sequence of polymer addition on the Figure 11. Effect of anionic polymer concentration
flocculation of blackwater at pH 7. Anionic d sequence
ar| of polymer addition on the flocculation
polymer (15% hydrolyzed PAM) dosage constant f blackwater
o at pH 7. Cationic polymer dosage
at 3 ppm. constant at 5 ppm.
135
appears to be much more important than that of the cationic polymer. As little as 3 ppm
anionic polymer was found to produce settling rates of 0.5 cm/sec. The A/C sequence
gave a lower turbidity value, similar to that found in Figure 10, though both sequences
gave very low turbidity values. The low turbidities with the A/C sequence can be
explained as follows: when the cationic polymer is attached last, it is available at the
extremities of the floe to capture any remaining fine particles in suspension.
3.4.6. Effect of Ions in Solution on Flocculation. These data are summarized in Table
4. With a nonionic flocculant, turbidities are decreased and settling rates are increased
in the presence of Ca"^^, SO^"^ or alum. In the absence of a flocculant, alum, by itself,
produces very low turbidity water but at very low settling rates, while Ca^^ and Al"^^
increase S.R. more effectively than does S04"^ with an anionic flocculant. Ca"*"^ produces
the lowest turbidity but at a sacrifice in settling rate. S04'^ gives the fastest S.R. and the
highest . The substantial increase in settling rate for the nonionic polymer in the
presence of a metal ion reinforces the findings of Rey (6) and the generalization for the
flocculation of fine particle suspensions given by Hogg (20) that more efficient flocculation
is achieved by first destabilizing the suspension with an inorganic multivalent ion prior to
flocculation with a polymeric flocculant.
Table 4
Joint Use of Polymeric Flocculant and Ions in Solution (pH 7) for Blackwater Flocculation
Nonionic 5 ppm Anionic 5 ppm
S.R. cm/sec S.R. cm/sec
Ion Conc'n ppm Teo NTU Teo NTU
None 0 25 0.5 30 1.6
400 12 1.0 15 1.2
4000 15 0.8 55 2.1
Alum 5000 15 2.0 - -
Alum 5000 --
Alum, no polymer 3 <0.1
4 CONCLUSIONS
The following conclusions may be drawn from this work:

1. The composition of the blackwater solids from nine Eastern U.S. preparation plants
was found to contain ' " 5 5 % coal, ""22% illite clay and lesser amounts (^"5%) each
of kaolinite. quartz and calcite. These data are similar to those reported by Bradley
et al. (1).
2. This high coal content indicates that plant operators need to pay more attention to
improving coal flotation.
136
3. Continuing the work of one of us (Rey, ref. 6), preparation plant thickener waters
were found to contain substantial amounts of Ca"*"^ (mean 150, range 60-470 ppm)
and S04*^ (mean 1500, range 60-4400 ppm), with lesser amounts of Mg"^^ (mean 27
ppm) and generally 1 ppm or less of most common heavy metal ions.
4. A synthetic blackwater mixture was used in testing because aging problems
prevented use of actual plant samples. Its mineralogical and size composition was
similar to that of actual plant samples.
5. Zeta potential of plant blackwater solids showed them to be negative over the range
pH 2-11. Only sample one was found to be positively charged at low pH (PZC 2.5).
6. The Pittsburgh seam coal used in preparing this synthetic blackwater had a PZC at
pH 4.7, whereas the mineral matter and the blackwater mixture showed negative zeta
potentials over the entire range pH 2-11, similar to the actual plant samples.
7. In the presence of 150-400 ppm Ca"^^, the Pittsburgh coal becomes less negative
above its PZC while the mineral matter becomes less negative over the entire range
pH 2-11.
8. In the presence of 1500-4000 ppm 804"^, the mineral matter fraction becomes
strongly negative while the coal becomes less strongly charged both above and
below its PZC.
9. The adsorption mechanism of Ca"^^ and 504'^ onto coal and onto mineral matter
must differ.
10. The flocculation of blackwater and its mineral matter component with a nonionic or
anionic Polyacrylamide (PAM) flocculant works reasonably well only in the range pH
3-8 and at pH 13. Conversely, coal was flocculated to some extent over the entire
range pH 3-13, likely due to the strong adsorption of PAM onto coal.
11. A cationic flocculant proved to be an excellent means of reducing supernatant
solution turbidity, but because of its low molecular weight (""600,000), its use
resulted in a suspension of very low settling rate.
12. An anionic PAM flocculant with a 25% degree of hydrolysis produced the best settling
results at a minimal flocculant dosage for the blackwater. However, the mineral
matter constituted alone was best flocculated with a 10% hydrolyzed PAM.
13. A mixture of a cationic and an anionic flocculant produced excellent blackwater
flocculation both in terms of settling rate and turbidity.
14. The presence of rather large quantities of 804'^ and, especially Ca"^^ and alum,
improved blackwater flocculation with PAM flocculants.
REFERENCES
1. P.B. Bradley, R. Hogg and F.F. Apian. Trans. AIME, 268 (1980) 1831.
2. W.C. Hirt and F.F. Apian, Proc. Util. High Sulfur Coal IV, P.R. Dugan, D.R. Quigley
and Y.A. Attia, eds., Elsevier, Amsterdam (1991) 339.
3. P.B. Bradley, M.F. Placha, R. Hogg and F.F. Apian, Trans. AIME. 268 (1980) 1836.
4. F.F. Apian. Chapt. 13 in Industrial Practice of Fine Coal Processing, R.R. Klimpel and
P.T Luckie. eds.. SME. Littleton. CO (1988) 99.
5. J.V. O'Gorman and P.L Walker. Jr.. Fuel 50 (1971) 135.
6. P.A. Rey. in Flocculation and Dewatering. B.M. Moudgil and B.J. Scheiner, eds.,
Engrg. Foundation, New York, (1989) 195.
7. K.J. Miller and A.W. Deurbrouck, U.S. Bureau of Mines. Rl 7102 (1968).
137
8. P.G. Meerman. paper A IV 13, 2nd Int'l. Coal Prep. Cong., Easen, 1954.
9. K.B. Randolph. L B . Key and R.C. Smith, Jr.. in Proc. Symp. Coal Cleaning to Achieve
Energy and Environmental Goals. EPA 600/7-79-0986 (1978) 824.
10. F.F. Apian and D.W. Fuerstenau, Chapter 7 in Froth Flotation - 50th Anniversary
Volume, D.W. Fuerstenau, ed.. AIME, New York (1962) 170
11. F.F. Apian. Trans. AIME. 294 (1993) 83; Mining Engrg. 45(1) (1993) 83.
12. B.J. Arnold and F.F. Apian, Int. Jol. Mineral Proc. 17 (1986) 243.
13. R.J. Mirville and R. Hogg, Polymer Adsorption and Flocculation in the Treatment of
Coal Preparation Waste Water. Preprint 79-61, SME. Littleton, CO (1979).
14. W.P. Foshee, M.J. Swan and R.R. Klimpel. Trans. AIME 272 (1982) 293.
15. R. Hogg, Chapter 11 in Fine Coal Processing, S.K. Mishra and R.R. Klimpel, eds..
Noyes Pubs., Park Ridge. NJ (1987) 269.
16. P.A. Rey. M.J. Engler and F.F. Apian, Fluid/Particle Separation Jol. 1(2) (1988) 124.
17. M.J. Engler. R. Hogg and F.F. Apian, paper E3 in Proc. Fifth Australian Coal
Preparation Congress, Newcastle. NSW. P.J. Lean, ed., Aust. Coal Prep. Soc,
Newcastle, NSW (1991) 181.
18. T. Onlin, M.S. Thesis, Penn State University. Thesis supervised by F.F. Apian (1984).
19. A.S. Michaels and O. Morelos. lEChem, 47 (1955) 1803.
20. R. Hogg, Process Design for Flocculation. Clarification and Thickening of Fine Particle
Suspensions, XVIII Int'l. Min. Proc. Cong., Sydney, NSW (1993), in press.
D e p r e s s i o n of Pyrite Flotation b y M i e r o o r g a n i s m s as a F u n c t i o n of p H
S. K. Kawatra and T. C. Eisele

Department of Metallurgical and Materials Engineering, Michigan Technological University
1400 Townsend Drive, Houghton, MI, 49931-1295 U.S.A.
ABSTRACT
It has been reported in the literature that microorganisms, particularly the bacteria Thiobacillus
ferrooxidans, can depress the flotation of pyrite particles during coal flotation. The study reported
in this paper was conducted to answer two questions that have not been adequately addressed in
the literature: 1. How much ability do the bacteria have to depress pyrite flotation in a normal
high-sulfur bituminous coal, under flotation conditions that are commonly used industrially; and
2. What is the effect of pH on the depression of coal-pyrite and mineral-pyrite flotation by
microorganisms. Results are given which show that, for a randomly-selected coal sample under
normal coal flotation conditions, and particularly at near-neutral or alkaline pH, pyrite depression
by microorganisms was of no signicant benet.
1. INTRODUCTION
When fine coal is cleaned by froth flotation, a large proportion of the inorganic sulfur is carried
into the froth product along with the clean coal [1,2]. This inorganic sulfur, which is mainly pyrite
particles a few micrometers in diameter, then causes a severe sulfur emissions problem when the
coal is burned. There has therefore been considerable interest in developing methods for
depressing the flotation of these fine pyrite particles [3,4]. However, while a number of potential
pyrite-depressing chemicals have been studied, none are being used in full-scale coal-cleaning
operations.
The main difficulty with chemical pyrite depressants in coal flotation has been that their
benefits are small to nonexistent in industrial-scale coal flotation operations [5]. Several
investigators have therefore turned to the study of microorganisms, particularly the bacteria
Thiobacillus ferrooxidans, as pyrite depressants [6-13]. The basis for this is that certain
microorganisms are reported to have a specific affinity for pyrite surfaces, and it is therefore
hoped that they can be made to attach to the pyrite in large numbers with a higher degree of
selectivity than is possible with chemical depressants. Once the pyrite surface is completely
covered by microorganisms, its recovery by froth flotation would then be depressed.
In this paper, the ability of two different microorganisms to depress pyrite flotation is
evaluated, using a high-sulfur bituminous coal, a carbon-free mineral pyrite, and a coal pyrite
under a range of pH conditions. The goal of this work was to determine the actual degree of pyrite
depression which could be expected from the bacteria in industrial coal flotation, and to
determine whether the effect varies significantly with changes in pH or with pyrite type.
140
2. T H E O R E T I C A L D I S C U S S I O N
The basic principle of froth flotation is the selective attachment of hydrophobic particles to
air bubbles. The bubbles then carry the attached particles to the surface for removal from the
process. In coal flotation, the coal is naturally hydrophobic and most of the associated
minerals are not, and so the clean coal is recovered from the froth product while the mineral
matter remains suspended in the flotation vessel.
There are three ways in which a pyrite particle can reach the froth product in coal flotation:
true flotation, entrainment, and locking (or "induced floatability") [14]. For true flotation to
occur, the pyrite surfaces must become hydrophobic, so that they can attach directly to the air
bubbles in the same manner as the coal. Entrainment occurs when small particles are
suspended in the water making up the bubble films, and are not actually attached to the
bubbles. Locking of pyrite particles to floatable coal particles will allow even large pyrite
particles to be carried into the froth when the coal they are attached to floats.
Of the three mechanisms of pyrite flotation, only the true flotation can be significantly
affected by chemical depressants, which work by altering the pyrite surface chemistry to make
it less hydrophobic. Both entrainment and locking are mechanical effects which have little to
do with the hydrophobicity of the particles involved. Entrainment can only be reduced by
reducing the amount of water carried into the froth or by increasing the settling rate of the
particles, and the effects of locking can only be reduced if the coal is either ground to a finer
size, or some coal recovery is sacrificed to avoid floating all of the locked particles [5,14].
The true flotation of pyrite from both synthetic coal/pyrite mixtures and high-sulfur coals
has been reported to be depressed by the bacterium Thiobacillus ferrooxidans [6-13]. This
organism has been extensively studied for its ability to dissolve pyrite by using it as a food
source. It was therefore originally investigated as a pyrite depressant because it has a
biological reason for having a specific affinity for pyrite surfaces. It is believed that this
bacteria specifically and selectively attaches to pyrite within a matter of minutes. Early work
[6] was carried out by conditioning coal/pyrite slurries with bacteria at a pH of 2, followed by
flotation over the pH range of 7-9. The rationale was that T. ferrooxidans would be most active
at a pH of 2, while it is well known that coal is most floatable at near-neutral pH [15]. Other
investigators have generally used a pH near 2 for both bacterial conditioning and for the
flotation step [7-13]. It has also been reported that organisms other than ferrooxidans are
effective pyrite depressants, as are a number of miscellaneous proteins, such as those found in
whey (a by-product of cheesemaking) [11,12].
The research described in this paper was intended to address the following points, which
have not been completely answered by the studies reported in the literature; 1. What is the
actual magnitude of the bacterial depression effect on the coal-pyrite in a particular high-sulfur
bituminous coal; and 2. What is the effect of pH on the depression of both coal-pyrite and
mineral-pyrite flotation by microorganisms? The answers to these questions will determine
whether microbial pyrite depression is a potentially useful industrial technique, or simply a
laboratory curiosity.
3. E X P E R I M E N T A L P R O C E D U R E
3.1 IVIaterials
Three materials were used in the froth flotation studies; a high-sulfur coal, a mineral-pyrite,
and a coal-pyrite. The coal was a bituminous coal from the Meigs Creek (or #9) seam,
141
collected from a mine in Ohio. This coal contained 18% ash, 4.8% total sulfur, and 2% pyritic
sulfur. After collection, the coal was stage-crushed to pass a 20 mesh screen, and stored in a
freezer at -20 C until it was used, to minimize oxidation. Immediately before use, the coal was
wet-ground in a laboratory rod mill at 37% solids, using distilled water with the pH raised to
12 with sodium hydroxide to kill any native bacteria in the coal. The coal was then filtered,
washed with 500 ml of distilled water, and filtered again. The final product was 97% passing
100 mesh (149 micrometers) and 7.75% passing 500 mesh (25 micrometers).
The mineral-pyrite was purchased from Wards Natural Science Establishment, and had.
been collected from a deposit in Custer, South Dakota. The pyrite was stage-ground and
screened to maximize the amount in the 150x200 mesh (105x74 micrometer) size fraction.
This size fraction was used in all experiments with this material, because it was fine enough to
be floatable but coarse enough to minimize entrainment effects. It was then stored at -20 C
until needed. The size fraction used consisted of 52% pyrite by weight, with the remainder
being calcium carbonate and silicates.
The coal-pyrite was hand-collected as coarse nodules from the jig refuse belt at the Empire
Coal Mine, Gnadenhutten, Ohio, which processes a mixture of bituminous coals from the
Lower Kittanning (#5), Middle Kittanning (#6), and Upper Freeport (#7) seams. The hand-
picked pyrite was then stage-ground, screened, and stored in the same manner as the mineral-
pyrite. The 150x200 mesh size fraction of the coal-pyrite contained 70% pyrite, with the
remainder being mainly coal and clay.
3.2. Organisms
Two species of microorganism were used; Thiohacillus ferrooxidans, and Saccharomyces
cerevisiae. The T. ferrooxidans was selected because it was the organism most commonly used
by other investigators, and because it is reported to have a specific affinity for pyrite surfaces.
The 5. cerevisiae was selected based on both its ready availability, and its high effectiveness as
a pyrite depressant in preliminary screening experiments [16]
The Thiohacillus ferrooxidans culture was originally obtained from EG&G Idaho (culture
DSM-83) and was grown in a nutrient medium with the following composition [17]:
Ammonium Sulfate, (NH4)2S04 0.4 grams

Potassium Phosphate, K2HPO4 0.4 grams
Magnesium Sulfate, MgS04-7H20 0.4 grams
Ferrous Sulfate, FeS04-7H20 33.3 grams
Distilled, Sterilized Water 1000 ml
Sulfuric Acid, H2SO4 To pH=2.0
The bacteria were cultured in this medium using an orbital flask shaker at 200 RPM and a
temperature of 30 C for approximately one week. The cell density of the culture used for coal
flotation tests was 2.5x10^ cells/ml, and the culture used for pyrite flotation tests was 3.4x10^
cells/ml, as determined with a Petroff-Hauser cell-counting chamber.
The Saccharomyces cerevisiae used was a commercially available active dry yeast, which
contained no additives [18]. Dosages of S. cerevisiae in flotation experiments were determined
by weighing the dry yeast with a standard 4-place analytical balance.
142
3.3. Coal Flotation Procedure

The coal was first divided into charges of 350 grams each, which were then individually
wet-ground, and filtered. Each charge was then added to a pachuca-tank reactor with a working
volume of 1.25 liters, and suspended to 26% solids at a pH of 2.0. These pachuca tanks had
been successfully used earlier for bacterial leaching experiments with the same coal prepared
in the same manner [16,19]. Two of the tanks were then inoculated with 100 ml of the T.
ferrooxidans culture, giving a bacteria concentration in the tanks of 7.1x10^ cells per gram of
coal. The remaining tank was reserved as a bacteria-free control. The pachuca tanks were then
used to agitate the coal/bacteria mixture for periods of 2 and 23 hours, with the control agitated
for 2 hours.
After the conditioning period for each tank was completed, its contents were filtered, and
the solids divided into three 100-gram flotation charges and one 50-gram head sample. Each
flotation charge was suspended in a Denver flotation machine with 1.9 liters of tap water (5%
solids) and conditioned for 3 minutes with MIBC as frother (0.3 kg/mt for all tests) and #2 fuel
oil as collector. Based on preliminary flotation tests, the collector dosages (0.22, 0.43, and 0.86
kg/mt) were selected to be just sufficient to recover the bulk of the coal, which is consistent
with normal industrial practice. Flotation was carried out at natural pH for the resuspended
coal, which was between 5.5 and 6.0 for each test.
3.4. IVlineral-pyrite and Coal-pyrite Flotation Procedure
Each test used 150 grams of pyrite sized to 150x200 mesh. This size fraction was selected
so that the pyrite would be fine enough to be flotatable by true flotation, but coarse enough to
minimize the effects of entrainment. Each charge was suspended in 1.9 liters of distilled water
(7.3% solids) in a Denver flotation machine, and treated as follows:
1. The pH was adjusted as desired with either sulfuric acid or sodium hydroxide solution,
and conditioned until the pH stabilized (about 5 minutes).
2. The desired microorganisms were added, and conditioned for 10 minutes.
3. The collector (#2 fuel oil, 3.0 kg/mt) was added, and conditioned for 2 minutes. A large
dosage of collector was used to ensure that all particles that were even slightly
hydrophobic would float.
4. The frother (MIBC, 0.2 kg/mt) was added, and conditioned for 30 seconds.
5. The pyrite was floated for 5 minutes, scraping the froth from the flotation cell by hand.
3.5. Analyses and Calculations
All flotation products were dried at 75 C, and weighed to the nearest 0.1 gram. The sulfur
content of the coal samples was determined using a LECO SC-132 sulfur determinator Ash
contents of the coal samples were determined using ASTM Standard Method D3174-82, and
the pyrite content of the coal was determined using ASTM Standard Method D2492-84[20].
Because of the very high pyrite levels in the mineral-pyrite and coal-pyrite samples, a
simplified procedure for measuring the pyrite content could be used. For each sample, two
portions of 1 gram each were weighed out. The first portion was leached by adding 50 ml of
4.8 hydrochloric acid solution, and boiling gently for 30 minutes. The second portion was
leached by adding 75 ml of 1.0 nitric acid solution, and boiling gently for 30 minutes. The
residues from each leach were then filtered, dried, and weighed to determine the percentage
weight loss. Since pyrite does not dissolve in hydrochloric acid, but dissolves completely in
nitric acid [21], the pyrite content of the sample is taken to be:
143
%Pyrite = (%wt. loss in HN03) - (%wt. loss in HCl)
Total weight % recovery (or yield) reporting to the clean coal product is calculated as:
^ Froth Wt.
Recovery,%Wt. = ^ ^ x 100
' Feed Wt.
Removals of ash and pyrite are calculated as:
(%Wt. in Feed Feed Wt.) - (%Wt. in Froth Froth Wt.)
^^^^^""^^ = (%Wt.inFeedxFeedWt.) ^
4. RESULTS AND DISCUSSION

4.1. Coal Flotation.
Table 1. Flotation results for the Meigs Creek coal after conditioning with T. ferrooxidans for
various times in pachuca tanks at a pH of 2. Flotation pH was between 5.5 and 6., and the coal
contained 18% ash, 4.8% total sulfur, 2.0% pyritic sulfur, and 2.8% organic sulfur. No
detectable amount of sulfur was dissolved by the bacteria in the course of the test. The
"control" tests used no bacteria, but were otherwise run identically to the 2-hour contact time
tests. While the increase in pyritic sulfur removal after 23 hours is large at the lowest collector
dosage, the loss of coal recovery due to reduced floatability is equally large. Increasing
collector dosage improves the recovery, but reduces the pyritic sulfur removal. The froth
%pyritic sulfur is only reduced by 0.1% sulfur by the bacteria after 23 hours, which is a barely
detectable improvement.
% Weight
Contact Collector Froth % Ash Froth % Pyritic S
Recovery
time (hours) (kg/mt) % Ash Removal % Pyritic S Removal
(Yield)
2 (control) 0.22 72.8 9.8 60.4 1.5 45.4

0.43 78.8 10.0 56.2 1.4 44.8
0.86 86.9 10.9 47.4 1.5 34.8
2 0.22 75.8 9.8 58.7 1.5 43.2
0.43 83.6 10.2 52.6 1.5 37.3
0.86 87.8 11.0 46.3 1.6 29.8
23 0.22 56.8 9.2 71.0 1.6 54.6
0.43 76.4 9.4 60.1 1.4 46.5
0.86 85.5 9.7 53.9 1.4 40.1
The coal flotation results given in Table 1 do not show any large systematic improvement in
sulfur rejection that can be attributed to the bacteria, even after 23 hours of contact with the
bacteria. At low collector dosage, the improvement in pyritic sulfur removal is due to the
decrease in the total % weight recovery which results from oxidation of the coal surfaces,
reducing its floatability. This is supported by the fact that the % pyritic sulfur content of the 23
hour froth is not lower than that of the control. Also, at all collector dosages the ash removal is
affected to the same degree as the pyritic sulfur removal, even though the bacteria are not
144
100 ' I ' I ^

o no microorganisms
80 h S. cerevisciae, 13.3 kg/mt
I 60 h
S. cerevisciae, 3.3 kg/mt
O T . ferrooxidans, -3.3 kg/mt
| . ferrooxidans, -1.1 kg/mt

^ 40 h a S . cerevisciae, 6.6 kg/mt
20 h
0 1
0 2 4 6 8 10 12 14
Flotation pH
Figure 1. Flotation of 150 200 mesh mineral-pyrite over a wide pH range, with varying
dosages of both Thiobacillus ferrooxidans and Saccharomyces cerevisiae. The ferrooxidans
dosage was estimated from cell counts, and is only approximate. A large dosage of
microorganisms is required to depress flotation at a pH of 2. At higher pH, the floatability of
this pyrite is lost and little effect is seen from microorganisms.
expected to have any specific affinity for the clay minerals that make up the bulk of the ash in
this coal. At higher collector dosages, the amount of pyrite in the froth product decreases
slightly with the 23 hour bacterial contacting, but no such effect is seen for the 2 hour contact
period. These results show that, even with extreme amounts of contact time allowed, the
Thiobacillus ferrooxidans produces only a minor improvement in flotation performance for
this coal.
4.2. Mineral-pyrite Flotation.
In the results shown in Figure 1, it is seen that the mineral-pyrite is very floatable under
acidic conditions, but that its floatability becomes negligible at neutral and alkaline pH. This
effect is believed to be due to the changes in solubility of iron hydroxides on the pyrite surface
as the pH changes. These hydroxides form as a result of partial oxidation of the pyrite, which
appears to occur almost immediately and make the pyrite surface hydrophilic and prevent its
flotation [1]. Under acid conditions, this coating dissolves, leaving a hydrophobic pyrite
surface [5].
The froth product at a pH of 2 contains virtually all of the pyrite, with the non-floating cell
product being silicates and carbonates with less than 1% pyrite remaining. Since coal flotation
is normally carried out at near-neutral pH, pyrite with surface chemistry similar to mineral-
pyrite will not be a problem in coal flotation because it will only float in acid solution. At a pH
of 2, the ferrooxidans was only able to slightly reduce the pyrite floatability, but the
effectiveness of the S. cerevisiae was much greater, mainly because it could be added in much
higher quantities. However, to achieve complete pyrite depression at a pH of 2, it was
necessary to add 6.6 kg of S. cerevisiae per metric ton of pyrite, a level that is likely to cause
145
100 ' 1 ' 1 ' 1

% weight recovery, no yeast
O % pyrite recovery, no yeast

% weight recovery, with yeast, 13.3 kg/mt
b ^ % pyrite recovery, with yeast, 13.3 kg/mt
0 -
, 1 , 1 , 1 . 1 , 1 , 1 ^ , '
0
0 2 4 6 8 10 12 14
Flotation pH
Figure 2. Flotation of 150 200 mesh Empire coal-pyrite, with and without added yeast
(Saccharomyces cerevisiae). The yeast produces a general depression of all components, and
is not selective towards pyrite, as is shown by the close similarity of the values for total weight
recovery and pyrite recovery.
problems such as excessive foaming in other parts of the coal processing circuit. At neutral pH,
the effect of S, cerevisiae was negligible, simply because there was no hydrophobic pyrite to be
depressed at this pH. Under alkaline conditions, the S. cerevisiae actually caused a slight
increase in the pyrite flotation, because the microorganism acts as a foaming agent under these
conditions. Because the T. ferrooxidans was largely ineffective at the acid pH where it was
expected to work best, it was not used in the neutral and alkaline pH flotation experiments
because it is much more difficult to grow and handle than the S. cerevisiae.
4.3. Coal-pyrite Flotation

The coal-pyrite was hand-collected as coarse nodules from the jig refuse belt at the Empire
Coal Mine, Gnadenhutten, Ohio. The behavior of the coal-pyrite was completely different
from the mineral-pyrite, as shown in Figure 2. First, the coal-pyrite was most floatable at near-
neutral pH, with over 60% of the total weight floating at a pH of 6 in the absence of
microorganisms, but less than 25% floating at either a pH of 2 or a pH of 12. This behavior is
very similar to that reported for coal [15], but very unlike that seen for the mineral-pyrite.
Second, there was no pH where the pyrite floated preferentially. The recovery of pyrite was
always very close to the total weight recovery, which shows that the pyrite particles were being
recovered at the same rate as the coal particles. When S. cerevisiae was added to the coal-
pyrite, it did depress the pyrite recovery. However, it also depressed the total weight recovery
to the same degree, showing that it was a general flotation depressant, and not a highly
selective one. The behavior of the coal-pyrite is consistent with the pyrite floating because the
particles have surfaces which are at least partially made up of hydrophobic coal, and not
146
because the pyrite itself is hydrophobic. If the actual pyrite surfaces were contributing to the
hydrophobicity, then the flotation of pyrite should have been considerably enhanced at a pH of
2, as was seen for the mineral pyrite.
5. CONCLUSIONS
Both Saccharomyces cerevisiae and Thiobacillus ferrooxidans can depress the flotation of
mineral-pyrite at acidic pH, but only at high dosage levels. However, ferrooxidans has not
been found to have any benecial effect on the sulfur rejection during flotation of a Meigs
Creek Seam bituminous coal at near-neutral pH, even with very long bacterial pretreatment
times at low pH. S. cerevisiae does depress coal-pyrite flotation at neutral pH, but the
depression is unselective between pyrite and coal particles and therefore unlikely to be
industrially useful.
6. ACKNOWLEDGEMENTS
Support for this research was provided by the State of Michigan Research Excellence Fund,
Consumers Power Co., Detroit Edison Co., and the Ohio Coal Development Office. The
Thiobacillus ferrooxidans culture was kindly provided by Dr D. R. Lucking of the MTU
Department of Biology. The authors would also like to thank Ms. J. F. Bird and Dr. Howard
Johnson of the Ohio Coal Development Ofce, and Dr. R. R. Klimpel of the Dow Chemical
Co., for their useful suggestions and critical discussion of this project.
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6. M. Elzeky and Y. A. Attia, Coal Preparation, 5 (1987) pp 15-37.
7. A. S. Atkins, E. W. Bridgewood, A. J. Davis, and F D. Pooley Coal Preparation, 5 (1987)
pp. 1-13.
8. N. Ohmura, K. Kitamura, and H. Saiki, Biotechnology and Bioengineering, 14 (1993) pp.
671-76.
9. C. C. Townsley and A. S. Atkins, Process Biochemistry 21(6) (1986) pp. 188-91.
10. C. C. Townsley, A. S. Atkins, and A. J. Davis, Biotechnology and Bioengineering, 30
(1987) p. 108.
11 A. C. Stainthoe, Biotechnology and Bioengineering, 33 (1989) pp. 694-98.
147
12. . S. Atkins, Bioprocessing and Biotreatment of Coal (ed. D. L. Wise) Marcel Dekker,
NY, 1990, pp. 507-548.
13. C. E. Capes, A. E. Mcllhinney, A. F. Sirianni, and I. E. Puddington, CIM Bulletin,
November 1973, pp. 88-91.
14. A. J. Lynch, N. W. Johnson, E. V. Manlapig, and C. G. Thorne, Mineral and Coal
Flotation Circuits: Their Simulation and Control, Elsevier, Amsterdam, 1981.
15. R. E. Zimmerman, Coal Preparation (J. W. Leonard, ed.), AIME, New York, 1979,
Chapter 10 part 3.
16. T. C. Eisele, Unpublished Results, 1992.
17. O. H. Tuovinen and D. R Kelly, Arch. Mikrobiol., 88 (1973) pp. 285-298.
18. Red Star, Inc., Personal Communication, February, 1992.
19. S. K. Kawatra, T. C. Eisele, and S. Bagley, Mineral and Metallurgical Processing, 4(4)
(1987) pp.189-192.
20. ASTM, Annual Book of ASTM Standards, Vol. 5.05, standards D2492-84 and D3174-
82, 1988.
21. C. S. Hurlbut and C. Klein, Manual of Mineralogy, 19th edition, John Wiley & Sons,
N.Y., 1977.
Processing preparation plant effluent using a packed column
V. Choudhry8, L. Khan b, D. Yang C , and D.O. Banerjeed
8Praxis Engineers, Inc.,

852 N. Hillview Drive, Milpitas, California 95035, United States of America
billinois State Geological Survey

615 E. Peabody, Champaign, Illinois 61820, United States of America
CMineral Technologies International, Inc.

One Volin Place, Houghton, Michigan 49931, United States of America
dillinois Clean Coal Institute

P.O. Box 8, Carterville, Illinois 62918, United States of America
ABSTRACT
This paper presents the results of testing conducted to demonstrate the feasibility
of using a packed column to recover clean coal from coal preparation plant waste
(effluent) streams. The research program was funded by the Illinois Clean Coal
Institute. In Phase I, effluent samples from four Illinois preparation plants containing
between 50 and 60% ash were tested using a laboratory-scale column. Typically, clean
coal containing 7-11 % ash was recovered at Btu recoveries of 91-98% and pyritic sulfur
rejection levels of 61-74%.
In Phase II, a new sample collected from one of the plants was characterized prior
to running bench-scale confirmatory tests at Michigan Technological University using
a 4-in. 1.0. x 10-ft tall column. The effluent sample, which contained 50-54% ash, was
processed to recover clean coal containing 5-10% ash. A 4-in. 1.0. x 20-ft tall column
and other equipment were installed at the Illinois State Geological Survey's Applied
Laboratory for pilot-scale testing. Extensive tests were conducted to study the effects
of primary variables (feed rate, percent solids, and reagent dosage) and operating
variables (air rate, wash water, and pulp level) with the objective of optimizing the
packed column performance using feed rates ranging from 20 to 108 Ib/hour.
Typically, clean coal products containing 7-10% ash were obtained at 40% yield for
column feed rates of 32.6-40.8 Ib/hour. The best results were obtained at a feed rate
of 35.5 Ib/hour (407 Ib/h/tf), with a clean coal product containing 5.3% ash and
2.52% total sulfur at 32.8% yield. The pyritic sulfur rejection level for this test was 87%
at 87% Btu recovery.
150
1. INTRODUCTION AND BACKGROUND
Coal preparation plants, especially those treating slow-floating Illinois-basin coals,

generate large quantities of effluent wastes which contain considerable amounts of
recoverable fine coal. The majority of coal cleaning plants in Illinois dispose of the
minus 100-mesh (150-micron) coal in ponds that occupy thousands of acres of land.
It is estimated that these fines could be processed to recover 4-6 million tons of clean
coal in Illinois alone (1). Due to their high pyritic sulfur content, these ponded
effluents pose considerable environmental problems which may require costly
remediation in the future. In addition, about 120 abandoned coal slurry pond sites
have been identified in Illinois which will eventually need to be reclaimed. The problem
has been compounded by an increase in underground mining which produces more
coal fines than does open-pit mining.
The major technical and economic reasons for discarding coal fines instead of
cleaning them by conventional flotation are (i) the slimes coating on the coal due to the
presence of clays, (ii) the difficulty of rejecting fine pyrite, and (iii) the high dosages of
oil required for slow-floating coals (2) (3). As a result, processing the coal fines
Is more expensive than the incremental cost of mining additional coal to make up for
their loss.
The need to recover coal from preparation plant refuse and effluents has been
addressed previously (4). Processing of impounded wastes to recover coal has
been demonstrated earlier using conventional and column flotation (5). Another
study based on a number of effluent samples from Kentucky and Virginia preparation
plants showed that a flotation column could be used effectively for this application
(S).
Because of their high moisture content, the fine coal concentrates recovered from
preparation plant effluents by flotation generally require dewatering. The cost incurred
during dewatering of these products is justified by the additional revenue they
generate. Dewatering tests carried out during the present work achieved filter cake
moistures of 23%. As such, two options for the utilization of recovered plant effluents
are envisioned: (i) as dewatered fine coal for blending with plant clean coal streams,
and (ii) as a slurry feed for coal gasification.
Due to a number of design advantages over conventional subaeration flotation,
conventional or open columns have found increasing acceptance in mineral
beneficiation (7) (8) and fine coal cleaning (9). The concept of using packing
in a column offers additional advantages such as (i) constantly breaking bubbles into
fine sizes, thus eliminating the need for a bubble generator, (ii) allowing repeated
bubble-particle interaction, (iii) preventing vertical mixing in the column, and (iv)
providing extensive froth support (10).
The packed-bed flotation system has been recognized by the U.S. Department of
Energy as the leading technology based on the results of interlaboratory comparison
tests to evaluate the performance of advanced physical froth flotation processes for
fine coal cleaning (see ref. 10). The design features and applicability of the process
to sulfide flotation and to the processing of gold, iron, fluorspar, and coal are
summarized by Yang ( H ) .
This paper presents the results of work completed under a research grant from the
Illinois Clean Coal Institute to recover coal from preparation plant effluents using a
packed column, also known as Michigan Technological University's (MTU) Static Tube
process.
151
2. RESEARCH OBJECTIVES
The primary objective of this research was to recover a low-ash, low-sulfur coal
from preparation plant effluents using a packed column. Other objectives were to
study (i) the ash and pyritic sulfur rejection levels achieved at a high combustible
matter recovery, (ii) the effect of process variables (feed rate, pulp density, and reagent
dosage), and (iii) the effect of machine variables (pulp level in column, air and wash
water rate) on packed column performance.
In Phase I, samples from four coal preparation plants (A through D) were collected
for bench-scale testing. Characterization of all as-received samples included particle
size analysis, proximate and ultimate analysis, and washability analysis of the +230-
mesh (62-micron) fraction of the total effluent sample. The minus 230-mesh material,
which typically has a high ash content, was discarded prior to sink-float centrifuging
since it is deleterious to a good separation. Since the effluent samples contained a
considerable amount of coarse material, they were comminuted to nearly 80% passing
200 mesh to allow comparison of the four samples on a uniform basis prior to flotation
in a 2-inch I.D. 8-ft tall packed column.
In Phase II, a new effluent sample consisting of plant tailings slurry at approximately
3% solids was collected from the plant which supplied Sample during Phase I bench-
scale testing and thickened (without flocculants) to approximately 25% solids. To
ensure that this sample was representative, a large number of increments were
collected over three weeks of plant operation. Prior to conducting pilot-scale tests,
confirmatory bench-scale tests were run using the new sample in a 4-inch I.D 10-ft
tall packed column at MTU.
A 4-inch I.D. 20-ft tall packed column, obtained from the manufacturers, GL&V
Ontario (formerly Dorr-Oliver of Canada), was installed along with other equipment at
the Illinois State Geological Survey (ISGS) Applied Laboratory facility in Champaign,
Illinois. A schematic of the pilot plant is shown in Figure 1.
The pilot plant included a mixing tank (not shown), in which the desired solids
concentration was achieved for each drum of slurry prior to transfer to the feed tank.
From the continually mixed and recirculating feed tank, slurry was delivered to an
agitated conditioning tank. The desired quantity of reagent was added to the
conditioning tank feed line based on the flowmeter readings. The conditioned slurry
was then gravity-fed to the flotation column. The flow rate and total slurry volume
pumped to the conditioning tank were monitored by a flowmeter in the delivery line.
The froth wash water, bottom water, and aeration rates were also measured by
flowmeters. The tailings discharge is typically controlled by a back pressure valve at
the bottom of the column. However, during pilot-scale testing, the pulp level and, as
a result, the depth of froth in the column were controlled by moving the tailings line up
or down. Also, bottom water was added to avoid sanding in the U-tube tailings line.
During pilot-scale testing, 3-minute full-stream clean coal product and tailings
samples were taken simultaneously. Full-stream sampling allowed determination of a
reconstituted feed rate for comparison with the column feed rate as measured by the
flowmeter. Periodically, samples taken from the feed slurry recirculating line were
dewatered, dried, weighed, and analyzed for ash, sulfur, and Btu content. Both the
152
COND I I ON I NG
TANK REAGENT
TANK
d o
DRAIN
i-D
CLEAN
COAL
PULP
LEVEL
CONTROL
TAILS
DRAIN
FLOW METERS
O
M) - )
LINE AIR LINE WATER
Figure 1. Schematic diagram of pilot plant.
primary and routine repeat analyses of these feed, product, and tailings samples were
performed at the ISGS laboratory using ASTM procedures.
Reconstituted feed ash, total sulfur, and pyritic sulfur values were calculated using
the product and tailings analyses for each test. Based on these values, the percent
ash rejection, pyritic sulfur rejection, and Btu recovery levels were calculated. The
following criteria were used to evaluate the performance of various tests:
(i) Selectivity index = %Btu recovery + % pyritic sulfur rejection - 100
(ii) Efficiency index = % yield % tailings ash % product ash
The selectivity index (SI) is useful in evaluating tests for pyritic sulfur rejection
performance, and the efficiency index (El) is useful in evaluating tests where percent
ash rejection and yield are the primary considerations.
153
4.1 Phase I Sample Characterization

T a b l e 1 p r e s e n t s t h e a s h a n d sulfur a n a l y s e s of t h e four s a m p l e s u s e d d u r i n g the
Phase I bench-scale w o r k performed at M T U . T h e a s h content of t h e four samples
r a n g e d f r o m 5 0 t o 6 0 % , w h i c h is t y p i c a l o f c o a l p r e p a r a t i o n p l a n t e f f l u e n t s . However,
e a c h s a m p l e w a s u n i q u e in t e r m s of p a r t i c l e s i z e d i s t r i b u t i o n , in p a r t i c u l a r , t h e quantity
of slimes ( m i n u s 2 3 0 mesh). For e x a m p l e , the slimes content of S a m p l e s A and C
were about 35-40%, whereas Samples and D contained over 7 9 % minus 230-mesh
fines by weight.
Table 1
Analvsis of material w e t - s c r e e n e d o n a 2 3 0 - m e s h U S standard screen
gample A Sample Sample C Sample D

f230M 230M Total +230M -230M Total +230M -230M Total +230M-230M Total
W t % 60.5 39.5100.0 26.8 73.2 100.0 65.3 34.7 100.0 28.2 71.8 100.0
Ash% 39.2 65.5 49.6 18.1 67.4 54.2 37.0 58.0 44.3 29.3 73.2 60.8
T S % 2.56 0.64 1.80 3.74 1.91 2.40 5.63 1.79 4.30 5.64 1.96 3.00
P S % 2.17 0.61 1.56 1.86 1.31 1.46 4.24 1.12 3.16 4.17 1.57 2.30
Btu/lb 7,973 4,516 6,607 11,080 3,974 5,878 8,311 5,376 7,293 9,326 3,245 4,960
T h e particle size distributions of S a m p l e s a n d D w e r e identical with approximately

50% passing 12 microns, while S a m p l e s A and C were 5 0 % passing 100 and 500
microns, respectively. Since S a m p l e C contained about 5 1 % material coarser than 30
m e s h , w h i c h is t o o c o a r s e f o r f l o t a t i o n , all o f t h e s a m p l e s w e r e g r o u n d t o 8 5 % passing
2 0 0 m e s h p r i o r t o P h a s e I b e n c h - s c a l e c o l u m n f l o t a t i o n t e s t i n g in o r d e r t o m a i n t a i n an
i d e n t i c a l f e e d p a r t i c l e s i z e f o r all t e s t s .
4.2 Phase I Bench-Scale Packed Column Flotation Tests

The results of b e n c h - s c a l e tests o n effluent samples A through D are given in
T a b l e 2. T h e s e d a t a indicate that t h e a s h c o n t e n t of t h e c l e a n coal p r o d u c t s recovered
f r o m different plant effluents varied b e t w e e n 5 a n d 1 4 % , a n d t h e sulfur c o n t e n t varied
b e t w e e n 1.0 a n d 3 . 3 7 % . T h e results also indicate that that a l t h o u g h t h e quality of t h e
c o a l r e c o v e r e d f r o m e a c h e f f l u e n t is u n i q u e , all o f t h e s a m p l e s a c h i e v e d p y r i t i c s u l f u r
rejections of 6 5 - 7 5 % at Btu recoveries greater t h a n 9 0 % . Grinding of t h e s a m p l e s may
h a v e c o n t r i b u t e d t o t h e high yields. In c o n v e n t i o n a l o n e - s t a g e flotation tests conducted
for c o m p a r a t i v e p u r p o s e s using t h e s a m e s a m p l e s , t h e p r o d u c t a s h a n d sulfur v a l u e s
a c h i e v e d w e r e inferior t o t h o s e o b t a i n e d u s i n g t h e p a c k e d column.
154
Table 2
Comparison of packed column process performance with subaeration flotation
Sample Procedure Product Analvsis Performance
%PS %Btu Sel Eff
Yleld% Ash% TotS% PS% Rel Ree Ind Ind
A-4 Packed column 57.0 6.5 1.13 0.50 74.1 99.6 73.7 800
A-6 Packed column 60.1 9.5 1.00 0.46 74.0 99.8 74.2 591
A-9 Froth flotation - 12.7 3.10 - - 92.5* - -
B-4 Packed column 48.3 8.5 3.15 1.2 67.6 91.2 58.8 505
B-6 Packed column 49.4 8.9 3.34 1.36 65.5 94.5 60.0 502
6-9 Froth flotation - 19.9 3.16 - - 86.3* - -
C-1 Packed column 43.7 4.4 2.86 0.91 76.4 88.8 65.2 883
C-2 Packed column 49.0 5.2 3.03 0.99 70.7 91.0 61.7 848
C-9 Froth flotation - 13.1 2.78 - - 85.8* - -
D-4 Packed column 39.9 11.0 3.32 1.46 74.4 94.0 68.4 332
D-5 Packed column 41.9 13.8 3.37 1.60 71.2 97.2 68.4 279
D-9 Froth flotation - 19.9 2.84 - - 85.3* - -
* Combustible matter recovery reported for frothflotationtests.
4.3 Phase II Sample Characterization

Of the 24 drums of sample obtained for Phase II testing from Plant B, the drum
used for bench-scale confirmatory testing contained 53.4% ash and 2.34% total sulfur.
The remaining drums of effluent sample used for pilot-scale testing had reconstituted
feed values of 50-57% ash and 2-2.7% total sulfur. The reason for this variation in feed
analysis is attributed to the changing mix of raw coal feed to the coal preparation plant,
which is typical of plant operation in the area.
4.4 Phase II Confirmatory Bench-Scale Tests

Prior to conducting the pilot tests, a batch of confirmatory tests was completed at
MTU using a 4-inch I.D. 10-ft tall column with the new sample collected from Plant B.
These tests were run using various feed rates, feed solids concentrations, and reagent
dosages while varying the machine operating parameters. The following conclusions
were drawn from these confirmatory bench-scale tests:
(a) Clean coal containing 6-8% ash can be recovered at a combustible

matter recovery of 71-77%.
(b) The best bench-scale results were obtained at reagent dosages of 6-12
Ib/T using a pine oil/fuel oil blend in the ratio 1:1.
(c) Feed solids concentrations of 10-20% yielded product ash values of 6.5-
7.5% at combustible matter recoveries of 74-77%.
155
4.5 Phase II Pilot-Scale Column Flotation Tests

A total of 79 tests were run in nine separate batches during the pilot test program
carried out at the ISGS Applied Laboratory facility. In the first three batch runs, a
cubical test design was used for initial screening. For the next two sets, an orthogonal
test design was used.
In one set of tests, incremental clean coal and tailings samples were collected to
establish the minimum time needed to achieve steady state, which was estimated at
15-20 minutes for machine variables such as the air rate, pulp level, and froth sprinkling
water. For the major process variables such as the feed rate, reagent dosage, and
pulp density, steady state was achieved after 60-75 minutes of column operation (4-5
times the longest anticipated residence time). This established the minimum operating
time before product samples could be taken.
The process and machine variables were changed over the following ranges to
achieve optimal conditions:
Process variables:
Feed rate: 20.8 to 107.6 Ib/h
Pulp density: 5 to 20% solids
Reagents: 3 to 26 Ib/T
Machine variables:
Pulp level adjuster position from feed inlet -100 to +50 cm
Wash water: 0 to 1.6 l/min
Air rate: 17.5 to 56.6 l/min
The range of reagent dosages tested was higher than anticipated due to an error
during calibration of the reagent feed pump. The results of the two best tests from
each batch are reported in Table 3 and the major findings are discussed below.
Pyritic Sulfur and Ash Rejection. Figure 2 shows the pyritic sulfur rejection (PSR)
and Btu recovery for the test runs. It indicates that high pyrite rejection levels of about
85-90% can be achieved at 75-80% Btu recovery. The best results, obtained at 5 and
12.5% solids, achieved 80% Btu recovery at 90% PSR. Figure 3 shows the product
ash content and Btu recovery under various test conditions. As expected, the product
ash content increased with increasing Btu recovery. A clean coal product containing
less than 7% ash was recovered at Btu recoveries of greater than 85%.
Effect of Pulp Density. Pilot testing was performed using a wide range of feed
slurry solids concentrations since 5% solids is typical of plant effluents and 20% solids
is representative of thickener underflow or reclaimed pond fines. In addition, since
flocculants used to thicken the underflow generally interifere with flotation performance,
selection of the appropriate flocculant is important. Figure 2 indicates that high pyrite
rejection can be achieved at high Btu recoveries with both 5 and 12.5% feed solids
concentrations. At a 20% feed solids content, however, pyrite rejection was lower.
Similar conclusions can be drawn from Figure 3 which indicates that at 5 and 12.5%
feed solids concentration, a clean coal ash content of less than 10% was achievable
at 85-90% Btu recovery. The test runs using a 20% slurry solids concentration also
yielded a low-ash product but at significantly lower Btu recoveries than were achieved
at lower solids concentrations. This decrease in performance is perhaps due to the
limited wash water used in these tests. It was concluded based on the available data
156
that under the conditions tested, low and intermediate slurry solids concentrations
achieve better separations.
Table 3
Two best test results from each batch based on efficiencv index (sample B)
Batch Feed (Calculated) Product Analvsis Performanpe
Test Ib/h Ash TS Yield Ash TS PS% PSR Btu SI El

% % % % % % Ree %
1.2 35.5 58.8 2.10 32.8 5.3 2.52 0.37 87.2 87.6 74.8 532
1.7 35.5 60.0 2.08 34.1 8.9 2.75 0.66 76.0 90.4 66.4 333
2.1 32.6 54.7 2.42 34.9 6.7 2.68 0.55 83.6 81.1 64.7 417
2.2 32.6 55.8 2.29 37.4 6.8 2.70 0.57 80.0 89.7 69.7 473
3.5 20.8 52.1 2.51 37.7 8.8 2.65 0.56 82.6 79.7 62.3 336
3.10 20.8 52.4 2.67 39.6 13.9 3.18 1.19 66.2 79.0 65.2 221
4.1 53.8 46.7 2.74 21.8 7.6 2.41 0.30 95.2 41.0 36.2 165
4.5 53.8 53.2 2.54 21.7 15.5 2.36 0.40 93.2 43.3 36.5 89
5.10 32.6 50.2 2.60 41.6 8.7 2.72 0.63 79.4 83.8 63.2 381
5.11 32.6 52.3 2.36 39.4 7.5 2.66 0.55 80.0 85.1 65.1 428
7.3 32.6 55.1 2.36 42.4 12.9 2.64 0.63 76.4 92.1 68.5 283
7.7 32.6 54.5 2.27 41.8 7.8 2.71 0.60 75.4 95.4 70.8 473
8.3 23.6 62.8 2.07 32.3 7.6 2.66 0.55 81.9 95.4 77.3 379
8.10 40.8 57.4 2.04 39.3 8.7 2.79 0.70 67.6 96.2 63.8 401
9.2 32.6 53.8 2.38 33.3 14.7 2.61 0.63 81.3 68.4 49.7 166
9.3 32.6 58.1 2.20 31.0 20.0 2.52 0.64 80.6 67.1 47.7 117
10.1 32.6 55.1 2.49 40.6 15.5 2.52 0.56 82.0 85.3 67.3 215
10.4 32.6 53.1 2.48 43.0 11.3 2.59 0.55 80.6 90.2 70.8 321
Effect of Reagent Dosage. A reagent consisting of a pine oil/fuel oil blend at a 1:1
ratio (established as a suitable combination during previous work) was used at three
dosages:
Low 3-10 Ib/T

Medium Between 10 and 20 Ib/T
High Over 20 Ib/T
Figure 3 shows the effects of reagent dosage on test performance at various solids
levels, and indicates that low to medium reagent dosages achieved better separations,
i.e., yielded a product with a lower ash content at comparable Btu recoveries. Reagent
dosages of 3 Ib/T resulted in products with 11-17% ash contents at Btu recoveries of
over 85%. These results were achieved using high pulp levels and significantly
increased cell aeration rates.
157
PERCENT PYRITE REJECTION PERCENT B t u RECOVERY
Sol d s Reagent
60
5% Low
50 5% High
12.5% Low
AO
o 12.5% High
30
X 12.5% Med i urn
Percent Sol i d s 20 20% High

5% +12.5% * 20%
8 12 16 20 24
4 28
PERCENT ASH IN PRODUCT
AO 50 60 70 80 90 100
PERCENT B t u RECOVERY Reagent Dosage in Ib/t

Low < 1 2 , Medium 12-26, High >26
Figure 2. Pyrite rejection versus Btu Figure 3. Btu recovery versus product
recovery. ash content.
Effect of Feed Rate. To study the impact of feed rate on performance, the column
was operated at feed rates ranging from 20.8 Ib/h (238 Ib/ft^/h) to 107.6 Ib/h (1233
Ib/ft^/h). A feed rate of 350-400 Ib/ft^/h is considered the typical area capacity of a
column for this application.
By definition, retention time is the mean residence time of all particles travelling with
the fluid from the inlet to the outlet of a machine or reaction vessel. For convenience,
an average retention time is usually calculated by dividing the vessel volume by the
volumetric flow rate of the feed slurry. The retention times for the tests presented in
this paper are in the range of 3-15 minutes. Since the packed column operates with
a very deep froth and the solids concentration of the feed slurry varies widely in these
tests, we elected to use the solid treatment rate through the column, i.e., Ib/h or
Ib/h/ft^, when comparing our test results with other published data obtained using
conventional column flotation.
In Test 1.2, using a feed rate of 35.5 Ib/h (407 Ib/h/ft^), a product containing 5.3%
ash and 2.52% sulfur was obtained at a PSR of 87.2% and a Btu recovery level of
87.6%. Good results were obtained in Batch 8 tests using a feed rate of 40.8 Ib/h
(468 Ib/h/ft^) which provided a 8.6% ash product at a clean coal yield of 39.7% and
Btu recovery of 96.0%. These tests indicate that the packed column can operate at
feed rates comparable to other columns and that the packing does not decrease the
cell throughput rate. In addition, in two tests run at the excessively high feed rate of
107.6 Ib/h (1233 Ib/h/ft^), the performance deteriorated significantly but did not result
in any plugging of the column.
Effect of Pulp Level. To study the effect of pulp level on performance, runs with
similar test conditions but varying pulp levels are plotted against the efficiency index
in Figure 4. These data indicate an optimum pulp level of 25 cm below the feed entry
158
point for the selected data pairs. A decrease in performance is observed at both lower
and higher pulp levels. The data pairs at the top left corner of Figure 4 used feed
slurry solids concentrations of 5% and 12.5% and low reagent dosages.
Effgpt Qf Air 9nd Wggh Wgter F I q w
EFFICIENCY INDEX Rate. Based on the test results, it was
500 concluded that an optimum air flow
rate of 25 to 30 l/min provided a high
450
degree of separation. Higher air flow
rates of 40-50 l/min resulted in
400
significant drops in the efficiency
350 h
index. The results also indicate that
the efficiency index increased with
300 h increasing wash water content.
As wash water is used in both
250 packed and non-packed columns, the
optimum reagent consumption is
200 h generally higher than that used in
conventional mechanically agitated
150 h flotation cells due to the wash water
dilution effect. The high air flow and
100
-75 -50 -25 25 50
feed used in these tests, while not
necessarily commercially acceptable,
PULP LEVEL, cm
were utilized to test the column under
extreme conditions.
5% 12.5% 20%
Figure 4. Effect of pulp level on efficiency

index.
5. CONCLUSIONS
This research program demonstrated that a packed column can be successfully

used to recover coal from preparation plant effluents. The specific conclusions drawn
from this work are given below.
Product ash levels of 7-10% were typically obtained at 80-85% Btu recovery
and 80% PSR using feed rates of 32.6-40.8 Ib/h (374-468 Ib/ft^/h).
The best product ash levels of less than 6% were consistently obtained at
33% yield and 80% Btu recovery at a feed rate of 35.5 Ib/h (407 Ib/ft^/h).
Tests were conducted at 5, 12.5, and 20% percent solids; the best
separation and high recoveries were obtained at 5 and 12.5% slurry solids
concentrations.
As the coal in the effluent samples is slow-floating, high reagent dosages

were required. The best results were obtained at 5-10 Ib/T reagent levels.
Lower reagent dosages (3 Ib/T) resulted in higher ash (11-17%) products.
While reagent levels greater than 12 Ib/T also resulted in higher product ash
content, no improvement in coal recovery was observed.
159
Improved performance was obtained with increasing wash water for the
range tested. The optimal pulp level was determined to be 25 cm below the
feed entry point. This is one of the special features of the packed column
involving mass transfer in a relatively deep froth where particle separation
takes place most effectively. The optimal air flow rate, between 25 and 35
l/min, was also identified.
Based on these tests, it was concluded that the optimal operating conditions of the
packed column for the coal samples tested are as follows:
Slurry solids concentration 5-12.5%

Reagent dosage (Sample B) 3-10 Ib/T
Feed rate 400-468 Ib/ft^/h
Wash water 0.6-1.2 l/min
Pulp level -25 cm from feed point (froth depth = 195 cm)
Air flow rate 25-35 l/min
The general conclusions from this research indicate that plant effluent streams,
which typically contain 55-60% ash and account for large quantities of coal commonly
lost to tailings ponds, may be processed to recover coal using a packed column. This
test program indicates that a 6-10% ash clean coal product can be recovered at high
Btu recoveries and pyritic sulfur rejection levels. The packed column was observed to
be capable of absorbing considerable variations in operating conditions without
adversely affecting product quality. The column was operated successfully at high feed
rates with some drop in performance when the column loading capacity was doubled
from about 20 to 40 Ib/h. Also, no plugging occurred during the entire test program,
even while operating at 160 Ib/h (1233 I b / f r / h ) , about three times the column's rated
capacity. This high feed rate did, however, result in a deterioration in performance, as
would be expected.
ACKNOWLEDGMENTS
This research was funded by the Illinois Coal Development Board (Department of
Energy and Natural Resources) via the Illinois Clean Coal Institute.
REFERENCES
1. Illinois State Reclamation Plan for Abandoned Mine Lands: Resource Document.
Cooperative Wildlife Research Laboratory, Southern Illinois University at Carbondale
for Abandoned Mined Lands Reclamation Council, June 1980.
2. F. F. Apian, "Coal Flotation-The Promise and the Problems." Chapter 11 in

Advances in Coal and Mineral Processing Using Flotation, S. Chander and R. R.
Klimpel, eds., SME, Littleton, Colorado, 1989, pp. 95-104.
160
3. "Standard Flotation Test Conditions," Chapter 6 in Coal Surface Control for

Advanced Fine Coal Flotation, Annual Report No. 1. Prepared by University of
California, Berkeley, et al for the U.S. Department of Energy, Pittsburgh Energy
Technology Center, February 28, 1990. Project No. DE-AC22-88PG88878.
4. L. A. Khan and J. W. Baxter, "Evaluating the Feasibility of Secondary Recovery of

Coal from Mine Wastes." Presented at the 1985 Symposium on Surface Mining,
Hydrology, Sedimentology, and Reclamation, University of Kentucky, Lexington,
Kentucky, December 9-13, 1985.
5. J. Hanna and R. Kalathur, "Recovery of Fine-Size Coal from Impounded Wastes."

Presented at the SME Annual Meeting, Denver, Colorado, February 25-28, 1991.
6. J. G. Groppo and B. K. Parekh, "Continuous Pilot-Scale Testing of Column Flotation

for Recovery of Fine Coal." In Mining Engineering, October 1989, pp. 1189-1192.
7. D. E. Zipperian and J. A. Christopherson, "Plant Operation of the Deister Flotaire

Column Flotation Cell." Presented at the 1985 SME-AIME Annual Meeting, New
York, New York, February 24-28, 1985.
8. D. J. Murdock and H. E. Wyslouzil, "Large-Diameter Column Flotation Cells Take

Hold." In Engineering and Mining Journal, August 1991, pp. 40-42.
9. G. H. Luttrell, M. J. Mankosa, and R. H. Yoon, "In-Plant Testing of Microbubble

Column Flotation." Presented at the SME Annual Meeting, Denver, Colorado,
February 25-28, 1991.
10. R. P. Killmeyer, R. E. Hucko, and P. S. Jacobsen, "Interlaboratory Comparison

of Advanced Froth Flotation Processes." Presented at the AIME Annual
Meeting, Las Vegas, Nevada, February 27-March 2, 1989.
11. D. Yang, "Technical Advantages of Packed Flotation Columns." In Proceedings

of Column '91, An International Conference on Column Flotation, Vol. 2, 1991,
pp. 631-643.
Coal Flotation Kinetics - Effect of Particle Size and Specific Gravity
M. Polat^ B. Amold^ S. Chander^ R. Hogg^ and R. Zhou^
^Penn State University, Mineral Processing Section, 115 Mineral Sciences Bldg.
University Park, Pa, 16802
^CQ Inc., P.O. Box 208, Homer City, PA 15748
To determine the flotation response for individual size-specific gravity fractions, the
products of flotation were analyzed in detail for a high volatile A coal. Flotation rates for
each size-specific gravity fraction were obtained using a classical first-order rate equation to
fit the data. The results were evaluated to determine the effect of size and specific gravity of
the coal particles on the flotation response.
1. INTRODUCTION
Probabilities of collision, attachment and detachment processes between the particles and
air bubbles in a flotation cell determine the rate of flotation. Successful attempts have been
made to predict the functional forms of these processes. The works of Sutherland (1948),
Tomlinson and Fleming (1963), Reay and Ratcliff (1973) and Flint and Howarth (1971) are
to mention only a few of many. Nevertheless, there is yet to be unifying model which would
successfully incoorate all these subprocesses to describe flotation. While micro-scale
flotation modeling is being pursued towards achieving such an objective, the need for a way
of predicting the flotation response of a given material has led to the development of
empirical flotation models. These models attempt to describe yield-time profiles of a given
sample based on a simple rate and recovery function to predict the flotation response. A
review of most of the present flotation models can be found in a study by Dowling et al.
(1985). general model which incoorates both batch and continuous flotation is given in
a paper by Huber-Panu et al. (1976).
Coal is a heterogenous substance which consists of organic constituents with imbedded
mineral matter. The response of a given coal sample towards flotation depends on the
composition of these organic and inorganic components as well as their respective ratios. An
increase in the mineral matter of coal may decrease the fraction of hydrophobic sites at the
surface as well as increasing the average density of the particles. Heavier particles float more
slowly than lighter ones with the same hydrophobicity since the probability of detachment is
proportional to the average particle density. Hence, floatability of coal particle will diminish
as its mineral matter content increases even though the organic fraction has sufficient
hydrophobicity (Trahar, 1981). In addition, the size of the coal particles is also important
in determining the rate of flotation. Even though larger particles will have a higher
probability of collision with the air bubbles, their size and generally reduced liberation from
162
the mineral matter will tend to facilitate detachment from the bubbles (Reay and Ratcliff,
1973; Jameson e t a l . , 1977).
It is clear that description of coal flotation using an empirical model for overall flotation
yield is not sufficient. Particles which fall into different size and specific gravity fractions
will response to flotation differently and any variation in the feed composition may cause a
change in the overall flotation rate. In order to characterize coal flotation to make better
predictions of the performance, a knowledge of the flotation response of the individual
particle types is required.
In this paper the experimental procedure for obtaining the flotation rates of the individual
size-specific gravity fractions is described. The results are evaluated to determine the effect
of size and specific gravity of the coal particles on the flotation response. One of the
objectives of this study was to determine rate parameters used in a coal flotation simulator
developed by Aspen Technology Inc. for the USDOE. The long-term objective is to relate
flotation response to liberation behavior.
2. MATERIALS AND PROCEDURES
2 . 1 . Materials
A high volatile A coal (Upper Freeport Seam) from the Helen Mine, Pennsylvania, was
used in this investigation. The as-received -1/4" sample contained 24.3% ash and 3.2%
sulfur.
Non-polar oils such as kerosene and fuel oil are the traditional collectors used in coal
flotation. In order to eliminate variations in the chemistry of the collector, dodecane with a
molecular weight close to that of fuel oil #2 was used in the experiments. Methyl Isobutyl
Carbinol (MIBC) from Shell was used as the frother.
2.2. Experimental Procedure

Flotation products obtained at various times were fractionated into various size-specific
gravity intervals and analyzed. A summary of the experimental procedure is given in Figure
1 and details are presented in the following paragraphs.
2.2.7. Sample Preparation, The as-received samples were reduced to -6 mesh and stored
in aluminum-laminated plastic bags of 15 kg capacity under an argon atmosphere. The 15
kg samples were further divided into samples of 500 grams as needed and stored in smaller
bags under the same conditions.
2.2.2. Grinding, To prepare the flotation feed, a rod mill was used to wet grind the coal
sample from -6 mesh to the desired size. The diameter and the length of the mill were 20
cm and 24 cm, respectively. The optimum grinding time to obtain a targeted nominal size
was determined from a series of grinding tests. For this puose, the Schumann k values for
each grinding were plotted as a function of the grinding time. A 250-gram sample was ground
at a solid concentration of 68% by weight, using a rod charge of about 7.5 kg. The rods were
22.5 cm long and their diameter varied between 1.1 cm and 1.8 cm. The mill was operated
at 60 rpm corresponding to 72% of its critical speed. The desired flotation size of nominal -
28 mesh was obtained using a grinding time of 50 seconds. The products from two succes
sive grindings were combined for those flotation tests in which 500 grams of feed was used.
163
I FEED (-6 MESB) 1
1 GRIN DING h
-28 MESB
FLOTATION PRODUCTS @
20, 40, 60, 120, 240 480 SEC.
H400MESB \ SCREENING -400 MESB
FILTERING* FILTERING*
^^DRYIN^^ DRYING
-400 MESB
SCREENING | -400 MESB
+400 MESB
SIZE & SPECIFIC G R A V I T Y
FRACTIONATION I
WEIGHING
ASH ANALYSIS 0
DATA
JjJANIPULATIO^
Figure 1. Experimental scheme for sample preparation, flotation,

and size-specific gravity analyses used in this investigation.
2,2,3, Flotation, Flotation experiments were conducted in a 5-liter cell using a Wemco
laboratory model flotation machine. The flotation cell was equipped with paddles on both
sides of the weir for automatic froth removal based on an earlier design by Miller (Luttrell
and Yoon, 1983 after Miller, 1980). The paddles were driven by a motor. The speed could
be adjusted from 2 to 200 m . Make-up water was added when necessary to maintain a
constant pulp level. In order to let the froth rise to an appropriate height, a lag time of 5
seconds was allowed between addition of air and start-up of the paddles for froth removal.
A summary of the experimental conditions for the flotation tests is given in Table 1. Both
the dodecane and the MIBC were injected into the cell with a micro-syringe.
Froth products from different time increments were wet screened using a 400 mesh
screen to remove the fine fraction and prevent caking during drying. Both the -h400 mesh
and -400 mesh fractions for each froth product were filtered and dried separately at 80 C
overnight. The +400 mesh material was dry screened to remove the misplaced -400 mesh
particles during wet screening. An overall -400 mesh material was obtained for each froth
164
Table 1
Experimental conditions for the flotation tests
Machine type: Wemco laboratory flotation cell.

Slurry volume: 5 liters
Rotor speed: 900 m .
Paddle speed: 40 m .
Aeration rate: 3000 ml/min.
Feed size: Nominal -28 mesh by wet grinding.
Amount of Solids: 250 grams to 750 grams (5% to 15% by weight).
Collector: Dodecane (0 to 0.30 kg/T).
Frother: MIBC (0.08 to 0.33 kg/T).
pH: 7.7 (Natural)
Flotation sequence: 3 minutes of initial conditioning; Oil addition - 3 minutes of
conditioning; Frother addition - 2 minutes of final
conditioning: Separate flotation products were obtained at
times of 20, 40, 60, 120, 240 and 480 seconds.
by combining the screen undersize from the wet and dry screening steps. Both the +400
mesh and -400 mesh material for each flotation product were stored separately for size-
specific gravity fractionation. It was clear in the beginning of the test work that some
size-specific gravity fractions might contain rather small amounts of material based on the
500 gram feed used in a flotation test. In order to increase the reliability of the analysis,
a given flotation test was repeated up to 10 times under identical conditions until a
sufficient amount of material was obtained.
2.2.4, Size specific gravity fractionation. The flotation products that were separated into
-h400 and -400 mesh fractions were subjected to size-specific gravity fractionation. The
size and specific gravity intervals used in this study were as follows: + 4 8 mesh, 48x100
mesh, 100x200 mesh, 200x400 mesh and -400 mesh; float @1.3, 1.3x1.5, 1.5x1.7,
1.7x1.9 and sink @1.9. The details of the procedure are given in another paper in this
proceedings, (Zhou et al., 1993). A total of 175 separate samples, each representing a
unique size-specific gravity interval, was obtained for each flotation product. Each
sample was analyzed for its weight and ash and sulfur contents. A complete mass balance
was obtained for each set of flotation tests to ensure that the data were self-consistent.
2.2.5. Flotation Kinetics. The yields for the individual size-specific gravity fractions
were plotted as a function of flotation time and the data were fitted to a classical first-
order kinetics model of the form
R = Rooil-e"^^]
where R is the cumulative fractional yield at time t, R, is the ultimate yield at time to^
and k is the rate constant. The classical first-order kinetics model was chosen to show the
trends observed in the data due to its simplicity and the relatively good fit it provided. A
165
commercial plotting and statistical software, Sigma Plot version 5.0 from Jandell
Scientific, San Rafael, CA, was used for curve fitting.
3.1 Flotation Behavior of the Overall Coal Sample

Some exploratory flotation tests were carried out to determine the flotation response
of the coal sample. Flotation conditions were selected so as to cover a wide range of
coal yields. The effects of different variables such as the concentrations of collector, solid
and frother were investigated. The selected concentration ranges were 0.00 to 0.30 kg/T
for the collector, 5 to 15% by weight for solids and 0.08 to 0.33 kg/T of the frother. The
rate of flotation increased slightly with the addition of collector resulting in higher yields
at shorter times while the ultimate yield remained the same, about 85%, for all cases
(Figure 2). It was observed that the coal sample was extremely floatable since essentially
no collector was required to obtain yields above 84%. There was an inverse relationship
between the solid concentration and the flotation rate (Figure 3). As the amount of solids
in the cell increased the flotation slowed down significantly most probably due to the
reduced ratio of the number of air bubbles to the coal particles. The differences in the
yield diminished with increasing flotation time as expected. Reducing the amount of
frother in the cell had an adverse affect on the flotation (Figure 4). A reduction of 20%
in the yield was observed at short times when the frother concentration was decreased
from 0.33 to 0.08 kg/T. Larger bubbles were observed at low frother concentrations and
the number of bubbles was decreased since the aeration rate was kept constant.
100 100
4 6
TIME, minutes TIME, minutes
Figure 2. Effect of collector Figure 3. Effect of solids concentration

concentration on the flotation on flotation response. Weight % solids:
response. C o n e , kg/T: - None; - 5%; V - 10%; - 15%.
v-0.15; -0.3.
166
Based on the experiments described in the preceding paragraph, three conditions,

covering a range of coal yields from about 25% to 90%, were selected for the flotation
tests conducted to generate samples for the subsequent size-specific gravity fractionation.
The conditions for these tests are given in Table 2.
Table 2
Experimental conditions for the flotation tests selected for size-specific gravity
fractionation.
Testal Test #2 Test #3
Dodecane Concentration 0.00 kg/T 0.30 kg/T 0.00 kg/T
Frother Concentration 0.33 kg/T 0.33 kg/T 0.08 kg/T
Solid Concentration 10% by wt. 10% by wt. 10% by wt.
* All the other conditions that are not listed here were kept constant and given in Table 1.
Up to 10 replicate tests were carried out in each of the conditions to obtain sufficient
material for the size-specific gravity fractionation. The yields obtained from each
replicate test were reproducible. A plot of the average yields for the three test conditions
selected is given in Figure 5 along with the 95% confidence intervals. For the cases
where the confidence interval is not shown, it was smaller than the symbol size.
100 r^ 1 r, 1 1 1 -
10 2 4 6 8
2 4 6 8
TIME, minutes TIME, minutes
Figure 4. Effect of frother concentration Figure 5. Average yields for the repeat
flotation response. Cone., kg/T: flotation tests with 95% confidence
-0.08; v-0.17; -0.33. intervals. - Test # 1 , a - Test #2;
- Test #3.
167
3.2 Flotation Behavior of the Individual Size-Specific Gravity Fractions

The flotation product was separated into different size-specific gravity fractions by the
method described in the previous section. The classical first-order equation was used to
obtain two distinct parameters, flotation rate, ky, and the ultimate yield, RQO.j for each
size-specific gravity fraction. The subscript i,j refers the various size-specific gravity
fractions. The results of Test #1 given in Figure 6 in terms of k^: and Roo,ij are plotted
as a function of size for the various specific gravity fractions. The plot of flotation rate
versus particle size shows that under the conditions used in Test #1 there is an optimum
size for flotation and it varies with specific gravity. Particles of low specific gravity, such
as the 1.3 float fraction, float easily with flotation rates as high as 5.5 min ^ at
comparably larger sizes whereas the particles of higher specific gravity show a maximum
in the flotation rate at fine sizes. Moreover, the flotation rate for a given size interval
increased with decrease in the specific gravity. For example, the flotation rate for
48x100 mesh fraction increased from about 0.5 min"^ to about 5.5 min"^ as the specific
gravity decreased. The ultimate yields given in the lower half of Figure 6 do not show a
size dependency for the particles of low specific gravity. The ultimate yield is about
100% for all size fractions. As the specific gravity of the middling fractions increases,
larger particles float slowly and the yield decreases. The increase in yield with decrease
in particle size for 1.9 sink materials is probably due to water carry-over.
30 50 70 100 300 500 30 50 70 100 300 500
PARTICLE SIZE, /mi PARTICLE SIZE,
Figure 6. Flotation rates and ultimate Figure 7. Flotation rates and ultimate
yields for Test #1 for individual size- yields for Test #2 for individual size-
specific gravity fractions. specific gravity fractions.
- Float @ 1.3; - 1.3x1.5; - 1.5x1.7; - Float @ 1.3; - 1.3x1.5; - 1.5x1.7;
- 1.7x1.9; - S i n k 1.9. - 1.7x1.9; - S i n k 1.9.
168
For the test designated as #2 in which 0.60 Ib/T of dodecane was used collector, the
results are presented in Figure 7. All the other conditions were the same as in Test # 1 .
The addition of collector significantly increased the flotation rates, especially those of
coarser particles at lower specific gravity fractions (1.3-float and 1.3x1.5). For example,
the flotation rate of the 1.3x1.5 specific gravity fraction at + 4 8 mesh increased from
about 2.0 min"^ at no collector to about 4.5 min"^ in the presence of the collector. The
size for maximum flotation rate was shifted towards larger values for these particles.
Surisingly, the flotation rate for particles in the specific gravity intervals of 1.5x1.7 and
1.7x1.9 decreased, especially at intermediate size ranges. These observations suggest that
larger particles with higher hydrophobicity benefit more from the presence of oil and
floats even more readily. Since there is only a limited number of air bubbles in the
flotation cell at a given time, an increase in the flotation rates of the highly floatable
fractions may reduce the rates for the middling particles by reducing the opportunity for
attachment. No significant differences in the flotation rates of the fine particles in the size
range of -400 mesh were noticed when compared to Test #1 since the amount of oil added
was very small and it was most probably consumed by larger particles. The ultimate
yields observed for Test #2 display a somewhat similar behavior to that observed for Test
#1. But the yields for particles below 48 mesh were higher than the yields for particles
above this size. It is important to note that a final yield of about 100% was reached for
all the particles below 48 mesh except for the 1.9-sink fraction. This suggests that the
flotation of fine intermediate gravity material is also favored by the presence of the
collector.
In the final experiment designated as Test #3, no collector was used while the amount
of the frother was decreased to 0.08 kg/T. This test was conducted to determine the
flotation response of the coal sample at low reagent dosages, especially frother. The
flotation rate decreased below 1.0 min'^ for all the size-specific gravity fractions except
for the 1.3-float material for which it was about 2.0 min ^ for + 4 8 mesh fraction (Figure
8). There was no significant size dependency for the flotation rates observed, suggesting
that larger particles suffered from the lack of frother as much as the finer ones. It was
surising to see that ultimate yields of above 80% were reached for particles below 100
mesh with a specific gravity less than 1.9. From these results one may conclude that
flotation of high rank coals could occur even under reagent depletion conditions if enough
time is given, but the grade might be poor. The detrimental effect of low reagent dosage
on flotation of coarse particles is obvious.
4. CONCLUSIONS
A series of flotation tests, followed by size-specific gravity analysis of the flotation

products was conducted for a high volatile A bituminous coal. The flotation yields for
each size specific gravity fraction were obtained for several different reagent dosages and
solids loading. The classical first-order rate equation was used to analyze the data using
two parameters, flotation rate, k^j and ultimate recovery, R Q O . j - On the basis of the
findings of this study the following conclusions were made:
1. The reproducibility of the flotation tests was quite satisfactory. For a given set of
replicate tests, the variation in the yield was no more than 1-2% within the
169
30 50 70 100 300 500
PARTICLE SIZE,
Figure 8. Flotation rates and ultimate yields

for Test #3 for individual size-specific gravity
fractions. - Float @ 1.3; - 1.3x1.5;
- 1.5x1.7; - 1.7x1.9; - Sink @ 1.9.
first 40 seconds of flotation and decreased further with increasing time of flotation.
2. The flotation rate decreased substantially with an increase in the specific gravity for
a given size interval. This was true for all the size fractions.
3. The observed effect of particle size on flotation kinetics for each specific gravity
interval indicates that the beneficial effect of collector was greater for the coarser
particles.
4. When both the collector and frother were present in desirable amounts (as in Test
#2), the ultimate yield for all specific gravity fractions was high and essentially
independent of particle size, except for the + 4 8 mesh fraction where lower
ultimate yields were obtained for the material with higher specific gravity.
5. Collector addition increased the ultimate yields for the intermediate specific gravity
fractions to almost 100%. For the 1.9-sink material of the -400 mesh fraction,
ultimate yields of approximately 60% and larger were obtained, showing the effect
of water carry-over.
6. A decrease in the amount of frother caused a substantial reduction in the flotation

rates for all the size-specific gravity intervals. The ultimate yields were still high,
over 70%, for all the specific gravity fractions especially at fine sizes.
170
REFERENCES
1. Dowling, . C , Klimpel, R. R. and Apian, F. F., 1985, "Model Discrimination in

the Flotation of a Porphyry Ore", Min. Metall. P r o c , vol. 12, pp. 87-101.
2. Flint, L. R. and Howarth, W. J., 1971, "The Collision Efficiency of Small Particles
with Spherical Air Bubbles", Chem. Engng. Sei., vol. 26, pp. 1155-1168.
3. Fuerstenau, D. W., Rosenbaum, J. M. and Laskowski, J., 1983, "Effect of Surface
Functional Groups on the Floatability of Coal", Coll. Surfaces, vol. 8, pp. 153-174.
4. Huber-Panu, I., Ene-Danalache, E. and Cojocariu, D. G., 1976, "Mathematical
Models of Bath and Continuous Flotation", Flotation - A.M. Gaudin Memorial
Volume, ed. by M. C. Fuerstenau, AIME, New York, pp. 675-724.
5. Jameson, G. J., Nam, S. and Moo Young, M., 1977, "Physical Factors Affecting
Recovery Rates in Flotation", Miner. Sei. Engrg., vol. 9, pp. 103-118.
6. Luttrell, G. H. and Yoon, R. H., 1983, "Automation of a Laboratory Flotation
Machine for Improved Performance", Int. J. Min. P r o c , vol. 10, pp. 165-172.
7. Miller, K. J., 1980, "Evaluation of Collector Addition in the Flotation of Various
U.S. Coals", Reports of Investigation, U.S. Department of Energy, PMTC-7(80).
8. Reay, D. and Ratcliff, G. ., 1973, "Removal of Fine Particles from Water by
Dispersed Air Flotation: Effects of Bubble Size and Particle Size on Collection
Efficiency", Can. J. Chem. Engng., vol. 51, pp. 178-185.
9. Sun, S. C , 1954, "Hypothesis for Different Floatabilities of Coals, Carbons and
Hydrocarbon Materials", Transactions AIME, vol. 199, pp. 67-75.
10. Sutherland, K. L., 1948, "Kinetics of Flotation Process", J. Phys. Chem., vol. 52,
pp. 394-425.
11. Tomlinson, H. S. and Fleming, M. G., 1965, "Flotation Rate Studies", P r o c 6th
International Mineral Proc. Congress, ed. by A. Roberts, Pergamon Press, pp. 563-
573.
12. Trahar, W. J., 1981, "A Rational Interetation of the Role Particle Size in
Flotation", Int. J. Miner. P r o c , vol. 8, pp. 289-327.
13. Zhou, R., Arnold, B. J., Chander, S., Hogg, R. and Polat, M. ,1993, "Problems in
Sink/Float Analysis of Fine Coal", Proc. High Sulfur Coal Conf., (an article
elsewhere in this publication).
On the native and induced floatability of coal and pyrite
Chengliang Jiang% Xiang-Huai Wang^S J.W. Leonard* and B.K.Parekh''
"Department of Mining Engineering

University of Kentucky, Lexington, KY 40506, U.S.A.
^Center for Applied Energy Research

University of Kentucky, Lexington, KY 40511, U.S.A.
ABSTRACT
The native and induced floatabilities of coal and pyrite have been systematically
investigated in order to elucidate the causes of the undesirable recovery of pyrite in coal
cleaning by flotation. Comparative flotation studies were conducted with coal, coal- and ore-
pyrite under various chemical conditions. In the absence of collectors, the Ky No.9 coal
exhibits moderate flotation in acidic media. The floatability of the coal decreases as pH
increases. The coal-pyrite and ore-pyrite samples (prepared by dry grinding) showed no
flotation in the absence of collectors. In the presence of fuel oil, coal shows a complete
flotation up to p H = 1 2 . The presence of fuel oil also increases the floatability of coal-pyrite,
especially for fine size fractions. However, the flotation of ore-pyrite is only slightly improved
by fuel oil. When xanthate is used as collector, the floatability of ore-pyrite is considerably
enhanced, particularly in neutral to alkaline media. For coal-pyrite, however, the flotation is
improved only in acidic media and is almost independent of the particle size. It was found that
xanthate can also increase the flotation of coal. The results demonstrate that the flotation
behavior of coal-pyrite is to a large extent determined by the coal/carbon coating. The recovery
of pyrite in coal flotation is mainly attributed to the oil-induced floatability due to the
hydrophobic coal/carbon coating on the surface rather than mechanical entrainment or
entrapment.
To whom all correspondence should be addressed.

172
INTRODUCTION
The amount of fine coal generated in coal mining and preparation processes has
increased all over the world in recent years. The utilization of these fine coals has been limited
due to the characteristics and the content of the associated impurities such as ash, sulfur and
other mineral matters. Particularly, the treatment of high-sulfur coal has encountered serious
problems due to the extremely "refractory" nature of the sulfur in the coal. Surface-based
physical separation techniques such as froth flotation have shown potential for removing pyritic
sulfur from coal effectively and economically [Rao and Bandopadhyay, 1980]. However, the
efficiency of this technique in rejecting pyrite from coal was significantly decreased for the
ultrafine coals with high pyrite content. It has been shown that even if the pyrite has been
completely liberated from coal, the effective rejection of pyrite by flotation can not be obtained
satisfactorily [Apian and Arnold, 1991].
The reasons for the difficulties of pyrite separation from coal are very complex and
have not been systematically investigated. It is known that the efficiency of pyrite rejection may
be low and vary from coal seam to coal seam. It was reported that coal-pyrite was much less
floatable than ore-pyrite when the conventional sulfide collector, xanthate, was used, especially
in neutral to acidic media [Chernosky and Lyon, 1972]. Coal pyrites require much higher
xanthate dosage for their flotation than do ore pyrites. More recent studies revealed that when
nonpolar collectors such as fuel oil were used in the flotation of coal, coal-source pyrite was
much more difficult to depress that ore pyrite, and the commonly used depressants for ore
sulfide were often not effective for coal pyrite [Apian and Arnold, 1991]. Moreover, pyrite
depressant usually not only depresses pyrite but also depress coal simultaneously to a certain
extent. Another factor complicating pyrite rejection was shown to be that large amounts of coal
froth produced in flotation also entraps the pyrite particles to the surface [Zimmerman and Sun,
1979]. In addition, the activation of ferrous or multivalent cations in the solution may affect
the flotation behavior of coal-pyrite [Lai, 1991].
A comparative study of native and induced flotation properties of coal, coal- and ore-
pyrite using microflotation technique is reported in this paper. Since the solution pH is the
major influential factor, the effect of solution pH on the flotation has been examined in detail
in the study. Two common flotation collectors, fuel oil and xanthate, were selected to
investigate the surface reactivity of coal- and ore-pyrite toward the reagents and their effects
on the flotation. Ultrasonic treatment of surface cleaning has been conducted to elucidate the
influence of surface oxidation and contamination on the flotation behavior of coal and pyrite.
The possible mechanisms underlying the different flotation phenomena of coal- and ore-pyrites
are then discussed in terms of the electrochemical measurements and solution chemistry of the
studied systems.
173
EXPERIMENTAL
Materials
Poritohedral ore-pyrite crystals, originated from Peru, were acquired from the Wards
Natural Science Establishment Inc. The ore-pyrite sample was of high purity and no further
cleaning was performed. Coal-pyrite and coal samples were obtained from Kentucky No.9 coal
seam. The coal-pyrite was in the form of lumps with visible coal particle attached to them. The
coal-pyrite sample was first crushed manually. Only the core lumps were selected without
visible coal contamination. The chemical analysis results of the pyrite and coal samples used
in the experiment are shown in Table 1 and 2.
The selected samples were first crushed to 20 mesh by jaw and roller crusher and
ground to -100 mesh with a laboratory pulverizer. The ground samples were screened to obtain
the different size fractions: i.e. -45^m, 45-74jLim, 74-100^m and 100-150m particle size
fractions for pyrites, and, -74jLtm and 100-150m size fractions for the coal. The prepared
samples were then stored in a refrigerator to minimize surface oxidation.
Table 1 Chemical analysis of the pyrite samples
Element, Wt%
Samples
Fe S C Ca Si Cu Pb Zn
Ore-Pyrite 42.0 49.6 <0.1 0.03 <.01 2.67 0.12 0.06

Coal-pyrite 30.0 39.0 4.33 6.60 <.01 0.02 <.01 <.01
Table 2 Analysis of the coal sample from Western Kentucky No.9 seam.
Analysis Dry basis, Wt%
Volatile Matter 39.1

Fixed Carbon 48,93
Ash 11.97
Total Sulfur 5.70
Pyritic Sulfur 2.97
Organic Sulfur 2.66
Sulfate Sulfur 0.08
174
Reagents:
Fuel oil was selected as one of the collectors to examine the oil-induced floatabilities
of coal and pyrites. In order to compare the different flotation responses of coal and pyrites
in the presence of different kinds of collectors, ethyl xanthate was chosen as the other collector
in the study. Methylisobutyl carbinol (MIBC) was used as the frother in all the flotation tests.
The pH adjustment was made by nitric acid H
(N
O3) and sodium hydroxide (NaOH). Distilled
water was used through all the flotation tests.
Flotation Tests:
The flotation tests were conducted in a micro-flotation cell with a volume of 100 ml.
The system consists of a nitrogen supply, pressure regulator, flow rate meter, flotation cell,
and a stirrer. One gram coal or pyrite sample with 60 ml distilled water was firstly introduced
in a beaker and conditioned for 2 min at the desired pH. It was observed that for coal-pyrite,
when the desired slurry pH was far apart from the natural pH, it was difficult to stabilize the
pH. In such cases, the condition time was longer than 2 min to allow the addition of extra acid
and base. Collector, either fuel oil or ethyl xanthate, was added and conditioned for 2 min.
MIBC was then added and the slurry was allowed further conditioning for 1 min. The slurry
was immediately transferred into the micro-flotation cell with pH adjusted water to flotation
level with the total volume of about 100 ml. The pH of water used during transference of
slurry was kept the same as that during conditioning period to avoid the pH change due to
dilution. 0.5 min conditioning was carried out prior to aeration. Froth was then collected for
3 min. After flotation, froth and tailing were filtered, dried and weighed, the froth weight
fraction was calculated as recovery. The pH of the tailing solution in the flotation cell was
measured and taken as flotation pH.
Electrochemical Measurements
Cyclic voltammetry was performed with standard three-electrode system. A pyrite

electrode was used as the working electrode and a platinum electrode as the counter electrode
is . The potentials were measured against a saturated calomel electrode(SCE). The
electrochemical system consists of an EG&G Princeton Applied Research (PAR) Model 273
potentiostat/galvanostat and a PAR model 660 rotating-disc electrode apparatus. The system,
including data acquisition, is operated by a computer. Before each experiment, the pyrite
electrode was polished using 4000 grit SiC polishing paper in air with deionized water, and
rinsed with deionized water. The measured geometric surface areas were used for calculating
the current density. Ore-pyrite electrode (PUPY) from Peru and coal-pyrite (KYPY) electrode
from Kentucky No.9 coal seam were prepared from natural crystals. 0.1 potassium
perclorate K
(C
O
I4) was used as the electrolyte solution.
175
100
90
MIBC: 5 0 m g / l
80
Size: ( m m )
A: - 0 . 0 7 4
70 : 0 . 1 - 0 . 1 5
>s
i-
> 60
o

< 50
c 40
o
o
30
o
u_
20
10
Fig. 1 Floatability of coal for different particle sizes as a function of pH in the presence
of frother. Note that no flotation has been observed for ore-pyrite and coal-pyrite
for different sizes in the same condition.
MIBC: lOOmg/1
Fig. 2 Flotation recovery as a function of solution pH for coal, coal- and ore-pyrite in
the presence of frother after surface cleaning by ultrasonication. Particle size:
coal -74^m; coal-pyrite and ore-pyrite 45-74jLtm.
176
RESULTS
Self-Induced Flotation of Coal and Pyrites
The native flotation behavior of coal and pyrites in the presence of only MIBC as a
function of pH for different particle sizes is presented in Fig.L Of the various particle sizes
studied, only the size fraction of -74 coal shows moderate flotation in acidic media in the
absence of collector. The maximum recovery is found to be about 55% in the acidic range
below pH 6. Above pH6, the recovery decreases drastically with increasing pH. The flotation
ceases at about pHlO. However, for coarse size fraction ( 1 0 0 - 1 5 0 m ) , the presence of 5 0 mg/1
MIBC is not able to induce its flotation. The results indicate that the native floatability of coal
depends strongly on the grain size. It is known that flotation is determined by many factors.
Besides the surface hydrophobicity which determines the thermodynamics of flotation, the
particle size controls the kinetics of flotation [Crawford and Ralston, 1988]. The moderate
flotation of fine coal (-4) would be attributed to the natural surface hydrophobicity of coal.
The lack of floatability of coarse coal particle (100-150jLcm) is probably due to the greater
probability of detachment from the bubbles in the flotation cell [Trahar, 1981].
In contrast to coal, in the absence of collector, the coal-pyrite and ore-pyrite of all the
size fractions studied exhibit no flotation in the whole pH range. This indicates that the
surfaces of the coal- and ore-pyrite are hydrophilic. It has been shown that this is due to the
formation of hydrophilic iron hydroxide layers on pyrite surfaces during grinding process
[Ramprakash et al., 1990, Smart, 1991], these layers can be removed by reacting with
complexing agent EDTA [Wang, 1989 and Wang and Forssberg 1990], or by ultrasonic
pretreatment [Wang et al, 1992b].
Figure 2 presents the flotation recovery of coal, coal-pyrite and ore-pyrite as a function
of pH in the presence of frother after ultrasonic pretreatment. It can be seen that after cleaning
the surface by ultrasonication, the ore-pyrite shows good flotation up to pHlO. However, the
coal-pyrite remains pooriy floatable. Compared with untreated coal (Fig. 1), it can be seen from
Fig.2 that ultrasonic treatment increases the floatability of coal (100-150 ^m) in alkaline
solutions. Interestingly, a depression valley exists in neutral media around pH6. The results
revealed that surface cleaning induces substantial flotation for ore-pyrite and coal, and minor
but visible flotation for coal-pyrite.
Oil-Induced Flotation
Nonpolar oily organic compounds such as fuel oil have been widely used as collectors
in the coal flotation to improve the hydrophobicity of coal surface. It is generally assumed that
the oily collectors would be adsorbed only on coal particle surfaces. There are no systematic
studies of the effects of oily collectors on the floatability of pyrites. Therefore, it is necessary
to examine the flotation response of pyrite in the presence of oily collectors.
177
100-| ===
90- F u e l oil: 5 0 m g / l
MIBC: 50mg/l
80-
Size: (mm)
A: - 0 . 0 7 4
70- B: 0.1-0.15
< 6 0 -
>
o
50-
i-
c 40-
o

30-
o
_
20-
10-
0-
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Fig. 3 Flotation recovery of coal as a function of solution pH and particle size in the
presence of fuel oil as collector. Dashed lines show the flotation recovery of
coal in the absence of collector as shown in Fig.l.
100-f
Fuel oil: 5 0 m g / l
90- MIBC: 50mg/l
Size:(mm)
80- A: - 0 . 0 4 5
B: 0 . 0 4 5 - 0 . 0 7 4
70-
> 60-
o
(J
0) 50-
c 40-
o

30-
o
u.
20-
10-
0-
Fig. 4 Flotation recovery of coal-pyrite as a function of solution pH and particle size

in the presence of fuel oil as collector.
178
Fuel oil: 50mq/l

MIBC: 50mg/l
Size:(mm)
A: -0.045
B: 0.045-0.074
Fig. 5 Flotation recovery of ore-pyrite as a function of solution pH and particle size

in the presence of fuel oil as collector.
100
Fuel oil: 50mg/l
MIBC: 50mg/l
pH: 6 - 7
<
Coal-pyrite \ / Ore-pyrite
0 20 40 60 80 100 120 140 160 180 200

Particle size,
Fig. 6 Effect of particle size on the floatability of coal-pyrite and ore-pyrite in the
presence of fuel oil as collector.
179
100-
90-
80-
70-
> 60-

( 5 0 -
-
C 40-

"
30-

-
2 0 - Ore-pyrite
10-
0-
Fig. 7 Comparison of flotation recovery of ne coal, coal- and ore-pyrite particles as

function of solution pH in the presence of fuel oil. Coal: -74^m; coal- and ore-
pyrite: -45 .
100
Q 1^"^^^
90
80
70
60 1\^
50
Xanthate:
50mg/l c ^ 11
MIBC-
50mg/l
40
Size:(mm)
30
A: 0.074-0.1
B: 0.045-0.074
20 C: -0.045
10-1
0
4 5 6 7 8 9 10 11 12 13 14
pH
Fig. 8 Flotation recovery of ore-pyrite as a function of solution pH and particle size

in the presence of ethyl xanthate as collector.
180
The floatabilities of coal, coal-pyrite and ore-pyrite as a function of pH in the presence

of fuel oil are presented in Figs.3-5, respectively. As has been shown above, except for the
fine size coal (-74), no flotation has been observed for the coal-pyrite and ore-pyrite in the
absence of fuel oil. When 50 mg/1 fuel oil was added, coal, coal-pyrite and ore-pyrite all
showed a good flotation behavior. Coal shows a complete flotation up to pHlO.5. Even at
pH12, the recoveries of the two different size coals are still 65% and 7 5 % , respectively.
Hence, the floatabilities of the coal was considerably improved by the presence of fuel oil.
The presence of fuel oil also induces considerable flotation for coal-pyrite, particularly
for fine particle size, as shown in Fig. 4. The floatabilities of the coal-pyrite are relatively high
in acidic range, and decrease as pH increases. It is interesting to note that the finer size
fraction (-45^m) of the coal-pyrite shows better flotation in alkaline solutions than the coarser
size fraction 45-75/-cm. Even up to pH12, 20% recovery of the coal-pyrite of size - can
still be observed, while flotation has ceased for the coarse size 45-4 at pHlO. Further
studies indicate that the flotation of the coal-pyrite increases with increasing the concentration
of fuel oil. For the ore-pyrite, both coarse and fine size fractions display a moderate flotation
in acidic solution, as can be seen from Fig.5. However, in the neutral and alkaline solutions,
no flotation can be observed for fine size ore-pyrite (-45m). The coarse size fraction (45-
74m) of ore-pyrite shows a flotation plateau of about 15% recovery Thus, the finer size
fraction of the ore-pyrite is less floatable than the coarser size fraction. This is contrary to that
of the coal-pyrite.
Figure 6 shows the effect of particle sizes on the floatabilities of coal-pyrite and ore-
pyrite in the presence of fuel oil at pH6-7. The effect of particle sizes on the floatabilities of
pyrites from coal and ore sources follows different pattern. For the coal-pyrite, the finer the
particle size is, the higher the floatability is, while for ore-pyrite, the floatability increases with
increasing particle sizes. When the particle size is below 45^m, the coal-pyrite reaches the
recovery of above 60%, but ore-pyrite shows no flotation at all. The results demonstrate that
the fine coal-pyrite has high affinity to fuel oil.
The floatabilities of fine coal, coal-pyrite and ore-pyrite as a function of pH in the

presence of fuel oil are compared in Fig.7. It clearly shows that in the presence of fuel oil coal
displays complete flotation, ore-pyrite has no floatability above pH5, while coal-pyrite lies in
the middle. It is worthwhile noting that the coal-pyrite and coal show considerable similarity
in their flotation characteristics. These results indicate that fuel oil adsorbs not only on the coal
surface but also on the coal-pyrite surface, rendering the surfaces hydrophobic, and thereby
reducing the selectivity of flotation separation.
Flotation with Xanthate
Xanthate flotation of pyrite has been successfully practised in the sulfide ore industry
for more than sixty years. Recently, there has been considerable interest in the reverse flotation
process to remove pyritic sulfur from fine-size coal, i.e. floating pyrite by xanthate while
181
100-
go- !^ Xanthate: 50mg/l

MIBC: 50mg/I
so-
^ 70H 1 Size:(mm)
^ 60 0 0.1-0.15
o 0.074-0.1
0.045-0.074
50 o -0.045
40
1 30
20

1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Fig. 9 Flotation recovery of coal-pyrite as a function of solution pH and particle size

in the presence of ethyl xanthate as collector.
100-
90- Xantahe: 50mg/l

MIBC: 50mg/l
80-
Size: (mm)
A: -0.074
70- X B: 0.1-0.15
>s
> 60-
O
O
50-
^
C
B 1\ ^
O 40-

30-
o
u.
20-
C] ^
10-
0-
0 1 2 3 4 5 6 7 8 9 10 1 1 1 2 13 14
pH
Fig. 10 Flotation recovery of coal as a function of solution pH and particle size in the
presence of ethyl xanthate as collector.
182
depressing coal by coal depressant [Miller, 1975]. Thus, it is of importance to examine the
flotation behavior of coal, coal- and ore-pyrite in the presence of xanthate as a collector.
Figure 8 shows the flotation recovery of the ore-pyrite as a function of pH in the

presence of 50 mg/l ethyl xanthate. It can be seen that all the particle sizes of the ore-pyrite
reveal complete flotation in the acidic solution of below pH6. However, their flotation depends
strongly on the xanthate concentration, particle size and pH. The coarser particle fraction (74-
lOO^m) floats completely up to pHlO. While the fine ore-pyrite particles (-45^m) can not float
well at pH > 6. The intermediate size fraction reveals partial flotation in the neutral pH range,
which is in good agreement with previous studies [Ball and Richard, 1976; Fuerstenau, 1981].
The flotation behavior of coal-pyrite differs significantly from that of ore-pyrite. As shown in
Fig.9, all the sizes of coal-pyrite display good flotation below p H = 6 . However, above pH6,
the recoveries of coal-pyrites decrease sharply. In the alkaline solution above pH6, only little
flotation can be observed for coarse sizes (100-150)Ltm and 74-lOOjum) and almost no flotation
is obtained for fine sizes (45-74^m and -45/xm).
Figure 10 presents the flotation recovery of coal vs pH in the presence of ethyl

xanthate. Compared with the results in the absence of collector (Fig. 1), the floatabilities of coal
are improved in acidic solution, particularly for coarse coal of size 100-150jLcm. It can be seen
that coal floats very well in the presence of xanthate. The recoveries drastically decrease with
p H > 6 . At p H > 6 , the coarse coal (100-150jLtm) is nearly nonfloatable, while the fine coal (-
74jLtm) ceases flotation at p H l l . It can be noticed that the flotation behavior of coal and coal-
pyrite is very similar in the presence of xanthate.
Electrochemical Oxidation of Pyrite
The electrochemical tests were conducted in the electrolyte solution of 0. IM potassium

perclorate of pH5.6. Figure 11 shows the typical cyclic voltammogram of an ore-pyrite
electrode (PUPY). It is interesting to note that a rotating dependent cathodic process occurs
on the ore-pyrite surface. At stationary condition, a distinct reduction peak is observed at a
potential of about 400 mV (vs SCE) in the negative-going scan. At a rotating electrode, the
peak disappears. Further studies show that this peak is noticed until about pHlO. The cyclic
voltammogram of coal-pyrite electrode (KYPY) is shown in Fig. 12. It is seen that the
electrochemical oxidation of the coal-pyrite is totally different from that of the mineral pyrite.
No well-defined redox peaks are observed on the voltammogram, even though the anodic and
cathodic current densities are much higher than that of ore-pyrite. There is no significant
difference in the voltammograms obtained for the stationary and rotating-disc electrodes. The
results are in agreement with the previous studies for other coal-pyrite electrode [Wang et al,
1992a]. Our further study also shows that the cyclic voltammograms of KYPY are almost
independent of the solution pH, but strongly dependent on the carbon content of the electrode.
183
0.10
FeS,. PUPY
CM
pH = 5.5. 2 0 m v / s
Rotation (RPM)
O A: O
B: 1 0 0 0
< 0.05
S
0.00
d
cu
Q
"2 -0.05
cu
u
-0.10
-1200 -800 -400 O 400 800
vs SCE (mV)
Fio 11 Cyclic voltammograms of ore-pyrite (PUPY) for stationary and rotating disc
electrode at p H = 5 . 6 .
FeS:. KYPY
pH = 5.6. 2 0 m v / s
Rotation (RPM)
A: 0
B: 2 0 0 0
-1200 -800 -400 0 400 800

VS SCE (mV)
Fig. 13 Typical cyclic voltammograms of highly coal-contaminated coal-pyrite (KYPY)

for stationary and rotating disc electrode at p H = 5 . 6 .
184
DISCUSSION
As shown in the above studies, the flotation behavior and the electrochemical reactivity
of coal- and ore-pyrite differ remarkably. The causes of differences are complex. However,
the principal difference in the chemical composition between the pyrites from coal and ore
sources is their carbon content. The chemical analysis results given in Table 1 shows that the
impurities contained in ore-pyrite are mainly heavy metals, mostly copper, lead, and zinc. The
S/Fe ratio of ore-pyrite is close to 2, the theoretical stoichiometric value. However, coal-pyrite
contains high carbon (4.33%) and calcium content, and the ratio of S to Fe is 2.26. The
compositional deviation of coal-pyrite from the theoretical value and the existence or incursion
of carbonaceous material might have resulted in great differences from ore-pyrite in the
crystalline, morphology, and surface property. The results from the cyclic voltammetric studies
demonstrate that coal-pyrite is more reactive than ore-pyrite. The surface of the coal-pyrite
possesses more characteristics of coal/carbon than pyrite itself. Studies found that coal-pyrite
shows higher oxidation rate than ore-pyrite [Lai et al, 1990; Wang et al, 1992b]. Dry ground
coal-pyrite surface was shown to be totally oxidized [Khan et al, 1992]. It is known that the
moisture content in coal is high due to its porous structure. It is expected that coal-pyrite in
coal deposits could have been exposed to more oxidizing environment than ore-pyrite. The
higher degree of oxidation might have occurred even in the interior of its crystal, particularly
to those particles finely disseminated in coal. This is consistent with the poorly induced
floatability of coal-pyrite even by ultrasonic surface cleaning (Fig. 2). Hence, the surface
properties of the coal-pyrite are mainly determined by two factors: the high degree of surface
oxidation and the coating of coal on the surface.
The flotation phenomena observed in the presence of xanthate can be explained from
the following two aspects: the solution chemistry of the iron-xanthate and the coal incursion
on the surface. First, let us examine the solution chemistry. Wang and coworkers [1989,
1989b, 1991] have demonstrated that a number of ferric-xanthate compounds can be formed
under normal flotation conditions. Figure 13 and 14 show the log(Concentration)-pH
distribution diagrams for the thermodynamic system of iron-xanthate at p e = 3 for different iron
concentration. The diagrams were computed using standard stability constants [Smith and
Martel, 1976; Sillen and Martel, 1970; Wang et al, 1991]. At a concentration of ethyl xanthate
3.3xlO'^M (50mg/l) and iron IxlO'^M, and in acidic solution, aqueous and liquid dixanthogen
is the predominant species of xanthate. In the neutral pH range of pH5-9 where the stable
insoluble ferric dihydroxo xanthate (Fe(0H)2EX) are formed, liquid dixanthogen completely
disappears, the quantities of aqueous xanthate are relatively small, at p H > 9 , xanthate ion is
the main form. At higher iron concentration of IxlO'^M, as shown in Fig. 14, liquid
dixanthogen disappears in the whole pH range. It can be seen that in the acidic solution below
pH4, the ferric xanthate, Fe(EX)3 is formed. Consequently, the conclusion that dixanthogen
is the only species responsible for pyrite flotation is justified [Fuerstenau, 1968; Fuerstenau
and Mishra, 1981; Ball and Richard, 1976]. The presence of metal xanthate species such as
ferric hydroxo-xanthate is more likely to determine the flotation behavior of pyrite in alkaline
solution [Wang, 1989; Wang et al, 1989b, 1991; Fornasiero and Ralston, 1992].
185
-2H
FeOHfEXWs) , , , ,
1^
, (EXMD \ / , -
(EX)2(I)
(EXMaq)
-6
O
HEX ^
o -8
1 2 3 4 5 6 7 8 9 10 11 12 13
pH
Fig. 13 log(Concentration)-pH distribution diagram for iron-ethyl xantahte system at

p e = 3 for total concentration of S.SxlO'^M xanthate and IxlO'^M iron.
-2H FeOH(EX)2(s)
' Fe(OH),EX(s)
Fe{ZXUs)\
Fig. 14 log(Concentration)-pH distribution diagram for iron-ethyl xantahte system at

p e = 3 for total concentration of 3.3xlO"*M xanthate and IxlO'^M iron.
186
The results obtained from the thermodynamic calculations can satisfactorily explain the
flotation results of pyrite by xanthate. Freshly ground coarse size (74-100m) ore-pyrite, which
hase a low degree of surface oxidation, shows complete flotation in the whole pH range (Fig.
8). For ne size fraction of ore-pyrite (-45/zm), two factors need to be considered. Firstly, it
is expected that a thicker layer of surface oxidation products could have been formed on the
pyrite surfaces. Hence, more ferric dihydroxo-xanthate is likely to be formed on the surface.
Secondly, as the particle size decreases, the surface concentration of xanthate will be
decreased. This is effectively equivalent to a decrease in xanthate concentration for the sample
particle size. Since Fe(0H)2EX is poorly hydrophobic (due to the hydroxyl groups), and as
shown in Figs. 13 and 14, under these conditions, the quantities of dixanthogen and xanthate
are extremely small. It is anticipated that the surface of fine coal-pyrite will remain poorly
hydrophobic. The flotation behavior of coal-pyrite for different particle sizes by xanthate is
extremely similar to that of fine ore-pyrite (Figs. 8-9). The high oxidation degree of coal-pyrite
produces a lot of oxidized products, the ferric ion concentration are high both on the surface
and in the solution under the normal flotation conditions. It is expected that much of xanthate
added will be consumed by the formation of ferric dihydroxo xanthate. This reduces the
floatability of coal-pyrite. The particle size independence of coal pyrite flotation with xanthate
suggests that the oxidation of coal-pyrite surface is very severe. It is not clear which xanthate
compounds are responsible for the coal flotation. The improvement of coal flotation by
xanthate in acidic solution may be due to the dixanthogen adsorption on the coal surface.
However, it should be noted that the coal sample contains 3% pyritic sulfur, as shown in Table
2. Since coal-pyrite shows no flotation at p H > 6 (Fig.9), the poor floatability of coal in
alkaline media using xanthate as a collector (Fig. 10) may be due to the contamination of
nonfloatable coal-pyrite on the coal surfaces. The exact reasons for this phenomena need to be
further studied.
The electrochemical studies show that the coal-pyrite surface is quite different from
that of ore-pyrite. Besides the oxidation of coal-pyrite itself, the presence of organic coal
compound at the surface of coal-pyrite may also be susceptible to the electrochemical reaction.
The oil-induced floatability of coal-pyrite by the addition of fuel oil may be due to the
adsorption of nonpolar fuel oil with the carbon/coal area on the surface. Since in the presence
of fuel oil, the flotation behavior of coal-pyrites is extremely analogous to that of coal, as
shown in Fig. 7. The area covered by coal/carbon on the coal-pyrite surface may change with
the particle size. Fine size coal-pyrite may have a larger surface area and expose more
hydrophobic carbon/coal sites than coarse size particle. Therefore, in the presence of fuel oil,
as the particle size decreases, the floatability of coal-pyrite significantly increases. Unlike coal-
pyrite, the ore-pyrite has no carbon/coal substances on its surface. Therefore, in the presence
of fuel oil, fine size ore-pyrite shows no flotation at all in neutral and alkaline solutions. The
moderate flotation with fuel oil for coarse size ore-pyrite may be ascribed to the hydrophobic
adsorption of oil with the sulfur formed by moderate oxidation of pyrite.
The flotation results suggest that there are two main reasons for the difficulty of pyritic
sulfur removal from coal using nonpolar oil as collector: one is the oil-induced floatability of
187
coal-pyrite due to the coating of carbon/coal on its surface; the other is the formation of
hydrophobic sulfur-rich pyrite surface layer due to the oxidation and surface dissolution. The
results indicate that the entrapment or entrainment effect of coal froth on coal-pyrite is
negligible. Therefore, fuel oil used in coal flotation is adsorbed non-selectively on both coal
and coal-pyrite surfaces. This increases the difculty in rejecting pyrite from coal by flotation
and explains why coal-pyrite is more difcult to depress than ore-pyrite. The depression of
ore-pyrite by depressants may be reached by the chemical reaction of depressant with the
pyrite surface to form hydrophilic layers, while for coal-pyrite, a large portion of surface is
occupied by coal/carbon and remains highly hydrophobic to be available to the adsorption of
nonpolar oil. More importantly, the surface covered by coal cannot be modified by using pyrite
modifying agents.
CONCLUSIONS
Coal-pyrite and ore-pyrite show no floatability in the absence of collector. Ultrasonic

surface cleaning can substantially induce the flotation of ore-pyrite and coal. Fuel oil can not
only completely float coal but also induces considerable floatability for coal-pyrite, especially
in alkaline media. The hydrophobic interaction of nonpolar oil with the carbon/coal coating on
coal-pyrite surface seems to be responsible for the oil-induced flotation. Xanthate is shown to
be effective collector for ore-pyrite in whole pH range. In the presence of xanthate, good
flotation is obtained for coal and coal-pyrite only in acidic solution. Coal-pyrite is easily
oxidized to produce excessive ferric and ferrous ions. The lack of floatability of coal-pyrite in
alkaline solution can be explained by the formation of weakly hydrophobic ferric dihydroxo
xanthate on the surfaces of coal-pyrite. The xanthate also increases the floatability of coal, the
interaction between them appears not to be very strong and the mechanism needs further
investigation.
ACKNOWLEDGEMENT
This work was conducted with the support of the project of the U.S. Department of
Energy under the Contract No. DE-FG22-90PC90295.
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Fuerstenau, Editor), Vol.1, AIME, New York, NY, pp.458-484.
3. Chernowsky, F.J., and Lyon, M., 1972, Trans. SME-AIME, Vol.252, pp. 11-14.
4. Crawford, R. and Ralston, J., 1988, International Journal of Mineral Processing.
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Vol.23, ppl.
5. Fornasiero, D. and Ralston, J., 1992, Electrochemistry in Mineral and Metal Processing
III.(R. Woods and P. Richardson, Editors), ECS, Pennington, NJ, pp. 191-220.
6. Fuerstenau, D.W. and Mishra, B.K., 1981, in: Complex Sulfides (M.H. Jones, Editor),
IMM, London, pp.271-278.
7. Fuerstenau, M . C , Kuhn, M.C. and Elgillani, D.A., 1968, Trans. AIME, Vol.241,
p.437.
8. Khan, S.U.M., Farley, T.J. and Bultrus, J.P., 1992, Electrochemistry in Mineral and
Metal Processing III.(R. Woods and P. Richardson, Editors), ESC, Pennington, NJ,
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Metallurgical Engineering, February, pp.43-48.
10. Miller, K.J,, 1975, Trans. SME-AIME, Vol. 258, pp30-33.
11. Ramprakash, Y. and Koch, D.F.A., 1990, Journal of Applied Electrochemistry,
Vol.21, pp.531-536.
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Somasundaran, Editor), AIME, New York, Vol.2, pp.977-989,
13. Sillen, L.G. and Martell, A.E., 1970, "Stability constants of Metal-ion complexes,"
London.
14. Smart, R . S t . C , 1991, Mineral Engineering, Vol.4, No.7-11, pp.891-909.
15. Smith, R.M. and Martell, A.e,, 1976, "Critical stability constants," Vol.4, Plenum
Press, New York,
16. Trahar, W.J,, 1981, International Journal of Mineral Processing, Vol.8, pp.289-327.
17. Wang, X.H., 1989, "The chemistry of flotation, activation and depression of iron-
containing sulfide minerals," Ph.D Thesis, Lulea University of Technology, Lulea,
Sweden.
18. Wang, X.H. and Forssberg, K.S.E. and Bolin, N.J., 1989, International Journal of
Mineral Processing, Vol.27, pp. 1-19.
19. Wang, X.H. and Forssberg, E., 1990, Journal of Colloid and Interface Science,
Vol.140, N o . l , pp,217-226.
20. Wang, X.H. and Forssberg, E., 1991, International Journal of Mineral Processing,"
Vol.33, pp,275-290,
21. Wang, X,H,, Jiang, C.L., Raichur, A.M., Parekh, B.K. and Leonard, J.W., 1992,
Electrochemistry in Mineral and Metal Processing III.(R. Woods and P. Richardson,
Editors), ECS, Pennington, NJ, pp.410-432.
22. Wang, X.H., Raichur, A.M. and Parekh, B.K., 1992, 10th International Pittsburgh
Coal Conference, Pittsburgh.
23. Zimmerman, R.E, and Sun, S . C , 1979, in: Coal Preparation (J.W. Leonard, Editor),
4th Edition, Port City Press, Maryland, p. 10-75.
Problems in Sink-Float Analysis of Fine Coal
R. Z h o u \ B. Arnold^, S. Chander^ R. Hogg^ and M. Polat^
^Penn State University, Mineral Processing Section, 115 Mineral Sciences Bldg.
University Park, PA 16802
^CQ Inc., P.O. Box 208, Homer City, PA 15748
A procedure for determining size and specific gravity distributions of the total
quantity, and the sulfur and ash content of fine coal is described. The procedure involves
cumulative fractionation by specific gravity followed by size separation by sieving. An
averaging procedure is used to minimize experimental error and a regression method is
employed in order to provide best estimates of the individual size-specific gravity fractions.
An example of the application of the procedure to analyze froth flotation products is
presented.
1. INTRODUCTION
So-called sink-float analyses are widely used for evaluating the size-specific gravity
distributions of coal samples. Such distributions reflect the degree of liberation of coal from
its associated mineral matter. The set of distributions obtained by progressive size reduction
of the coal defines the potential for physical coal cleaning, i.e., the washability of the coal.
The procedures for sink-float analysis become increasingly difficult as particle size is
reduced. In particular, problems are encountered due to:
aggregation, especially between coal particles and fine mineral matter such as
clays.
reduced rate of separation for fine particles.
Aggregation obviously leads to misplacement of material either into the float or sink
products and must be minimized through proper dispersion of the particles in the heavy
liquid. The latter can usually be accomplished by mechanical agitation and ultrasonic
conditioning together with appropriate additions of chemical dispersant such as surfactants
(Dunmi and Hogg, 1987 a,b).
The low sedimentation velocities for fine near-gravity particles lead to excessive
separation-time requirements. For example a 5-^m particle whose specific gravity differs by
0.05 from the liquid would require about 20 hours to settle (or float) through a distance of
5 cm. The use of centrifuges to increase the separation rates to more realistic levels is
usually mandated (Cavallaro and Killmeyer, 1988; Dyrkacz, et al., 1992).
190
The primary objective of the work described in this paper was to develop and evaluate
a practical, reliable procedure for performing sink-float analyses on fine coal samples.
2. APPROACH
The determination of size-specific gravity distributions generally involves density

(sink-float) separations using heavy liquids, in combination with size separation by sieving.
There are several ways, however, by which this can be accomplished. For example, size
separation can be performed first, followed by gravity separation on the individual size
fractions, or the reverse; density separation followed by sieving of the specific gravity
fractions. Furthermore, the gravity separations can be carried out incrementally or
cumulatively. In the former case a single sample is separated repeatedly at progressively
increasing (or decreasing) density. The cumulative method, on the other hand, involves a
single density separation on each of a set of discrete samples.
The various different approaches have their own relative advantages and
disadvantages. For example, density separations become difficult at fine sizes so there is
some advantage to pre-sizing the material. On the other hand, the density separations are
time-consuming and involve toxic, heavy liquids (usually organic) so it is advantageous to
minimize the number of separations to be made. The cumulative method of gravity
separation offers several advantages over the incremental approach. Because each separation
involves a separate sample, the resulting replication leads to a reduction and, to some extent,
permits quantification of the sampling errors. In addition, the series of single separations
provides larger sink and float samples for subsequent analysis, e.g., for sulfur and ash
content. It should be cautioned, however, that the cumulative method can lead to anomalous
results such as apparently negative quantities in certain size-specific gravity fractions where
there is little or no material. The fact that such anomalies cannot arise with the incremental
method, should not be regarded as an advantage of this approach. The experimental and
sampling errors which lead to such results are still present, more so in fact since the analysis
is normally based on a single sample. Furthermore, since the incremental analysis is
conducted by successive separation of the sample, experimental errors introduced at an early
stage in the process are propagated through the remainder of the analysis leading to a
consistent bias in the results. In any separation there is inevitably some misplacement of
material in both directions (heavy reporting tot he light fraction and vice versa). In the
cumulative approach, these lead to random error in the results which tend to compensate but
can lead to the kinds of anomalies noted above. In the case of incremental analysis, however,
material misplaced in the first separation is automatically misplaced in each subsequent
separation leading to systematic bias in the results.
We have adopted a hybrid approach to the analysis in which the material is first sieved
at 400 mesh (37 m) to minimize the problems of heavy liquid separation of fine particles.
The coarse and fine fractions are then subjected to cumulative gravity separation at the
required densities followed, for the coarser fractions, by sieving at the appropriate sizes.
3. EXPERIMENTAL PROCEDURE
3.1. Sample Pretreatment
Each of the samples to be analyzed was first divided into minus and plus 400-mesh
191
size fractions by wet screening. Both size fractions of materials were then dried in an oven
set at 80 overnight. After drying, the +400 mesh fraction was dry screened at 400 mesh
on a Ro-Tap Sieve Shaker to remove near-size particles remaining from the wet-screening
operation. The resulting -400 mesh material was combined with that obtained from the
original wet-screening step.
3.2. Size-Specific Gravity Fractionation
The material obtained by the procedure described in the previous section was
fractionated into various gravity fractions by the following procedures:
a) The dried samples were placed in a 250-ml glass beaker, to which 150 ml of heavy
liquid with the desired specific gravity was added. The heavy liquids used in this
research were prepared by dissolving 2 % (w/w) diocty 1 sodium sulfosuccinate (AOT-
100) in the organic liquids which are available commercially from Interstate Chemical
Co. Inc. (Heritage, PA), under the trade name of Certigrav. The specific gravity of
the heavy liquid was checked daily at room temperature. The solids concentration
was maintained at no more than 2.0% (v/v) (about 2.4 % (w/w)) for the +400 mesh
fraction and no more than 0.9% (v/v) (about 1.0 % (w/w)) for the -400 mesh size
fraction. The sink-float separations were conducted at specific gravities of 1.3, 1.5,
1.7, and 1.9.
b) The slurry thus prepared was ultrasonically conditioned for 2 minutes with stirring.
Then, the slurry was transferred to a 1000-ml polypropylene centrifuge bottle and
more heavy liquid was added to give a total volume of 800 ml. The slurry was stirred
for another 10 seconds before it was placed in the centrifuge.
c) The slurry was centrifuged in a RC-3B Refrigerated Centrifuge, Sorvall Instruments
(Du Pont), for 30 minutes at 1500 m (500 G). The temperature of the refrigerated
centrifuge was set at room temperature ( 22 5C).
d) After centrifugation, the float product was separated from the sink by suction using
a vacuum pump, taking care not to disturb the sink product. The float and sink
products were vacuum filtered and dried overnight in an oven at 80C. The float and
sink portions of the -400 mesh size fraction were weighed and prepared for sulfur and
ash analysis. The +400 mesh size materials were further separated into four size
fractions ( + 4 8 , 48x100, 100x200 and 200x400 Tyler Mesh) by screening in 8"
diameter standard sieves for 10 minutes using a Tyler, Ro-Tap sieve shaker. Then,
the products in each size-specific gravity fraction were weighed and prepared for
sulfur and ash analysis.
3.3. Sulfur and Ash Analysis
The total sulfur content for each size-specific gravity fraction was determined using
a Leco Sulfur Analyzer, with a Sulfur Titrator, Model 532-500, Laboratory Equipment Corp.
(St. Joseph, MI). The ash content was determined using a Fisher Coal Analyzer, Model 490.
The overall flow scheme for the evaluation of the yield, sulfur, and ash distributions
of the various samples is given in Figure 1.
192
Fk>tatioB
Product
+ 400-meeh sening
Screening b - 400-mesh
@400
I I I I I I I
(same as for S.G. 1.3) Float
Screening Screening
@4e-mesh @ 4 - mesh
1
1
@100 -mesh
@200 -mesh
Sink
Figure 1. Flow scheme for determining the size and specific gravity distribution of
flotation products.
4. DATA MANIPULATION
In the present study, the original coal sample was first separated into seven products
by froth flotation. These were then sub-divided by size and specific gravity to give a total
of 280 individual fractions. Each of the separation and analytical steps was of course, subject
to experimental error. Furthermore, there were inevitably cases where insufficient material
was available for complete analysis of some fractions. In order to obtain the best estimates
of the size-specific gravity distributions, some data smoothing is required and it is critical to
ensure a material balance both on the individual flotation products and on the overall sample.
In the present study, there were seven products to be analyzed for each flotation test,
which included the froth flotation products collected at 20, 40, 60, 120, 240, and 480
seconds, and the tails. An example of a complete data analysis for a flotation test on a
sample of -28 mesh coal (Upper Freeport) is presented in this paper. The sink-float tests
were conducted at the separation gravities of 1.3, 1.5, 1.7 and 1.9. The size fractions
consisted of + 4 8 , 48x100, 100x200, 200x400 and -400 mesh. When the amount of sample
from a single flotation test was not enough for all four sink-float tests, replicate flotation tests
were performed. The sink-float analysis at various specific gravities were conducted on the
individual samples so obtained without blending.
One result of the use of the cumulative method of sink-float analysis in which each
separation is performed on a separate sample is that subsequent size separations yield a set
of measured overall size distributions, one for each specific gravity tested. Ideally, these
193
should be identical since they are true replicates but, in practice, sampling and experimental
errors lead to discrepancies. In order to take advantage of the additional information thus
generated, we have adopted the following procedure for preliminary smoothing of the size-
specific gravity distributions:
a) Sieve analysis of the float and sink products obtained by gravity separation at
density pj leads to sets of Fy" and Sy" values in which Fy" is the weight percent of
the total sample which floats at pj and falls into size interval i, and Sy is the
corresponding weight percent which sinks at pj.
b) The sum, Fy'-hSy "=Qy" is the overall weight percent of the sample which falls in
size interval i, and should be the same, regardless of the separation density pj.
c) A refined estimate of the amount floating at density pj which, to some extent,
compensates for experimental error can be obtained using
F/ = 0 - S." (1)
where Q is the average over all j , i.e., the average overall percent falling in size
interval i:
J j=l
J is the total number of gravity separations carried out, 4 in the present study.
The raw data Fy" and refined estimates Fy' for the seven froth flotation products are
compared in Tables 1.1 and 1.2, 2.1 and 2.2, etc. For the most part, the differences are
small but, based on overall experience with these measurements, we feel that the refined
estimates are generally more reliable and consistent than the raw data.
Further examination of the data reveals that some anomalies remain. Physically, the
cumulative amount floating must increase monotonically with specific gravity. However, this
is not always reflected in the data, raw or refined. For example, the results for the -h48
mesh material in the 20-second product (Table 1.2) indicate more material floating at 1.5 than
at 1.7 and, for the 100x200 mesh fraction, more floats at 1.7 than at 1.9. Obviously, such
anomalies can arise whenever the sampling/analytical errors are comparable in magnitude to
the amount of material in a given specific gravity interval (1.5x1.7 and 1.7x1.9, respectively
in the above examples).
To eliminate these anomalous results, we have developed a regression procedure for
further smoothing of the data. Examination of a large number of sets of cumulative float data
indicates that they can generally be fitted to a function of the form:
194
where A, and c are constants for a given set and can be estimated by non-linear regression
of the (refined) data F^'. Given these parameter estimates, the final estimates of F^j can be
obtained by direct substitution into Equation 3. Some comparisons of the raw (Fy"), refined
(Fjj) and final (F^j) estimates are shown in Figure 2. More complete comparisons between
F-j and Fy estimates are given in Tables 1 through 7. It can be seen that this approach gives
reasonable estimates which do not vary widely from the original, raw data and automatically
satisfy the monotonicity constraint.
A similar approach has been taken in the analysis of the sulfur and ash data. For
these two cases, it is convenient to work in terms of sulfur or ash units A^j, By defined such
that Ajj is a measure of the relative amount of the total sulfur (or ash) content of the sample
which falls into size interval i and floats at specific gravity j and Bjj is the corresponding
value for the sink fraction. Thus,
Ay = ayFy (4)
where a^j is the measured weight percent sulfur (or ash) in the size i, pj float fraction.
Similarly,
By = b , ( Q , - F , ) (5)
where b^ is the sulfur (or ash) content of the size i, pj sink fraction. Individual values for
ajj and b^ are included (for both sulfur and ash) with the raw data given in Tables 1 to 7.
For those cases where the value of a^ is missing, the appropriate Ay value is estimated
using
(A^+B^)/K] -By k^j (6)
where the sum is determined for those float and sink pairs (K altogether) where both ay and
by are known. Similarly, when by is not known, the corresponding By value can be estimated
from Equation 7.
Table 1
The weight, ash and sulfur distribution in various size - specific gravity fractions of the 20-second flotation product
Table 1.1 The experimental data

II Weight, % II Sulfur, % Ash, %
Gravity Size Size Size
fraction +48 48x100 100x200 200x400 - 400 +48 48x100 100x200 200x400 - 400 +48 48x100 100x200 200x400 - 400
13 F 15.03 21.65 18.04 6JB2 3.31 93 86 82 82 7" 2.79 2.08 2.05 2.46 5.05
1.3 S 5.61 6.41 4.81 3.01 15.30 2.86 3.38 4.17 4.59 1.66 23.50 16.40 19.40 21.40 15.80
1.5 F 21.02 27.77 21.21 6.75 13.96 1.14 1.13 1.08 1.06 0.74 4.28 3.69 3.39 3.58 4.59
1.5 S 0.96 1.35 1.35 0.96 4.65 5.76 9.35 11.33 12.77 4.24 53.80 47.50 49.20 51.40 38.60
1.7 F 21.68 28.91 21.37 5.97 16.57 1.53 1.27 1.20 1.17 0.84 8.86 4.29 3.89 4.74 6.57
1.7 S 1.26 0.94 0.63 0.63 2.05 * * * * 7.84 * * * * 62.10
1.9 F 21.90 30.40 18.96 6.54 16.92 1.44 1.39 1.35 1.32 0.95 6.35 4.35 7.79 4.87 6.97
11.9 S II 0.98 0.65 0.98 0.98 1.691 * * * * 9.13a * * * * 71.50
Table 1.2 Refined estimates

I I Weight, % II Sulfur Unit II Ash Unit
fraction +48 48x100 100x200 200x400 - 400 + 48 48x100 100x200 200x400 - 400 + 48 48x100 100x200 200x400 - 400
1.3 F 16.50 23.11 17.03 4.91 3.31 15.42 19.88 13.97 4.06 2.35 46.25 48.08 34.94 12.17 16.94
1.5 F 21.15 28.17 20.49 6.95 13.96 23.55 31.76 22.19 7.27 10.41 88.41 103.70 69.65 24.55 64.54
1.7 F 20.86 28.58 21.21 7.28 16.57 32.24 36.33 25.08 8.27 13.46 186.72 122.72 81.29 33.49 105.27
1.9 F 21.13 28.87 20.86 6.93 16.92 30.71 40.18 28.49 9.49 16.43 135.40 125.74 164.42 35.01 120.55
Total I 22.11 29.52 21.84 7.91 18.61 I 31.59 43.29 35.41 19.21 28.46 171.54 162.17 130.63 77.22 214.76
Table 1.3 Final estimates

[ Weight, % [ Sulfur Unit || Ash Unit =

1.3 F 16.58 23.11 17.04 4.95 3.35 15.33 19.89 13.99 4.06 2.35 45.29 48.07 33.24 12.12 16.64
1.5 F 20.66 28.10 20.54 6.86 14.06 25.02 31.63 21.92 7.17 10.27 111.71 105.27 58.09 25.51 68.25
1.7 F 21.07 28.61 20.90 7.07 16.02 29.30 36.60 25.61 8.47 13.73 140.00 119.01 97.69 31.61 98.91
1.9 F 21.32 28.91 21.11 7.19 17.30 32.29 40.03 28.21 9.38 16.29 160.25 127.90 158.87 36.00 123.63
Total II 22.11 29.52 21.84 7.91 18.611| 33.17 43.14 35.12 19.10 28.32 ll 196.39 164.33 125.08 78.20 217.83
* - insufficient material available for analysis.
195
196
Table 2
Trie weight, ash and sulfur distribution in various size - specific gravity fractions of the 40-second flotation product
Jable2.1 The experimental data

II Weight, % ||~ Sulfur, % || Ash, %
fraction +48 48x100 100x200 200x400 -400 +48 48x100 100x200 200x400 -400 +48 48x100 100x200 200x400 -400
IT? 255 19^28 15.28 5T64 2.61 0.92 0.82 0.72 0.91 0.70 2.80 2.20 2.80 2.50 3.80
1.3 S 6.55 7.28 5.64 3.64 21.53 2.71 3.73 4.21 5.14 2.06 25.97 21.30 22.70 25.90 19.90
1.5 F 15.95 24.31 22.18 7.78 17.37 1.11 1.04 1.02 0.96 0.74 4.40 3.76 3.36 3.40 5.00
1.5 S 1.36 1.56 1.56 1.17 6.77 6.29 7.16 9.49 10.68 4.60 55.70 49.00 49.60 46.50 40.80
1.7 F 16.07 25.39 22.50 7.71 20.52 1.41 1.31 1.14 1.09 1.12 5.54 4.71 4.01 4.61 9.90
1.7 S 0.96 0.96 0.96 1.29 3.62 * * * * 6.54 * * * * 65.40
1.9 F 15.65 27.09 18.97 7.83 21.27 1.46 1.31 1.24 1.17 0.98 6.71 4.85 4.65 5.27 8.90
1.9 S I 2.11 2.11 1 51 0.60 2.87| 6.84 8.26 12.24 * 8.86II 78.20 73.30 * * 70.20

I I Weight, % II Sulfur Unit II Ash Unit
1.3 F 11.25 19.72 16.51 5.28 2.61 10.47 16.25 11.91 4.78 2.11 31.87 43.59 46.34 13.14 11.48
1.5 F 16.44 25.44 20.59 7.75 17.37 17.59 25.95 20.85 7.30 12.64 69.73 93.84 68.68 25.86 85.40
1.7 F 16.84 26.03 21.18 7.63 20.52 23.03 33.39 23.75 8.64 22.40 90.49 120.04 83.56 36.53 198.03
1.9 F 15.70 24.89 20.64 8.31 21.27 24.27 33.80 26.13 9.49 21.50 111.55 125.14 97.99 42.77 195.26
Total I 17.80 27.00 22 15 8.91 24.141 32.34 43.67 39.27 22.43 40.981 203.75 212.73 163.37 97.28 349.61

I II Weight, % |[ Sulfur Unit II Ash Unit
1.3 F 11.38 19.82 16.55 5.25 3.02 10.43 16.20 11.91 4.78 2.08 31.99 43.53 46.43 13.06 10.24
1.5 F 15.85 24.96 20.44 7.61 17.08 18.14 26.87 20.77 7.32 14.22 68.75 96.19 68.18 26.43 105.68
1.7 F 16.33 25.49 20.84 7.92 20.00 22.00 31.54 23.92 8.60 19.31 92.11 115.01 84.29 35.63 163.64
1.9 F 16.62 25.80 21.07 8.12 21.94 24.80 34.79 26.03 9.51 23.12 110.78 127.92 97.67 43.18 211.77
Total I 17.80 27.00 22 15 8.91 24.1411 32.87 44.66 39.17 22.44 42.601 202.98 215.51 163.04 97.70 366.12

Table 3

I [ Weight, % II Sulfur, % II Ash, %
1.3 F 9.28 13.34 12.76 6.96 6.64 0.94 0.79 0.72 0.80 0.90 2.43 2.19 2.01 2.27 2.29
1.3 S 7.83 9.28 7.25 4.93 21.72 3.83 3.60 4.84 5.33 2.25 27.30 22.20 25.60 29.10 25.00
1.5 F 14.15 21.82 20.34 6.78 18.81 1.18 1.18 1.06 1.05 0.94 5.90 5.11 4.55 4.39 6.51
1.5 S 2.36 2.65 2.36 1.18 9.54 6.38 9.56 11.00 * 4.27 61.80 54.50 55.00 * 45.50
1.7 F 12.97 22.23 21.93 7.10 23.04 1.24 1.27 1.33 1.16 1.08 6.55 5.44 4.94 5.56 9.48
1.7 S 1.54 2.16 1.85 1.85 5.32 5.78 7.92 9.35 13.30 6.04 70.90 66.20 65.30 64.30 60.80
1.9 F 12.92 23.88 19.39 7.87 22.91 1.53 1.31 1.33 1.33 1.07 8.47 6.61 6.12 6.51 9.71
1.9 S I 2.53 1.97 2.25 0.84 5.441 6.84 8.96 12.80 * 6.73J 80.20 78.20 75.50 * 75.30

I II Weight, % II Sulfur Unit II Ash Unit
1.3 F 8.07 15.05 14.78 4.45 6.64 7.64 11.94 10.69 3.58 5.97 19.76 33.11 29.85 10.15 15.20
1.5 F 13.54 21.68 19.67 8.20 18.81 15.61 25.33 20.60 8.10 18.14 78.06 109.69 88.44 33.86 125.65
1.7 F 14.35 22.17 20.18 7.53 23.04 17.15 28.15 26.49 9.40 23.69 90.59 120.57 98.40 45.07 207.93
1.9 F 13.37 22.37 19.78 8.54 22.91 21.72 29.58 26.88 11.10 25.30 120.23 149.27 123.67 54.33 229.55
[Total I 15.90 24.34 22.03 9.38 28.351 33.37 45.29 50.24 28.04 57.021 256.82 286.37 261.47 139.98 584.49

I II Weight, % If Sulfur Unit II Ash Unit
1.3 F 8.13 15.12 14.85 4.47 6.64 7.69 11.94 10.67 3.59 5.96 19.91 33.16 29.93 10.16 14.95
1.5 F 13.23 21.47 19.44 7.71 19.30 14.92 25.39 21.26 7.95 18.55 74.10 105.88 85.06 33.70 134.12
1.7 F 13.83 22.16 19.92 8.11 21.93 18.46 28.01 25.07 9.71 22.82 98.29 128.87 105.48 45.36 192.22
1.9 F 14.20 22.58 20.21 8.35 23.64 21.04 29.67 27.67 10.94 25.78 116.22 144.66 119.82 54.18 237.50
Total ll 15.90 24.34 22.03 9.38 28.351 32.69 45.37 51.03 27.88 57.50 II 252.81 281.76 257.62 139.83 592.44
197
198
Table 4

I I Weight, % II Sulfur, % II Ash, %
1.3 F 8.10 10.92 10.57 5.46 6.47 1.05 1.13 0.80 0.84 0.81 2.90 4.40 2.32 2.48 2.86
1.3 S 9.69 10.22 8.28 5.11 25.17 3.13 3.90 3.20 6.19 2.43 30.30 26.20 28.80 32.60 29.40
1.5 F 13.23 18.32 17.13 6.28 19.73 1.26 1.26 1.13 0.91 0.97 7.23 6.58 5.27 5.12 6.16
1.5 S 4.07 3.73 3.39 2.20 11.91 6.06 8.55 10.40 10.50 4.23 60.80 57.20 57.30 57.90 50.90
1.7 F 14.00 20.67 17.67 5.00 22.76 1.40 1.33 1.28 1.44 1.11 8.37 7.06 6.36 6.81 8.98
1.7 S 3.00 3.00 3.00 2.00 8.89 7.36 8.33 11.50 13.10 5.41 74.50 73.20 70.90 69.20 64.70
1.9 F 13.82 21.29 15.69 7.84 24.54 1.65 1.59 1.55 1.49 1.17 9.58 8.14 7.19 8.00 10.50
11.9 S II 2.24 2.61 2.61 2.24 7.111| 5.02 7.71 11.20 13.30 6.66|| 80.70 78.40 78.00 75.10 70301

I I Weight, % |[ Sulfur Unit II Ash Unit 1
1.3 F 7.35 12.47 11.31 3.93 6.47 7.71 14.11 9.08 3.34 5.22 21.29 54.94 26.33 9.87 18.43
1.5 F 12.97 18.96 16.19 6.83 19.73 16.33 23.81 18.22 6.00 19.18 93.68 124.35 84.99 33.74 121.78
1.7 F 14.04 19.69 16.59 7.03 22.76 19.68 26.13 21.31 9.94 25.18 117.66 138.70 105.90 46.99 203.73
1.9 F 14.80 20.08 16.97 6.79 24.54 24.33 31.95 26.30 10.56 28.77 141.27 163.59 121.98 56.71 258.22
[Total I 17.04 22.69 19.59 9.03 31.6|| 35.84 51.96 55.65 36.44 75.761| 326.34 367.01 326.42 202.84 7541221

I [I Weight, % || Sulfur Unit II Ash Unit
1.3 F 7.34 12.49 11.35 3.98 6.44 7.75 14.19 9.13 3.25 5.22 21.31 55.00 26.34 9.86 18.09
1.5 F 12.96 18.90 16.13 6.59 19.77 15.89 22.96 17.67 6.61 19.32 92.50 121.61 84.75 33.86 125.20
1.7 F 14.06 19.65 16.65 6.90 22.69 20.46 27.68 22.31 9.00 24.90 120.06 144.63 106.40 46.78 198.24
1.9 F 14.75 20.10 16.97 7.09 24.59 23.94 31.16 25.80 10.99 28.92 139.99 160.30 121.71 56.81 260.77
Totaj_J| 17.04 22.69 19.59 9.03 31_,65j| 35.45 51.17 55.15 36.87 75.91 II 325.06 363.72 326.15 202.94 756T7
Table 5
Tbe weight, ash and sulfur distribution in various size - specific gravity fractions of the 240-second flotation product

I Weight, % II Sulfur, % II Ash, % I
1.3 F 5.49 8.42 6.59 3.66 0.64 1.01 0.83 0.84 0.63 * 3.33 2.59 2.69 3.01 *
1.3 S 13.55 14.65 9.89 6.59 30.51 3.85 4.18 5.81 6.80 2.47 45.80 33.30 40.70 41.90 35.70
1.5 F 16.08 18.18 11.88 5.94 14.80 1.24 1.33 1.15 1.35 0.92 8.16 8.61 7.49 7.35 6.76
1.5 S 4.89 4.54 4.19 3.15 16.34 5.68 7.92 8.95 9.49 3.92 60.40 57.30 57.60 60.30 51.30
1.7 F 16.08 18.20 12.44 6.07 13.39 1.36 1.33 1.52 1.33 1.10 11.10 9.56 9.82 9.01 10.60
1.7 S 5.46 3.94 3.64 3.03 17.75 6.43 9.00 10.70 13.30 3.36 67.80 71.20 70.60 70.50 50.80
1.9 F 16.07 20.37 14.63 6.02 21.28 1.77 1.70 1.69 1.54 1.04 10.70 10.70 10.60 10.20 11.00
JL9S ll 3.44 3.16 3.16 2.01 9.871| 7.16 9.48 12.30 12.90 6.181 78.00 78.40 76.60 75.60 7_7^4]

I I Weight, % ~|| Sulfur Unit II Ash Unit
1.3 F 6.71 8.22 6.72 2.53 0.64 6.89 6.90 5.69 1.59 5.80 22.73 21.52 18.21 7.59 17.51
1.5 F 15.37 18.32 12.41 5.97 14.80 18.24 23.72 14.17 7.82 12.01 120.03 153.58 92.31 42.59 88.27
1.7 F 14.81 18.92 12.97 6.09 13.39 21.46 25.44 19.78 8.61 18.47 175.12 182.83 127.82 58.31 178.02
1.9 F 16.82 19.71 13.45 7.11 21.28 29.09 33.86 22.71 10.63 20.24 175.86 213.13 142.45 70.42 214.04
Total I 20.27 22.87 16.61 9.12 31.14|| 56.52 61.80 61.68 39.21 92.451 474.62 444.16 385.10 237.88 1118,46]

I I Weight, % II Sulfur Unit 11 Ash Unit 1
1.3 F 6.83 8.31 6.77 2.52 0.83 7.00 6.93 5.67 1.59 5.71 22.68 21.52 18.17 7.59 16.05
1.5 F 14.71 17.84 12.32 5.79 13.06 17.15 22.38 14.46 7.56 12.76 126.96 151.78 94.41 42.55 98.46
1.7 F 15.78 19.12 13.02 6.47 16.79 23.31 28.22 19.27 9.19 17.24 160.39 186.79 123.56 58.39 162.89
1.9 F 16.44 19.92 13.44 6.90 19.46 28.20 32.36 22.97 10.31 20.83 183.93 210.92 144.73 70.38 220.76
Total I 20.27 22.87 16.61 9.12 31.141 55.62 60.30 61.93 38.88 93.041 482.69 441.95 387.39 237.83 1125.181
* insufficient material available for analysis.
199
200
Table 6
The weight, ash and sulfur distribution in various size - specific gravity fractions of the 480-second flotation product.

I Weight, % | Sulfur, % II Ash, %
1.3 F 7.71 6.94 3.08 0.77 0.00 1.22 1.08 0.82 0.82 0.00 5.34 3.33 2.40 3.54 0.00
1.3 S 21.96 18.88 10.40 4.24 26.02 4.81 5.56 6.05 7.46 3.39 44.60 43.90 47.00 48.80 48.40
1.5 F 17.48 15.27 8.28 3.68 6.90 1.35 1.37 1.06 1.10 0.88 7.66 9.00 8.61 8.19 8.40
1.5 S 9.20 8.65 6.99 4.42 19.12 4.64 7.71 10.50 10.40 4.20 58.20 63.10 65.10 66.80 60.10
1.7 F 19.60 19.05 9.06 4.44 10.41 1.64 1.68 1.50 1.32 0.86 11.00 12.00 13.20 12.10 10.90
1.7 S 7.03 6.10 4.99 3.70 15.61 6.96 9.66 12.30 11.90 4.78 73.50 70.80 71.20 73.40 70.40
1.9 F 22.45 18.03 9.38 3.86 13.14 1.40 1.92 1.88 1.56 0.97 16.00 15.00 14.20 14.10 12.80
1.9 S I 7.73 5.52 4.23 2.76 12.881 5.38 10.50 11.80 15.40 5.4611 78.00 76.40 75.90 75.80 76.40

I II Weight, % |[ Sulfur Unit II Ash Unit
1.3 F 6.33 5.73 3.71 2.73 0.00 8.05 6.16 3.06 2.01 0.00 35.25 18.99 8.97 8.68 0.00
1.5 F 19.09 15.96 7.12 2.55 6.90 25.16 22.11 7.68 3.21 6.07 142.75 145.26 62.40 23.88 57.92
1.7 F 21.26 18.51 9.11 3.27 10.41 33.60 30.39 13.29 4.54 8.91 225.34 217.07 116.96 41.59 112.89
1.9 F 20.56 19.09 9.88 4.21 13.14 30.31 37.13 18.83 6.27 12.75 346.42 290.07 142.20 56.65 168.19
Total I 28.29 24.61 14.11 6.97 26.021 66.03 92.49 67.13 51.69 83.101| 864.22 692.91 452.90 280.21 1152.61

Ii Weight, % || Sulfur Unit II Ash Unit I
1.3 F 6.60 5.70 3.74 2.45 0.00 8.05 6.16 3.02 2.03 0.00 37.95 19.21 8.45 8.49 0.00
1.5 F 18.64 16.14 7.25 2.92 6.89 26.62 22.04 7.81 3.17 5.77 133.54 142.54 67.32 24.58 57.67
1.7 F 20.49 18.09 8.86 3.44 10.36 30.11 30.51 13.15 4.58 9.41 235.96 221.57 109.23 40.75 113.23
1.9 F 21.65 19.34 10.01 4.02 13.14 32.36 37.07 18.88 6.26 12.52 342.40 287.94 145.75 56.97 168.04
Total I 28.29 24.61 14.11 6.97 26.021 68.07 92.44 67.18 51.68 82.87 [ 860.19 690.78 456.45 280.54 1152.461
Table 7
The weight, ash and sulfur distribution in various size - specific gravity fractions of the tails

I I Weight, % || Sulfur, % II Ash, % I
1.3 F 7.52 1.58 0.59 0.40 0.00 1.08 * * * 0.00 8.40 2.90 * * 0.00
1.3 S 51.22 17.80 6.72 2.77 11.40 6.66 7.55 8.59 10.10 ** 58.10 61.80 69.80 69.50 **
1.5 F 16.91 3.38 0.68 0.45 0.00 1.45 1.59 * * 0.00 11.70 15.00 * * 0.00
1.5 S 41.48 16.23 6.99 2.48 11.40 6.35 9.02 9.88 10.70 ** 67.90 71.70 76.00 76.00 **
1.7 F 23.57 5.24 0.87 0.44 1.02 1.85 2.06 * * 1.18 17.00 21.40 * * 12.30
1.7 S 39.50 13.31 4.36 1.31 10.38 7.94 9.95 9.15 9.16 4.29 74.40 76.00 77.80 77.20 79.60
1.9 F 19.98 9.05 2.64 0.75 1.94 2.50 4.59 3.49 * 1.12 21.00 24.00 29.60 * 16.80
11.9 S I 33.55 13.20 7.16 2.26 9.461 10.20 12.00 12.90 13.90 4.111 78.70 77.60 78.00 77.20 82.0o|

I Weight, % ||~ Sulfur Unit || Ash Unit
1.3 F 7.21 2.15 0.78 -0.05 0.00 7.85 2.25 0.85 0.03 0.00 61.08 6.03 4.47 0.15 0.00
1.5 F 16.95 3.72 0.52 0.23 0.00 23.27 6.76 1.91 0.82 0.00 187.78 63.74 16.76 7.18 0.00
1.7 F 18.93 6.64 3.14 1.40 1.02 38.12 11.98 2.65 1.39 1.03 350.34 124.45 22.90 11.99 10.74
1.9 F 24.88 6.75 0.34 0.45 1.94 60.04 32.72 4.95 2.44 2.22 504.37 171.09 41.96 19.07 33.33
Total I 58.43 19.95 7.51 2.71 11.401 411.07 186.54 83.48 28.57 40.921 3212.81 1165.79 516.82 164.18 805.51

I I Weight, % ||~ Sulfur Unit II Ash Unit
1.3 F 7.27 2.08 0.79 0.03 0.00 8.35 1.75 1.03 0.03 0.00 59.32 5.56 3.12 0.02 0.00
1.5 F 16.05 4.25 1.26 0.54 0.21 22.00 5.13 3.10 1.30 0.20 193.24 66.38 23.74 10.29 1.36
1.7 F 20.61 5.82 1.36 0.71 0.87 39.33 13.47 4.14 2.19 0.92 344.37 120.77 34.50 18.23 10.25
1.9 F 24.02 7.13 1.42 0.83 1.98 59.64 32.38 4.92 2.97 2.25 506.55 172.66 43.00 25.46 33.43
iTotal I 58.43 19.95 7.51 2.71 11.401| 410.67 186.20 83.45 29.10 40.951 3214.99 1167.36 517.86 170.58 805.60

** - sample not to be analyzed.
201
202
Q
-J
UJ
>-
1.4 1.6 1.8

SPECIFIC GRAVITY
Figure 2. Yield distribution in the floats as a function of specific gravity

for the 20-second flotation product. Open symbols - experimental data; solid
symbols - refined estimates; Line - final estimates; o, - +48 mesh;
V, - 48x100 mesh; . - 100x200 mesh; , a - 200x400 mesh; O , - -400 mesh.
BiJ = (7)
5:(A^-B^)/K
k
The sulfur and ash units, obtained using Equations 4, 5, 6 or 7 as appropriate, are given in
Tables 1.2, 2.2, etc.
In some cases, notably for the flotation tails, there are too many missing values for
Equations 6 and 7 to give reliable estimates. Examination of the complete data set obtained
in this study reveals that the sulfur and ash content of the various specific gravity fractions
(1.5 floatete.,) is relatively independent of particle size, especially for the long-time flotation
products and the flotation tails. Consequently, we have simply assigned values to these
missing entries based on the average sulfur or ash content of those samples in that fraction
of that particular flotation product for which actual values are available. Since, by definition,
these values belong to fractions containing very little material, the overall errors introduced
by this estimation procedure are generally negligible.
The sulfur and ash units should also increase monotonically with specific gravity for
any given size. Again, examination of the results indicates cases where this constraint is
violated. For example, in Table 1.2, the sulfur units for +48 mesh, 1.7 float are greater
than for the 1.9 float. Further smoothing of the data using an analog of Equation 3 was
adopted, therefore, to eliminate these anomalies in the sulfur and ash data. Examples of the
203
i

-J
D
SPECIFIC GRAVITY SPECIFIC GRAVITY
Figure 3. Sulfur distribution in the floats Figure 4. Ash distribution in the floats as
as a function of specific gravity for the a function of specific gravity for the
120-second flotation product. Symbols - 120-second flotation product. Symbols -
refined estimates; Line - final estimates, refined estimates; Line - final estimates,
o - + 4 8 mesh; - 48x100 mesh; o - + 4 8 mesh; - 48x100 mesh;
V - 100x200 mesh; - 200x400 mesh; V - 100x200 mesh; - 200x400 mesh;
- -400 mesh. - -400 mesh.
smoothed data are shown in Figures 3 and 4 for sulfur and ash respectively. The complete
results are given in Tables 1.3, 2.3, etc..
5. MATERIAL BALANCE
As final check on the reliability of the approach, material balances were conducted on
the individual froth flotation products and the original feed coal. Direct sulfur and ash
measurements were also performed on composite samples of the feed and products. The
results of the material balances are summarized in Table 8.
Table 8
Material baUince for the overall froth products
Assay. %
Product Weight Direct measurments Refined estimates Final estimates
% Ash Sulfur Ash Sulfur Ash Sulfur
20 sec. 23.37 7.32 1.50 7.48 1.57 8.01 1.70
40 sec. 12.18 9.89 1.81 10.21 1.78 10.45 1.88
60 sec. 7.23 12.05 1.89 15.45 2.17 15.24 2.14
120 sec. 12.26 18.16 2.27 19.77 2.56 19.75 2.55
240 sec. 11.11 23.74 2.90 26.60 3.12 26.61 3.11
480 sec. 11.22 31.10 3.66 34.43 3.60 34.16 3.62
tails 22.63 60.12 7.51 58.65 7.51 58.46 7.49
Total 100.00 25.75 3.42 26.62 3.50 26.69 3.54
6. SUMMARY DISCUSSION
A procedure to determine size and specific gravity distributions was developed to
analyze froth flotation products. This method was used to determine the rate of flotation of
204
individual size-specific gravity fractions and the results are discussed in another article in this
publication. A cumulative, rather than incremental procedure was used because errors are
obscured in the latter. Because of the nature of the raw coal sample used in this study, the
quantity of material in some size-gravity fractions was small. Such a situation led to
anomanlous results. Data smoothing procedures were developed to estimate the errors and
eliminate the anomolous results. The reliability of our approach was tested by conducting
an overall material balance on the individual froth flotation products and the original feed
coal.
7. REFERENCES
Dyrkacz, G.R., Ruscic, L., and Fredericks, J., 1992, "An investigation into the process of
centrifugal sink/float separations of micronized coals. 1. Some interferences for coal
maceral separations," Energy and Fuel, 6:720-742.
Cavallaro, J.A. and Killmeyer, R.P., 1988, "Development of a centrifugal float/sink

procedure for gravimetric evaluation of ultrafine coals," Journal of Coal Quality, No. 2,
7:55-61.
Dumm, .F. and Hogg, R., 1987a, "Washability of ultrafine coal," Minerals and
Metallurgical Processing, February, pp. 25-32.
Dumm, .F. and Hogg, R., 1987b, "Distribution of sulfur and ash in ultrafine coal,"
Processing and Utilization of High Sulfur Coals II, Eds., Y.P. Chugh, R.D. Caudle,
Elsevier, NY, pp. 23-32.
LIST OF SYMBOLS
Pj - specific gravity of Certigrav.
Fij",Fij', Fij - the raw, refined, and final estimates of the weight percent of the total
sample which floats at pj and falls into size interval i.
Sj",Sj', Sj - the raw, refined, and final estimates of the weight percent of the total
sample which sinks at Pj and falls into
size interval i.
Qij" - the overall weight percent of the sample which falls into size interval i.
Qi - the average overall weight percent of the sample which falls into size
interval i.
A,B,c - constants for a given set of data smoothing (Fy = A(pj-B)0.

205
ay - the measured weight percent sulfur (or ash) in the size i, Pj float
fraction.
by - the measured weight percent sulfur (or ash) in the size i, pj sink
fraction.
Ay - sulfur (or ash) units, a measure of the relative amount of the total sulfur
(or ash) content of the sample which falls into size interval i and floats
at Pj.
By - sulfur (or ash) units, a measure of the relative amount of the total sulfur
(or ash) content of the sample which falls into size i and sinks at pj.
Selective flocculation of aqueous coal suspensions with polyethylene oxide
V^. R. VanBemmel and T. D. Wheelock
Iowa State Mining and Mineral Resources Research Institute and

Department of Chemical Engineering, Iowa State University, Ames, Iowa 50011
Aqueous suspensions of Colchester Seam coal from Illinois were flocculated at 25C and
95C by using polyethylene oxide (PEO) having a molecular weight of about 100,000.
Turbidity measurements on coal suspensions showed that raising the suspension temperature
from 25 C to 95C increased the degree of particle aggregation. Coal particles were
selectively flocculated from mixed suspensions of coal and kaolin particles by using PEO at
both 25C and at 95C. In general, coal recovery was higher at 95C than at 25''C for a
given dosage of PEO. Increasing the solids concentration in the range of 1.6 to 4.0%
reduced the amount of PEO required to achieve a high coal recovery while not greatly
affecting the separation efciency.
1. INTRODUCTION
Various methods based on particle surface chemistry have been proposed to clean coal
nes in aqueous suspensions. Among these methods are selective oil agglomeration,
microbubble flotation, flocculation, and coagulation. Selective flocculation has been achieved
by using long chain polymers which selectively adsorb onto the surface of specic kinds of
particles and form bridges or links between particles. Attia and Driscoll [1] reported
selective flocculation of coal by using a hydrophobic polymer having a molecular weight of
less than one million. A polymer dosage of only 0.02 mg/g of coal was required for
selective flocculation, while sodium metaphosphate was used to keep the mineral particles
in suspension.
Yoon et al. [2] reported the separation of coal and mineral matter particles by selective
coagulation of the coal particles in an aqueous suspension using no flocculating agent. It was
believed that coagulation of the coal particles was due to a positive hydrophobic interaction
force. The hydrophobic interaction was thought to be caused by the tendency of water to
form an ordered structure due to hydrogen bonding. Hydrophobic particles are forced
together in order to maximize the ordered structure of the water molecules.
Gochin and Lekili [3] studied the flocculation mechanism of anthracite coal particles in
suspension using polyethylene oxide (PEO) with a molecular weight in excess of 5 million.
It was reported that PEO adsorbed onto the coal surface and caused particle flocculation by
bridging. However, oxidized coal could not be flocculated with PEO due to poor adsorption
onto the oxidized surface. It was also found that particle flocculation with PEO was
increased by the addition of soluble salts.
208
The effect of temperature on flocculation of mineral particles rendered hydrophobic by

ionic surfactants was studied by Lu and Song [4]. They found that the degree of flocculation
increased with increasing temperature, and explained the behavior in terms of the
thermodynamics of the system. The free energy change (AG) accompanying particle
aggregation would be related to the enthalpy change () and entropy change (AS) at a given
temperature (T) by the well-known relation,
AG = - TAS W
For a positive entropy change which is large enough so that
|TAS| > | A H | , (2)
the free energy change would be negative and flocculation would take place spontaneously.
Moreover, as the temperature increased, the negative free energy change would become
greater which would cause even more flocculation.
Napper [5] studied flocculation of sterically stabilized latex particle suspensions by
lowering the solubility of the stabilizing species by changing the suspension temperature. It
was reported that a suspension stabilized with PEO in an aqueous salt solution was
flocculated upon heating the suspension above the theta temperature. At the theta
temperature, the enthalpy change accompanying the close approach of two particles becomes
small compared to the entropy change. When a system flocculates upon increasing the
temperature, the entropy change accompanying flocculation is positive.
From the literature cited, it is apparent that increasing the temperature of an aqueous
suspension of hydrophobic particles may increase the degree of particle aggregation.
Furthermore, heating a particle suspension stabilized with PEO may induce particle
aggregation.
Previous work in our laboratory showed that fine coal particle suspensions were stabilized
with Triton NlOl surfactant from Rohm and Haas [6]. Heating coal suspensions that were
stabilized with the surfactant above the cloud point temperature of the surfactant solution
resulted in flocculation of the coal particles. Furthermore, coal particles were selectively
flocculated from mixed suspensions of coal and kaolin particles. However, large amounts
of the surfactant (at least 10% of the coal weight) were required to obtain a good separation
of coal and kaolin.
In the present investigation, the effects of PEO concentration and temperature on the
stability of suspensions of fine coal particles were determined by monitoring the turbidity of
the suspensions as they were heated from 25 to 95C. Since the turbidity of a suspension
is proportional to particle concentration, a decrease in the turbidity was indicative of particle
aggregation or flocculation. In addition, the use of PEO to promote the selective flocculation
of coal, particularly at an elevated temperature, was evaluated by conducting flocculation
tests with artificial mixtures of coal and kaolin particles and determining the recovery of coal
and "ash" in the flocculated product. The "ash" largely reflected the amount of kaolin
present.
209
100
Nominal Diameter, m
Figure 1. Cumulative particle size distribution for ground Colchester coal.
2. MATERIALS AND EXPERIMENTAL METHODS
A handpicked sample of moderately hydrophobic coal was obtained from the Colchester
Seam in Schuyler County, Illinois. The coal had a moisture free ash content of 4.0% and
a total sulfur content of 2.3%. The coal was crushed and then ground in a high speed impact
mill to - 1 2 5 particle size. It was then wet ball milled to a volume media diameter of
about 12 ^m. The particle size distribution for the ball milled coal was determined with a
Mitrotrac particle size analyzer (Leeds and Northrup, Model 7991-01) and is shown in Figure
1. The ball milled coal was stored as a filter cake containing 50% water in a refrigerator
at a temperature of about 0C. Acid washed kaolin powder from Fisher Scientific was used
in separation tests. When the kaolin powder was heated to the coal ashing temperature of
725C, it suffered a 12% loss in weight so that the original material appeared to have an
"ash content" of 88%. Polyox WSR NIO polyethylene oxide having a molecular weight
of about 100,000 was obtained from Union Carbide. A 0 . 1 % aqueous solution of PEO,
prepared from the dry powdered material, was used in the experiments. Dilute solutions of
hydrochloric acid and sodium hydroxide prepared from Mallinkrodt reagents were used for
pH adjustment.
To determine the effect of PEO on the stability of a coal suspension, 2 g (dry weight) of
ground coal was first blended with 250 ml of deionized water for 5 min. using a 14-speed
kitchen blender operated at the lowest speed setting. Prior to blending, sufficient sodium
hydroxide was added so that the suspension pH was from 9 to 10 after blending. The higher
pH helped disperse the coal. After blending, the suspension was transferred to a 600 ml
210
beaker where other reagents including PEO were added. The suspension was diluted to
500 ml, and the pH was adjusted to the desired value. The beaker was placed on a
combination hot plate/magnetic stirrer and heated at a rate which caused the temperature to
rise at about 4C/min. At the same time the suspension was stirred at a moderate rate, a
small stream of the suspension was pumped through a turbidity measuring cell of a
photometric dispersion analyzer (PDA 2000 manufactured by Rank Brothers, Ltd.). After
passing through the cell, the stream of material was returned to the beaker. A peristaltic
pump was used for pumping the suspension. The output signal from the dispersion analyzer
was recorded continuously.
Mixed suspensions of coal and kaolin particles were prepared for separation tests by
blending 4, 8, 12, or 16 g of coal with 4 g of kaolin in 250 ml of water adjusted to pH 9-10.
Blending was accomplished with a 14-speed kitchen blender operated at the lowest speed
setting for 5 min. The suspensions were diluted to 500 ml to produce suspensions which
contained 1.6, 2.4, 3.2, and 4.0% solids having an apparent ash content of 46, 33, 26, and
2 1 % , respectively. After the preceding dilution, a PEO solution was added to each
suspension. The pH was adjusted next to the desired value for a given test. The suspension
was then stirred magnetically while flocculation took place. Some of the suspensions were
heated to 95C for flocculation and settling. Others were flocculated and settled at 25C.
The suspensions were allowed to settle for 2-5 min., depending on how long it took to form
a distinct interface between the settling particles and the clear supernatant. The upper 400 ml
of liquid was then withdrawn and filtered. The remaining suspension was also filtered. The
recovered solids were dried, weighed, and analyzed for ash content.
Coal recovery in the settled material on a dry, ash-free (daf) basis was calculated by
means of the following expression:
x^Mi
Coal recovery (%) = 100 (3)
XjMj + X2M2
where Mj = mass of dry, settled solids, g

M2 = mass of dry solids in the supernatant, g
Xj = organic content of dry, settled solids, %
X2 = organic content of dry solids in the supernatant, %.
The recovery of ash in the dry, settled material was determined by a similar expression
shown below.
yiMi
Ash recovery (%) = 100 W
where y^ = ash content of dry, settled solids, %

y2 = ash content of dry solids in the supernatant.
211
For calculating coal recovery, the organic content of the solids was estimated by using the
following approximate relation:
Xi = 100 - y- (5)
The separation efficiency was determined by subtracting the ash recovery from the coal
recovery.
The effects of temperature and PEO concentration on the stability of ground coal
suspensions are indicated by Figure 2. It can be seen that the turbidity of the suspensions
decreased gradually as the temperature was raised from 25C to 65C and then more steeply
as the temperature was raised further. In addition, the turbidity was lower when PEO was
present initially, and the rate of decrease of turbidity with respect to temperature was greater
when PEO was present. A PEO concentration of 5 ppm seemed to have a greater effect than
a concentration of 25 ppm on the turbidity except at temperatures of 90 ""C and greater.
These results indicated that small concentrations of PEO tended to destabilize coal
suspensions by promoting particle aggregation, especially at higher temperatures.
The effects of PEO concentration and temperature on coal suspension stability were
investigated further, and the results shown in Figure 3 were obtained with two different
batches of ground coal. The different batches produced results which were generally similar;
the slight differences between batches may have been due to surface oxidation which was not
controlled completely by storing the wet, ground coal at 0C. In conducting the tests which
are represented by Figure 3, it was observed that the turbidity of some suspensions continued
to decrease after the temperature peaked at 95C and was going down. Therefore, the
turbidity reported for the higher temperature was actually the minimum turbidity observed
either at 95C or shortly after this temperature was passed. It is apparent that the turbidity
observed at 95''C or beyond was considerably lower than that observed at 25''C. In addition,
it can be seen that the turbidity at 25C declined as the PEO concentration was increased to
5-10 ppm and then increased with a further increase in PEO concentration. At the higher
temperature the turbidity decreased with increasing PEO concentration until a concentration
of 10-20 ppm was reached and then leveled off.
All of the preceding results were obtained at pH 8. Other tests showed that in the absence
of PEO the stability of a coal suspension was slightly greater at pH 9 than at pH 8 [6]. Also
at pH 9 the stability of a coal suspension decreased only slightly over a temperature range
from 25 to 95C. In addition, it was observed that in the absence of PEO, kaolin
suspensions were stable above pH 6, whereas they coagulated below this pH. Therefore, a
pH of 8 or higher was used for the selective flocculation tests which followed.
To investigate the effects of several important parameters on the separation of coal and
kaolin by selective flocculation, a series of flocculation tests was carried out in which the
suspension temperature, solids concentration, and PEO dosage were varied, and the coal
recovery and separation efficiency were determined. The results are presented in Figures
4 to 7 for different solids concentrations.
212
100
Temperature, C
Figure 2. Effects of initial PEO concentration and temperature on turbidity of coal

suspensions at pH 8.
o batch l , 2 5 o C
batch l , 9 5 o C
A batch2, 2 5 o C
batch 2, 9 5 o C
20 30 50
PEO Concentration, ppm
Figure 3. The effect of PEO concentration on Colchester coal suspensions at pH 8.

213
The results achieved at the lowest solids concentration (1.6%) are indicated in Figure 4.
In this case for each flocculation test 4 g coal and 4 g kaolin were used which was equivalent
to starting with a coal with 46% ash when the apparent "ash" contents of both the coal and
kaolin were taken into account. It can be seen that for any given PEO dosage coal recovery
was considerably greater at 95C than at 25C. At a PEO dosage of 5 g/kg daf coal, the
recovery at 95C was 87% in comparison to a recovery of 62% at 25C. At either
temperature the separation efficiency was 3 3 % . Increasing the PEO dosage increased coal
recovery only slightly at 95C and actually decreased the recovery at 25C, while having
little effect on separation efficiency.
When the solids concentration was increased slightly to 2.4%, the results shown in Figure
5 were obtained. Compared to the previous case, coal recovery and separation efficiency
were both greater, especially at lower PEO dosages. For example, at 95C with a PEO
dosage of 1.25 g/kg daf coal and a solids concentration of 2.4%, the recovery and separation
efficiency were 88% and 45%, respectively, whereas with the same PEO dosage and a solids
concentration of 1.6%, the recovery and separation efficiency were 6 1 % and 28%,
respectively. A larger dose of PEO had only a slight effect on coal recovery and separation
efficiency at 95C. On the other hand, at 25C the results were much more sensitive to a
change in PEO dosage, and the maximum recovery (78%) and separation efficiency (49%)
were achieved with a PEO dosage of 3.75 g/kg daf coal. With this dosage the difference in
results achieved at different temperatures was small, whereas with either higher or lower
dosages the difference in results was much greater.
A further increase in solids concentration to 3.2% achieved the results presented in Figure
6. Again it can be seen by comparing these results with the previous ones that an increase
in solids concentration resulted in an increase in coal recovery at both 25" and 95C. At
the higher temperature, coal recovery reached 95% with a PEO dosage of 1.25 g/kg daf coal
or more, and a recovery in excess of 90% was realized with a PEO dosage of only 0.6 g/kg
daf coal. Although coal recovery was less at the lower temperature than that at the higher
temperature, it approached that achieved at the higher temperature as the PEO dose was
increased. Consequently, the recoveries observed at different temperatures were nearly the
same for a PEO dosage of 2.5 g/kg daf coal.
While the increase in solids concentration from 2.4% to 3.2% increased coal recovery at
both 25C and 95C, it affected the separation efficiency differently. A comparison of
Figures 5 and 6 for PEO doses in the range of 0.6 to 2.5 g/kg daf coal shows that an
increase in solids concentration resulted in a slight decrease in separation efficiency at 95C
and in an increase in separation efficiency at 25C, although the increase in separation
efficiency was negligible at the highest PEO dosage.
A final increase in solids concentration to 4.0% produced the results indicated by Figure
7. In this case only results obtained at 25C are presented. Two sets of results are
indicated, one having been obtained at pH 9 and another at pH 10. A comparison of the
results obtained at pH 9 with those shown in Figure 6 for a lower solids concentration shows
that the increase in solids concentration again resulted in an increase in coal recovery. On
the other hand, the separation efficiency was not affected noticeably by the increase in solids
concentration. Therefore, a coal recovery of 92% and a separation efficiency of 44% were
achieved with only 1.25 g PEO/kg daf coal at the higher solids concentration.
Figure 7 shows that an increase in pH from 9 to 10 substantially reduced both coal
recovery and separation efficiency for a PEO dosage of 0.6 g/kg daf coal. However, with
214
100
60 h
^ ^ e c . . 250C
Ig 40
20 h
0.0
1- J
2.5
1
5.0
Êff.,25oC
7.5 10.0
PEO Dosage, g/kg daf coal
Figure 4. Results of flocculation at pH 8 with PEO using Colchester coal/kaolin suspensions

containing 1.6% solids with an apparent ash content of 46%.
100
2 4

containing 2.4% solids with an apparent ash content of 3 3 % .
215
100

; 80 -
-""^Rec., 250C
Êff^25oC
g Ol -0
Eff.,95oC
20 h
1

^ 100 1
Rec.,pH9^
80 -
! RecpHlO
I ^^,,^^-^-'*" EffpH9
^,^"^ff..pH10
S 40
20 h
Figure 7. Results of flocculation at 25 ""C with PEO using Colchester coal/kaolin suspensions
216
a PEO dosage of 1.25 g/kg daf coal, the increase in pH resulted in only a slight decrease in
recovery and separation efficiency.
4. CONCLUSIONS
Dilute suspensions of fine particles of Colchester Seam coal from Illinois were destabilized
by low concentrations of PEO, especially as the temperature increased to 95C. Particle
aggregation or flocculation seemed to be in accord with the effect of temperature on the free
energy change for the process as indicated by equation 1. In other words, particle
flocculation increased with increasing temperature because the negative value of the free
energy change became greater which meant that TAS had to be larger than for the
process. While this result suggests that adsorption of PEO on the coal surface increased the
hydrophobicity of the coal and thereby promoted hydrophobic coagulation of the particles,
this mechanism does not seem very likely because PEO is water avid. Even more unlikely
is that flocculation was due either to particle bridging or electrical charge neutralization by
PEO since the material was nonionic and of relatively low molecular weight. Another
possibility is that PEO served as a dispersant for mineral slimes or kaolin particles, which
interfered with the hydrophobic coagulation of the coal particles. Obviously, further work
is needed to provide a satisfactory explanation of the mechanism.
Separation of coal and kaolin mixtures by selective flocculation with PEO showed that
coal recovery and separation efficiency were affected by particle concentration, PEO dosage,
and temperature. As particle concentration increased in the range of 1.6 to 4.0%, coal
recovery with a given dose of PEO increased substantially, whereas separation efficiency was
affected less. Coal recovery was always greater at 95C than at 25C. With smaller
amounts of PEO, coal recovery increased with increasing PEO dosage, but beyond an
optimum dosage the recovery either decreased or remained unaffected by a further increase
in dosage. The maximum coal recovery (95%) was achieved by using an optimum PEO
dosage (1.25 g/kg daf coal), the highest temperature (95C) and a relatively large particle
concentration (3.2%). For this set of conditions the separation efficiency was 38%. With
a more economical PEO dosage of 0.6 g/kg daf coal, coal recovery was reduced only slightly
to 91 % and the separation efficiency was increased to 41 %. Except with the lowest particle
concentration, the separation efficiency generally ranged between 40 and 50%. Separation
efficiencies over 50% were achieved by using a particle concentration of 2.4%, PEO dosage
of 2.5 g/kg daf coal or more, and temperature of 95C. For these conditions coal recovery
was 82-91%.
The separation efficiency was low in part because a relatively crude method was used to
separate the flocculated solids from the other material. Therefore, it should be possible to
improve the separation significantly by improving the system hydrodynamics or by employing
other methods such as column elutriation.
Although the preceding results are of a preliminary nature, they show that it is feasible
to separate coal and kaolin particles by using PEO to promote selective flocculation and that
the process depends on temperature as well as particle concentration and PEO dosage. Of
course, the process needs to be demonstrated with other types of coal and with other
minerals. Also it needs to be shown that the method will clean dirty coals as well as separate
artificial mixtures. These aspects as well as the mechanism require further study.
217
ACKNOWLEDGMENT
This work was supported (in part) by the Iowa State Mining and Mineral Resources
Research Institute through the Department of the Interior's Mineral Institutes program
administered by the U.S. Bureau of Mines under Allotment Grant No. Gl 114119.
REFERENCES
1. Y. Attia and K. Driscoll, Coal Preparation, 9 (1991) 37-50.

2. R. H. Yoon, R. Q. Honaker, and G. H. Luttrell, Fizykochemiczne Problemy Mineralurgii,
24 (1991) 33-45.
3. R. J. Gochin and M. Lekili, Coal Preparation, 2 (1985) 19-33.
4. S. Lu and S. Song, Colloids and Surfaces, 57 (1991) 49-60.
5. D. H. Napper, Journal of Colloid and Interfacial Science, 32(1) (1970) 106-114.
6. W. R. VanBemmel, "The effect of temperature on coagulation and flocculation of aqueous
coal suspensions," M.S. Thesis, Iowa State University, Ames, lA (1992).
An Electrochemical Investigation of Surface Reactions of Coal- and Mineral-

Pyrite in Aqueous Solutions
D.P. Tao, P.E. Richardson, G.H. Luttrell, and R.-H. Yoon
Center for Coal and Minerals Processing, Virginia Polytechnic Institute and State University,
VA 24061-0258
Abstract
Oxidation and reduction processes occurring on polished and freshly fractured coal- and
mineral-pyrite have been studied using electrochemical techniques with the aim of
understanding the reactions that control its hydrophobicity and flotation. Ring-disc studies
show that 1) the kinetics of oxygen reduction on pyrite depends on its source; 2) two distinct
soluble reduction products (ferrous hydroxide and HS") are generated on pyrite in alkaline
solutions (pH 9.2) during cathodic sweeps; and (3) one distinct soluble oxidation product
(also ferrous hydroxide) is produced during anodic sweeps (pH 9.2). The voltammetry
behavior of polished pyrite at moderate overpotentials is dominated by the oxidation and
reduction of ferrous and ferric hydroxides, respectively, and not by the oxidation and
reduction of pyrite. To study the initial oxidation processes occurring on pyrite itself, fresh
surfaces were created by fracturing electrodes under the electrolyte. This procedure avoided
complications from the iron oxides and hydroxides present on polished electrodes.
Chronoamperometry immediately after fracture and subsequent cyclic voltammetry were used
to elucidate the initial oxidation reaction producing hydrophobic sulfur species on pyrite.
1. INTRODUCTION
In recent years, numerous studies have been directed at developing a low-cost froth
flotation process to remove pyritic sulfur from coal. These studies have been stimulated by
increasingly stringent restrictions on sulfur dioxide emissions from coal red power plants
and the recognition that pyrite (FeS2) is one of the major sources of sulfur in coal.
However, development of a practical flotation process for pyrite rejection has proven to be
more difficult than expected. Yoon et al. [1] and Luttrell and Yoon [2] established that a
major factor complicating pyrite rejection is the considerable hydrophobicity it acquires due
to superficial oxidation. Thus, in most flotation processes, a significant fraction of the
pyrite floats with the coal.
The oxidation of sulfide minerals, including that of pyrite, is controlled by mixed
potential, corrosion-type electrochemical reactions, in which the mineral undergoes anodic
oxidation while oxygen is cathodically reduced. Oxygen serves as an electron scavenger, so
the kinetics of its reduction is important in determining the rate of pyrite oxidation and the
mixed potential at which it occurs.
220
Biegler and his co-workers [3-4] studied the kinetics of oxygen reduction on a number of
sulfide minerals, and found that mineral-pyrite is the most active of the sulfides for oxygen
reduction. Doo and Sohn [5] studied oxygen reduction on mineral-pyrite at acidic pH's using
d-c polarization and a-c impedance techniques and showed that hydrogen peroxide is formed
as a reaction intermediate. Lai et. al [6] conducted cyclic voltammetry on mineral- and coal-
pyrite at pH 9.2 and concluded that coal-pyrite is not electroactive towards oxygen reduction.
The anodic oxidation of pyrite has been investigated extensively; however, the results are
often controversial and inconclusive. Hamilton and Woods [7], using voltammetry, observed
the formation of a monolayer of elemental sulfur at pH 9.2 and 13, and multilayers at pH
4.6. Peters [8] showed that oxidation of pyrite to sulphate requires high overpotentials and
occurs at significant rates only at potentials at which sulfur can also be a product. Based on
cyclic voltammetry and a-c impedance spectroscopy work, Chander and his co-workers
[9,10] proposed that iron oxide/hydroxide overlays a sulfur-rich layer on pyrite. These
investigators also suggested that simple abrasion due to stirring is sufficient in removing the
hydrophilic overlayer, thereby exposing the sulfur-rich layer underneath and giving rise to
self-induced (or collectorless) flotation [1,11-13]. The nature of the sulfur-rich surface has
been the subject of controversy. The XPS and Laser Raman spectroscopic studies conducted
by Yoon et al. [1], Zhu et al. [14], and Mycroft et al. [15] showed that iron polysulfides
( F e S i j , > 2) are the most likely oxidation products of sulfur. On the other hand, Buckley
and Woods [16-17] suggested that the sulir oxidation product is better represented by a
metal-deficient sulfide surface (Fei.xS2).
Many investigators showed that coal-pyrite exhibits significantly different electrochemical
behavior than mineral-pyrite because of differences in morphology, carbon inclusions and
heterogeneity [18-20]. Wang et al. [20] showed that the rate of oxidation of coal-pyrite
decreases when it contains carbon inclusions. Lai et al. [6] showed that coal-pyrite exhibits
significantly different flotation and electrochemical behavior than mineral-pyrite. Zhu et al.
[21] showed that voltammograms of coal-pyrite have fewer anodic and cathodic waves than
those of mineral-pyrite but the current densities on coal-pyrite could be 10-100 times larger
than those of mineral pyrite.
In the present work, oxidation and reduction processes on coal- and mineral-pyrite were
studied as part of an overall effort to control the surface chemistry of pyrite and, hence,
enhance pyrite rejection during flotation. Studies were conducted on both polished and
fractured pyrite electrodes. Special effort was placed on creating fresh surfaces by fracturing
electrodes in-situ (in the electrochemical cell). Most of the electrochemical studies conducted
in the past used electrodes prepared by polishing in air. Polishing is known to cause
extensive oxidation of the surface of sulfide minerals [22-23] and to alter the semiconducting
properties of pyrite [23].
2. EXPERIMENTAL
2.1. Materials
Large specimens of mineral pyrite, originating from Huanzala, Peru, were obtained
through Ward's Scientific Co. The Pittsburgh No. 8 coal-pyrite was originally a chunk of
2.5" X2.3" X 2 " pyrite found in a run-of-mine coal sample. This pyrite sample contains
approximately 3% coal on the surface. The coal pyrite specimen from Sichuan, China
contained no visible specks of coal and had the appearance of mineral pyrite.
221
2.2. Ring-disc electrodes

The ring-disc electrodes were constructed using core drilled discs of pyrite (0.7 cm
diameter) and pure gold rings. The disc was separated from the ring by a small gap of
nonconductive epoxy resin. The discs were contacted with a copper electrical lead. After
mounting the ring-disc assembly, the surfaces were abraded and polished with successively
finer grades of silicon carbide paper from 240 to 600 grit. The samples were cleaned with
acetone, hydrochloric acid and distilled water. Solutions were purged with N2 for at least
one hour prior to each experiment. A pine RDE-4 double potentiostat was used to control
the potential and a pine rotating ring-disc assembly was used to rotate the electrode. The
electrode rotation speed was 2000 rpm and voltammograms were recorded on the second
cycle, unless otherwise specified. Voltammetry curves and ring currents were recorded on
a Linseis LY 181(X) recorder.
The collection efficiencies (N) of the three electrodes made of different pyrite specimens
were determined using freshly prepared 1.0 x 10"^ CuCl2 in 0.5 KCl solution [24]. The
pyrite electrodes were held at 0.1 V (SHE) at which no significant current arises from
reactions of pyrite itself and Cu^"*" reduction is under diffusion control. The values of for
the mineral-, Pittsburgh No. 8 coal-, and Chinese coal-pyrite were 0.38, 0.28 and 0.36,
respectively.
A saturated calomel electrode (SCE) was used as the reference electrode and a platinum
wire as the counter electrode. Potentials are expressed on the standard hydrogen electrode
(SHE) scale by adding 0.245 V.
2.3. In-sUu fractured electrodes

The mineral pyrite samples for in-situ fractured electrodes had dimensions of
approximately 3 x 2 x 10 mm. Copper lead-wire was connected to one of the 3 x 2 mm faces
using a conducting silver epoxy. The assembly was then mounted at the end of a 7 mm
diameter glass tube with non-conducting epoxy (Torr Seal, Varian). After the electrode was
inserted into the electrochemical cell, the projecting portion was subjected to a sharp blow
through a glass rod resting on it, resulting in a freshly fractured surface which was usually
flush with the epoxy.
2.4. Electrochemical-microflotation cell

Figure 1 illustrates the electrochemical-microflotation cell in which a compacted pyrite bed
is used as the working electrode. A detailed description has been provided elsewhere [25].
The main advantage of using the particulate bed instead of a single specimen as the working
electrode is that electrochemical studies and flotation tests can be done in the same system
under conditions close to the actual flotation environment. In addition, the solution can be
continuously circulated between the cell and UV spectrophotometer so that the solution phase
can be monitored. The bed used in the present study consisted of a 1.5 g sample of -14-1-20
mesh particles. The bed potential was controlled with a PAR 273 potentiostat and the
voltammogram recorded on a Linseis LY 18100 recorder.
2.5. Reagents
Buffer solutions used in all tests were prepared in double-distilled water using reagent
grade chemicals with the following compositions:
222
A mectrolyte inlet
Luggin inlet
C Electrolyte outlet
D Flotation gas inlet
Glass frit
F Platinum lead
G Flotation head
Counter electnxie
compartment
Figure 1. Illustration of the electrochemical-microflotation cell.
pH 4.6; 0.5 C H 3 C O O H and 0.5 CHjCOONa

pH 6.8; 0.05 Af KH2PO4 and 0.0224 NaOH
pH 8.0; 0.05 KH2PO4 and 0.0461 NaOH
pH9.2; 0 . 0 5 M Na2B407
Dowfroth M-150 was used as frother at a dosage of 10 ppm in microflotation tests. Fresh
iron(II) solutions were prepared by dissolving FeCl2 in deoxygenated distilled water.
3.1. Oxygen reduction on pyrite

Studies of oxygen reduction on pyrite electrodes were conducted with the RRDE. Figure
2 (top) shows the current resulting from linear potential sweeps from 0.25 to -0.75 V on the
Chinese coal-pyrite disc electrode at pH 9.2 for various rotation speeds in a solution
saturated with oxygen. The current was negligible in the absence of oxygen in this potential
range. At the beginning of the sweeps, the current is controlled by electron transfer
223
(activation control) and is

only slightly dependent on
rotation rate . As the
250 potential becomes more
500 negative, the diffusion of
oxygen to the disc surface
1000
gradually predominates
1500 over charge transfer in
2000 determining the reaction
rate and, hence, the current
3000 is increasingly dependent
4000 on rotation speed. At
-0.8 -0.6 -0.4 -02 O more negative potentials,
Potential ( V, vs. SHE ) the current is diffusion-
limited. The onset of the
250
1000 5.0 diffusion-limited current
4000 shifts to more negative
potentials with increasing
rotation speed. The
Figure 2. Ring-disc voltammograms for oxygen reduction on l i m i t i n g current l
Chinese coal-pyrite at pH 9.2 (ring at 0.25 V, the inset (mA/cm^) is given by the
represents limiting current vs. electrode rotation speed). Levich equation [3],
1/2 (1)
where is the number of electrons in the rate determining step, F the Faraday's constant,
D the diffusion coefficient for the relevant species undergoing oxidation or reduction, the
kinematic viscosity, C|j the concentration of the electroactive species in the bulk solution, and
is the angular velocity of the electrode. Biegler et al. [3] have shown that Equation (1)
can be written for oxygen reduction in air-saturated aqueous solutions as,
0.0457/^^ (2)
where I I is in units of mA. A plot of I I v s . ^^^ is linear (Figure 2, inset), in agreement

with Equation (2). The value of calculated from Equation (2) is 3.5, suggesting that the
reduction of oxygen proceeds to OH" primarily by the 4-electron process.
4e-=WH- (E=l.229-0,059pH). (3)
The presence of a single wave on the disc voltammograms indicates that no intermediate
soluble species is generated during oxygen reduction at pH 9.2. This is substantiated by the
absence of a ring current from 0.25 to -0.55 V when the ring was held at 0.25 V, which is
positive enough to oxidize any hydrogen peroxide ( H 2 O 2 ) produced on the disc. The small
ring current observed at potentials <-0.55 V is due to the cathodic decomposition of pyrite
and will be discussed later. The results obtained with Pittsburgh No. 8 coal- and mineral-
pyrite are similar with regard to the shape of the disc voltammograms and the ring response.
Mineral- and Chinese coal-pyrite electrodes show nearly identical disc currents for oxygen
224
reduction that are higher

than those exhibited by
Pittsburgh No. 8 coal-
pyrite.
At pH 6.8, the features
of the voltammograms of
oxygen reduction on pyrite
are similar to those at pH
9.2 for all three pyrite
samples studied, with no
evidence of the formation
of hydrogen peroxide. The
magnitude of the disc
currents at equivalent
overvoltages at pH 6.8 is
in the order: Pittsburgh
No. 8 coal-pyrite >
Chinese coal-pyrite
mineral-pyrite.
Figure 3. Ring-disc voltammograms for oxygen reduction on In acidic solution,
Chinese coal-pyrite at pH 4.6 (ring at 0.85 V, dashed line is oxygen reduction on pyrite
the current in nitrogen sparged solution). proceeds via a different
route. Figure 3 shows the
linear sweep voltammograms for oxygen reduction on Chinese coal-pyrite at pH 4.6. In the
activation-controlled region, there are two distinct cathodic reduction processes occurring,
as evidenced by the change in slope of the curves at about 0 V. The current on the ring,
which was held at 0.85 V during the potential sweep, shows that a soluble intermediate
species is produced at disc potentials < -0.15 V. This can be attributed to hydrogen peroxide
produced on the disc by the reaction,
2H^ + 2 ^ - = H2O2 (^=0.695-0.059/70) (4)
followed by its re-oxidation on the ring. The ring current reaches a maximum at a disc
potential of -0.25 V. When the limiting current on the disc is reached ( < - 0 . 3 V), the
overpotential is large enough that hydrogen peroxide is reduced at the disc to OH", with less
diffusing to the ring. Consequently, the ring current decreases. At more negative potentials
( < - 0 . 5 V), significant cathodic decomposition of pyrite occurs, producing decomposition
products which are oxidized at the ring.
Mineral-pyrite shows a behavior similar to that shown in Figure 3. However, on
Pittsburgh No. 8 coal-pyrite, most of the oxygen is reduced all the way to water, with only
a small amount of hydrogen peroxide escaping the disc surface. The electroactivity towards
oxygen reduction at pH 4.6 for the three pyrite samples is in the same order as at pH 6.8.
The above results are in general agreement with data obtained by Biegler et al. [3] on
mineral pyrite using the rotating disc electrode. They suggested the formation of hydrogen
peroxide during oxygen reduction in acid solutions from the change in the slope on the
voltammetry curves. Under neutral or alkaline conditions iron hydroxide/oxide may catalyze
the decomposition of peroxide on the pyrite surface [25]. It is clear that coal-pyrite is
225
electroactive with respect

to oxygen reduction, con
trary to the conclusion of
Lai et al. [6]. The differ
ence in electroactivity for
oxygen reduction among
three pyrite samples may
be attributed to differences
in crystalline defects and
the morphology of the
surface. While Chinese
-0.8 -0.6 -0.4 -0.2 O 0.2 coal-pyrite exhibits a mor
Potential ( V, vs. SHE ) phological appearance
similar to mineral pyrite,
Pittsburgh No.8 coal-pyrite
appears very different in
that it is much more porous
and poorly crystallized. It
is believed that in neutral
and acidic solutions, the
more porous nature of
pyrite may hinder the
diffusion of hydrogen
peroxide away from the
disc, fostering its further
Rgure 4. Ring-disc voltammograms of Chinese coal-pyrite on reduction to OH" before it
different cycles at pH 9.2 (ring at 0.25 V). can be convected to the
ring. At pH 9.2, the elec
troactivity of Pittsburgh No. 8 coal-pyrite to reduce oxygen is lower than that of the other
two pyrites. It is possible that in alkaline solutions, the pores of Pittsburgh No. 8 coal-pyrite
become blocked with reaction precipitates.
3.2. Pyrite oxidation/reduction on ring-disc electrodes

Figure 4 shows the first five consecutive voltammetry curves on Chinese coal-pyrite in
nitrogen sparged solution at pH 9.2. Previous studies with mineral pyrite at pH 11 [13] and
at pH 9.2 [14,21] suggested that the anodic peak I at -0.4 V is due to ie oxidation of
elemental iron to Fe(OH)2 by the reaction,
Fe + 20H- = Fe{0H)2 ^ 2^" (E=-0.047-0.059pi?). (5)
Elemental iron is produced by the cathodic reduction of pyrite or of iron oxidation products
during the negative going sweep. Anodic currents in this potential region may also be
associated with tiie reaction.
226
Fe + HS- + OH- = FeS + H2O + 2 ^ " (=-0.578-0.03/7-0.03/^[5"]), (6)
where H S ' is also produced during the cathodic decomposition of pyrite on the negative
sweep.
The current () on the anodic sweep at potentials above 0.25 V has been attributed to the
oxidation of pyrite itself to form sulfate and ferric hydroxide [7,8,13,27] by the reaction,
FeS2^nH20=Fe{OH)^^2SOl~^l9H^^\5e- (=0.412-0.0749/?7/+0.00781og[5(94"]). (7)
Monolayer quantities of elemental sulfur may also form in this range by the reaction,
FeS2 + 2>0H- = FeipH)^ + 2S^ + 3 ^ " (=0.628-0.059/7^0. (8)
Pyrite reduction takes place at potentials more negative than -0.65 V, which is indicated
by a consistent increase in cathodic current (VI). The reactions are [13,21,28],
FeS2 + H2O + 2e- = FeS + HS- + OH- (=-0.403-0.03;7H-0.031og[H5"]), and (9)
FeS2 + 2H2O + 4 e " = Fe + 2HS- + 2 0 H " (=-0.491-0.03;7r-0.031og[i/5"]). (10)
From the standpoint of pyrite flotation, perhaps the most significant reactions are repre-
sented by peaks II and IV in Figure 4. Peak , which occurs at 0 V on the anodic sweep,
is generally attributed to the oxidation of Fe(0H)2 to Fe(0H)3 by the reaction,
Fe{0H)2 + OH- = FeiOH)^ + e " (=0.271-0.059pf). (H)
This reaction presupposes that pyrite has been oxidized and formed a layer of Fe(0H)2 on
the surface which is further oxidized to Fe(0H)3. Janetski et al. [29] reported that peak II
is observed on sweeps commencing at potentials negative of the peak, even when a fresh
surface is generated by repolishing. They established that pyrite oxidizes to some extent
when the surface is expose to air, acquiring an iron oxide layer. Hamilton and Woods [7]
studied pyrite abraded under nitrogen to prevent oxidation and found an oxidation peak at
approximately 0 V at pH 9.2. They attributed this peak to reaction (8), i.e., pyrite itself is
oxidized to Fe(0H)3 and elemental sulfur. From XPS studies [16], Buckley and Woods
concluded that moderate oxidation of pyrite leaves sulfur in normal lattice sites, creating a
state of metal-deficiency (Fei.xS2). However, Yoon et al. [1] observed significant flotation
of pyrite at potentials slightly above -0.1 V and suggested from XPS and electrochemical
studies that polysulfides (FeS^) are more likely oxidation products. Studies on freshly
fractured surfaces, presented in the following section, show that pyrite itself begins to oxidize
at approximately -0.15 V. It is believed that when a surface has previously oxidized, the
current due to pyrite oxidation on voltammetry curves is largely masked by the oxidation of
Fe(0H)2 to Fe(0H)3.
The cathodic peak IV occurring at about -0.32 V in Figure 4 is the reverse of reaction
(11). In addition, if sulfur is present on the surface in the form of a polysulfide, elemental
sulfur, or excess lattice sulfur, it may also be reduced over the same potential range as
reaction (11) to reform an iron sulfide.
227
^2e- = FeS ^ lOH' (^=0.456-0.059p). (12)
It was reported [7,21] that in basic solution, peaks II and IV are independent of solution
convection (rotation speeds) and contain the same charge. This indicates that the species are
insoluble surface products. It is not surprising, therefore, that standard voltammetry
techniques could not separate reactions (11) and (12). When electrodes are prepared by
routine polishing techniques in air, reaction (11) predominates, masking reaction (12) which
is more relevant to flotation.
Figure 4 (bottom) shows the current observed at the gold ring held at 0.25 V. During the
cathodic sweep, a ring current commences at -0.1 V which is clearly associated with
oxidation of the species reduced over peak IV. The major reduction product for this peak
is F e ( 0 H ) 2 , which has a fmite solubility at pH 9.2. Using the measured collection
efficiency, approximately 10 to 20% of the species reduced over peak IV is reoxidized on
the ring.
It is believed that more than one reduction process is associated with peak IV, one being
the reverse of reaction (11) which produces a soluble ferrous hydroxide that can be
reoxidized on the ring; the other producing an insoluble iron sulfide, e.g., reaction (12).
Peak rv depends on the total amount of Fe(0H)3 and sulfur (as excess sulfur in the lattice,
polysulfide, or elemental sulfiir) produced on the prior anodic sweep, while the ring current
only depends on the amount of
Fe(0H)3 that is reduced to a
soluble ferrous hydroxide.
Support for assigning at least
two reduction processes to
peak IV is provided in Figure
5, where the anodic limit has
been increased. It is known
that pyrite oxidation can occur
via two paths, reactions (7)
and (8), where the relative
yield of S and S04^" depends
-04-01 0 02 on the anodic limit. Higher
Potential { V, vs. SHE ) potentials favor sulfate forma
tion and thus lead to a reduc
tion in the quantity of insol
uble, reducible sulfur species
on the electrode relative to the
quantity of Fe(0H)3. On the
reverse cathodic sweep, a
lower surface concentration of
LO
reducible sulfur species should
decrease the current due to
reaction (12) and increase the
_^ c ^ u cr^w i amount of soluble ferrous hy-
Figure 5 Ring-disc voltammograms of Chmeseco^^^^^^^ ^^^^.^^ ^^^^ ^^^.^.^
at^pH 9.2 with varymg upper potential hmit (nng at 0.25 ^.^ ^^^^^^^^^
228
with Figure 5 which shows that the ring current increases with increase in the anodic limit,
while the charge associated with peak IV changes only slightly with the anodic limit.
It is of particular interest that on the subsequent anodic sweep, an additional oxidation
current is observed on the ring (Figure 4). This indicates that a double oxidation process
occurs, i.e., a soluble oxidation species is generated at the disc on the initial portion of the
positive going sweep, and this oxidation product is further oxidized at the ring. This double
oxidation process is entirely consistent with the known electrochemistry of pyrite and the
existence, as shown above, of a soluble ferrous hydroxide reaction product. When pyrite,
or previously existing iron oxides or hydroxides on pyrite are reduced at potentials near -0.7
V, elemental iron is formed. On the return anodic sweep, iron is oxidized to yield Fe(0H)2
and possibly FeiOH)"^. The ring current on the initial portion of the anodic sweep thus
results from the oxidation of a soluble ferrous hydroxide. Essentially, the same species
(soluble ferrous hydroxide) is responsible for the ring current on the cathodic sweep, where
it is produced by reduction of Fe(0H)3, and for the ring current on the anodic sweep, where
it is produced by the oxidation of elemental iron.
Figure 4 also shows that a ring current is associated with the reduction process labeled VI,
and possibly with peak V. Peak V has been attributed to the reduction of sulfur [21] that is
produced on the positive going sweep; the current increase at VI to the decomposition of
pyrite by reactions (9) and (10). Both reactions produce HS" and thus the ring current on
the cathodic sweep at disc potentials < - 0 . 6 V is due to the oxidation of HS" to S.
Mineral- and Pittsburgh No. 8 coal-pyrite exhibit voltammograms similar to those for the
Chinese coal-pyrite at pH 9.2. However, both of the coal-pyrites appear significantly more
reactive than mineral-pyrite. Figure 6 shows the second-cycle disc voltammograms and ring
current for comparison of the three pyrites. The oxidation of mineral-pyrite produces more
-04 -02 0 02
Potential ( V. vs. SHE )
Chinese coal-pyrite
Pittsbui^ No. 8 ooal*pynte
Mineral-pyrite
Figure 6. Ring-disc voltammograms of Figure 7. Ring-disc voltammograms of

different pyrite samples at pH 9.2 (ring at Chinese coal-pyrite at pH 9.2 in the
0.25 V). absence/presence of ferrous chloride (ring at
0.25 V).
229
soluble species than coal-pyrites.

The effect of ferrous chloride on the disc voltammograms and the ring response is shown
in Figure 7. It can be seen that with the addition of Fe^"*", the cathodic peak on the disc
voltammograms at -0.32 V increased considerably, confirming the suggestion that part of the
peak results from the reduction of ferric compounds. A second cathodic peak is also
resolved at -0.65 V and can be attributed to the reduction of ferrous hydroxide to elemental
iron. The additional ring current observed during both the cathodic and anodic sweeps
indicates that the addition of Fe^"*" leads to an increase in Fe(OH)3 formation during the
anodic sweep at potentials near 0 V (apparent on the voltammogram), and a subsequent
increase in the concentration of soluble ferrous hydroxide produced during the cathodic
sweep (also evident on the voltammogram). The addition of Fe^"*" also increased the ring
current during the subsequent anodic scan, indicating a larger amount of elemental iron is
produced at the negative potential limit which can then be oxidized to form the soluble
ferrous hydroxide species.
Figure 8 demonstrates the disc voltammograms and ring responses for three pyrite
specimens at pH 6.8. Chinese coal-pyrite behaves similarly to mineral-pyrite but Pittsburgh
No. 8 coal-pyrite exhibits considerably different characteristics. For mineral- and Chinese
coal-pyrite, the cathodic peak on the disc voltammogram is observed at -0.1 V, resulting in
the ring current. This behavior is similar to that at pH 9.2, with the peak shift due to the
pH dependence of the reaction. Two small anodic peaks at -0.25 V and 0.1 V are
distinguishable using a more sensitive current scale (not shown). The ring current is
significant at the beginning of the anodic sweep and seems to be relatively constant up to
0.15 V, but no peak is present, in contrast with the observation at pH 9.2. However,
pyrite exhibits a cathodic
peak at -0.28 V which does
not yield a corresponding
ring current, implying that
no soluble species is
formed during cathodic
reduction. The voltam
metry curves and ring
currents on the three
pyrites clearly establish
that the oxidation and
reduction processes on
\-0l6 -04 -02 0 02 04 06 Pittsburgh No. 8 coal-
Potential ( V, vs. SHE ) pyrite are considerably
Chinese coaFpyrite different than those on
Pittsburgh 8 coaFpyrite mineral pyrite and those on
Mineral-pyrite well-crystallized Chinese
05 A coal-pyrite. Pittsburgh No.
8 coal- pyrite is much
more reactive than the
other pyrites and the pro-
Figure 8. Ring-disc voltammograms of different pyrite ducts of the reaction appear
samples at pH 6.8 (ring at 0.25 V).
230
to be different since no soluble reaction products are detected at the ring during the
voltammetry sweeps.
The increased reactivity and absence of soluble reaction products on Pittsburgh No. 8 coal-
pyrite may be due to its large surface area, with the reactions taking place internally in
pores. This large surface area would increase the apparent reactivity, whereas the reactions
in pores would hinder diffusion of soluble products to the surface where they could be
convected to the ring to undergo further reaction.
At acidic pH's, pyrite exhibits a considerably different electrochemical behavior than at
pH 9.2. Figure 9 illustrates the disc voltammograms and ring currents between -0.4 V and
0.55 V at pH 4.6 when the potential of the ring electrode was held 0.25 V. Hamilton and
Woods (7) showed that a step is present on mineral pyrite at 0.4 V in pH 4.6 solutions
during anodic sweeps on stationary electrodes but not on rotating electrodes. The step was
attributed to the reaction,
F^^^ + 3H20 = Fe(OH)^ + 3^ + e~ (E=0.97l-0.l77pH-0.059log[Fe^'']) (13)
and its absence on rotating electrodes was explained by the convection of the reactant away
from the surface. In agreement with Hamilton and Woods [7], there is no step at 0.4 V on
rotating electrodes of mineral- and Chinese coal-pyrite in Figure 9. However, a distinct
oxidation peak is observed at this potential on the Pittsburgh No. 8 pyrite. There is a
corresponding reduction process on the subsequent negative going sweep that begins at 0.3
V and is believed to repre
sent the reverse of reaction
(13). This provides further
evidence tiat Pittsburgh
No. 8 coal-pyrite is differ
ent from mineral-pyrite and
Chinese coal-pyrite.
Again, this difference can
be accounted for by assum
ing that the surface area of
the Pittsburgh No. 8 coal-
pyrite is much larger than
0.02 mA that of the other pyrites
due to pores and that the
-0.4 -0.2 0 0.2 0.4 0.6 diffusion and convection of
Potential ( V. vs. SHE ) soluble reactants and pro
Chinese coal-pyrite ducts in the pores are hind
Pittsbuigh 8 coal-pyrite ered.
Mineral-pyrite Distinct reduction pro
cesses are observed at
potentials < - 0 . 3 V on the
voltammetry curves for the
mineral- and coal-pyrite
electrodes. The reduction
_ ^ - . .... , currents in this range of
Figure 9. Rmg-disc v o t a o g i a m s of different pynte .^^ ^^^^^^
samples at pH 4.6 (nng at 0.25 V). ^
231
be primarily due to the reduction of excess sulfur produced by anodic reaction at potentials
> 0 . 4 V. Since the formation of Fe(0H)3 is suppressed by dispersion of Fe^"^ on the
rotating electrode, the major insoluble reaction product formed at anodic potentials is excess
sulfiir, i.e., there is no Fe(0H)3 to be reduced on the mineral- and Chinese coal-pyrite. On
these two pyrites, the reduction of excess sulfur and oxidation of the reduction product gives
rise to a finite ring current. On the Pittsburgh No. 8 coal-pyrite, a broad reduction process
begins at about 0.3 V on the cathodic sweep and continues until the cathodic limit is reached.
Both Fe(0H)3 and excess sulfiir are present on the surface at the beginning of the cathodic
sweep and the broad reduction process initially represents the reformation of an iron sulfide
(FeS) when these products are reduced. It is believed that the Fe(0H)3 is depleted before
the excess surface sulfur. Thus, at more negative potentials, a sulfur species is reduced to
H 2 S and its reoxidation produces a small ring current. The H 2 S does not appear to be
trapped in the pores. This may be because the production of gaseous H 2 S builds up
sufficient pressure to force the product out of the pores.
3.3. Pyrite oxidation/reduction on in-sUu fractured electrodes

The electrochemical behavior of freshly fractured pyrite could be different from that
observed with abraded or polished pyrite. Abrasion could generate intense local heating and
may produce a relatively thick surface layer which may be heavily oxidized and may possess
more lattice defects than fractured surfaces [22-23,30]. To study the incipient oxidation of
pyrite itself rather than the oxidation of polished pyrite that already has oxidation products,
fresh surfaces were created by fracturing pyrite in the electrochemical cell. The electrodes
were potentiostated at a predetermined value during fracture to prevent or minimize pyrite
1 \ \ \ 1 1 r I I
oxidation/reduction following fracture.
A first cycle voltammetry curve
obtained on the fresh surface of a
pyrite electrode that was held at 0.15
V is shown in Figure 10. Figure 10
(inset) also shows the current passed
when the electrode was fractured.
Oh The charge passed during the first two
minutes after fracture is approximately
460 /xC/cm^, based on the geometric
surface area of the electrode. This
charge indicates that pyrite itself
/ / i'
oxidizes at 0.15 V to a significant
extent (possibly a monolayer or two).
-4L After holding the electrode at 0.15 V
for approximately four minutes after
fracture, the voltammetry curve was
0 , 0, Tipiefepc)" obtained, with the potential sweep
.... 1 i \ \
-0.6 -04 "02 O 02 0.4 starting in the negative direction to
Potential (V, vs. SHE) reduce the oxidation products pro
Figure 10. Voltammogram of mineral-pyrite duced at 0.15 V. There is a broad
electrode freshly fractured at 0.15 V at pH 9.2 reduction process beginning at about
(inset is the chronoamperometry curve upon -0.05 V with an integrated charge of
fracture).
232
about 1300 ^C/cm^ between -0.05 and -0.55 V. This reduction current confirms that solid
oxidation products were produced on pyrite during oxidation at 0.15 V. Several electrodes
fi-actured at this potential produced similar results with approximately the same charge
density passed at nocture and on the subsequent negative going potential scan. However,
on some electrodes, a distinct reduction peak has been observed at -0.32 V.
Other electrodes have been fi^ctured while holding the potential at -0.35 V (Figure 11).
The current passed on a freshly fractured surface at this potential is negligible on most
samples although a slightly cathodic current with a charge of 50 to 100 /? has been
observed on a couple of electrodes. On the first positive going sweep after fracture at -0.35
V, an oxidation current begins near -0.15 V. This clearly represents the oxidation of pyrite
itself to Fe(0H)3, with the sulfur present being excess in the lattice, elemental sulfur, or a
metal polysulfide. It is important to note that in this case, pyrite was not subjected to
oxidation or reduction prior to the first anodic sweep and, therefore, no elemental iron or
ferrous hydroxide should be present on the surface.
Importantly, these experiments establish that pyrite itself oxidizes at potentials above about
-0.15 V. Based on the first sweep voltammetry curves on pyrite surfaces produced by
fracture, Fe(0H)3 is one of the oxidation products. From the standpoint of flotation,
Fe(0H)3 is hydrophilic and should depress pyrite. However, the oxidation state of sulfur
at the surface should also change when pyrite is oxidized to F e ( 0 H ) 3 . The sulfur product
resulting from pyrite oxidation has not been identified in this work, but it has been sugges
ted to be metal polysul
fide [1], excess sulfur
in the surface region
dissolved in pyrite
[16], or elemental sul
fur [7]. It is also signi
ficant that a soluble
ferrous hydroxide is
produced on pyrite in
alkaline solutions. It is
< known that sulfides are
neither strongly hydro
c phobic nor strongly
t
3 hydrophilic [31] and
CJ that slight changes in
the surface can have a
large effect on their
floatability. Oxidation
produces both hydro
philic species, Fe(0H)3
and hydrophobic sulfur
-0.4 -0.2 0.0 0.2 species. The formation
Potential ( V, vs. S H E ) of soluble iron com
pounds may provide a
Figure 11. Voltammogram of mineral-pyrite electrode freshly mechanism which ex
fractured at -0.35 V at pH 9.2 (inset is the chronoamperometry plains why pyrite can
curve upon fracture).
233
exhibit self-induced flotation in alkaline solutions. Essentially, the loss of soluble iron
species coupled with the retention of sulfur at the surface increases the net hydrophobicity.
3.4. Electrochemical notation

Microflotation tests were conducted with -14+20 mesh mineral pyrite using an
electrochemical flotation cell shown in Figure 1. The potential was controll^ by means of
a potentiostat rather than adding oxidizing or reducing agents. As shown in Figure 12, the
onset of flotation occurs at approximately 0.1 V at pH 4.6 and the maximum flotation occurs
in the potential range of 0.35 to 0.65 V. As suggested in the foregoing sections, a sulfur-
rich surface in the form of either elemental sulfur, polysulfides, or metal-deficient sulfides
may be responsible for the observed flotation. The loss of floatability at higher potentials
is probably due to oxidation of sulfur to thiosulfate and/or sulfate. An important conclusion
drawn from Figure 12 is that pyrite can be depressed by maintaining the potential under
either reducing or strongly oxidizing conditions.
According to reaction (8), collectorless flotation should occur above -0.2 V at pH 9.2 and
above 0 V at pH 6.8. However, no flotation was observed with this particular pyrite sample
because the hydrophobicity caused by the
formation of a sulfur oxidation product is
reduced by the presence of iron oxide/hy
droxide, also formed as part of the oxida
tion mechanism. The net hydrophobicity
is probably insufficient in lifting the large
particles used in the present work.
Luttrell and Yoon [1] showed that a
-65+100 mesh mineral pyrite sample
floated at alkaline pH's, without collector,
when the potential was chemically con
trolled. Preliminary electrochemical flota
tion experiments conducted with -65 +100
mesh mineral pyrite showed considerable
floatability in alkaline and neutral pH's.
Electrochemical flotation tests conduc
ted with -14+20 mesh coal-pyrite samples
did not exhibit flotation even at pH 4.6.
It is possible that coal-pyrite is less
-0.6 -02 02 0.6 hydrophobic than minerad-pyrite; XPS
spectra obtained with freshly fractured
Potential (V, vs. SHE)
coal pyrite showed the presence of iron
oxide/hydroxide [1]. It is also possible
Figure 12. Effect of potential on flotation that sulfoxy compounds are present on
recovery of mineral-pyrite at different pH values coal pyrite due to the fast oxidation
(particle size -14-20 mesh). kinetics.
234
4. CONCLUSIONS
L Hydrogen peroxide is an intermediate product of oxygen reduction on pyrite at pH

4.6; however, at pH 6.8 and 9.2 oxygen is directly reduced to hydroxyl ions.
2. Chinese coal-pyrite shows almost the same electroactivity as mineral-pyrite towards
oxygen reduction at all pH's studied. Pittsburgh No. 8 coal-pyrite is considerably
more electroactive than the Chinese coal-pyrite and mineral-pyrite towards oxygen
reduction at pH 4.6 and 6.8 but less active at pH 9.2.
3. The rates of oxidation and reduction of Pittsburgh No. 8 coal-pyrite are higher than
those of Chinese coal-pyrite and mineral-pyrite, which may be attributed to its high
surface area and coal inclusions.
4. The voltammograms of polished electrodes of mineral and coal- pyrite exhibit anodic
and cathodic peaks at 0 and -0.32 V (respectively) at pH 9.2, which are characteristic
of the iron oxide/hydroxide formed during electrode preparation.
5. The voltammograms recorded with freshly fractured pyrite surfaces show anodic
currents due to oxidation of the mineral itself rather than oxidation of ferrous
hydroxide. At moderate overpotentials, this must give rise to a sulfur-rich surface
in the form of polysulfides, metal deficient sulfide, or elemental sulfur, or formed by
prior anodic or cathodic treatment at moderately high overvoltages.
6. Significant ring currents are observed during cathodic reduction of all three pyrite
electrodes at pH 9.2, which are attributed to soluble ferrous hydroxide species. The
same soluble species are observed during anodic oxidation at pH 9.2.
7. Electrochemical flotation experiments conducted with relatively coarse mineral pyrite
exhibited strong self-induced flotation at pH 4.6 above 0.1 V, which is in agreement
with voltammetric results. No flotation is observed at pH 6.8 and 9.2 with this
sample, which may be attributed to the iron hydroxide formed as an oxidation product
and the large particle size.
5. ACKNOWLEDGEMENTS
The authors gratefully acknowledge the support of the United States Department of Energy
under grant No. DE-AC22-92PC92246 which made this work possible.
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The simultaneous use of a single additive for coal

flotation, dewatering, and cake hardening
W.W. Wen^ H. Cho^ and R.P. Killmeyer^
Û.S. Department of Energy, Pittsburgh Energy Technology Center, P.O. Box

10940, Pittsburgh, PA 15236-0940
^Mineral Processing, The Pennsylvania State University, University Park, PA 16802.
ABSTRACT
The Pittsburgh Energy Technology Center (PETC) has previously patented a new
concept, termed the in situ cake hardening process, in which a binding agent is
added to a clean fine coal slurry ahead of the dewatering device to simultaneously
improve dewatering efficiency. More importantly, it moderately agglomerates, or
hardens, the clean fine coal so that, upon drying, its dustiness would be significantly
reduced and its handling improved. PETC has recently expanded on this concept by
going back one step in the flowsheet and also applying this same binding agent to
the flotation process, where it acts as a collector. It then remains with the clean coal
through dewatering and cake hardening. Thus, a single dose of additive contributes
to three consecutive fine coal unit operations in a coal preparation flowsheet. This
paper describes the preliminary laboratory results of using Orimulsion, a heavy
bitumen crude oil emulsion, as one additive for flotation, dewatering, and dust
reduction.
1. INTRODUCTION
Typical coal cleaning processes strive to prepare coal at particle sizes convenient
for both optimal cleaning and handling, which basically means avoiding the
production of fines. However, the quantity of fines has increased as a result of
mechanical coal-mining methods and fine grinding techniques to liberate pyrite and
other ash-forming mineral matter from coal. Because fine coal is more difficult and
costly to dewater and handle than coarse coal, significant effort has recently been
devoted to understanding and improving dewatering and reconstitution processes for
fine coal [1,2,3]. One such effort at Pittsburgh Energy Technology Center (PETC)
resulted in the patenting of a combined method for simultaneously dewatering and
reconstituting fine coal [4]. Often reported as an in situ cake hardening process, it
238
provides improved dewatering, enhanced cake strength, and decreased dustiness

during handling through the addition of emulsified asphalt prior to the dewatering step
[5,6,7].
In searching for low-cost binding agents to further improve the economic feasibility
of the in situ cake hardening process, preliminary tests indicated that an emulsion of
an heavy crude oil (bitumen) can be as effective a binding agent as emulsified
asphalt. The emulsion can also be used effectively as a collecting reagent for
flotation. Although previous tests have shown improved filtration dewatering and cake
dust reduction with emulsified asphalt, the asphalt did not show flotation selectivity
and failed to provide adequate dewatering and dust reduction when the slurry
temperature was low. This paper describes the preliminary laboratory test results of
using an inexpensive bitumen emulsion in fine coal flotation, dewatering, and
reconstitution. A comparison of dewatering and reconstituting minus 74 micron (200
mesh) fine coal with Orimulsion and asphalt emulsion at different slurry temperatures
is also included. Thus, the potential exists for a single dose of additive to contribute
to three consecutive fine coal processing unit operations in a single coal preparation
flowsheet .
2. MATERIALS AND METHODS
2.1. Coal Samples

The three coal samples used in the flotation study were from the Pittsburgh No.8
seam (23 % ash, 6.5 % sulfur), Belmont County, Ohio, the Illinois No. 6 seam (14.2
% ash, 4.9 % sulfur), Randolph County, Illinois, and the Upper Freeport seam (11.5
% ash, 1.5 % sulfur), Indiana County, Pennsylvania. All coal samples were stage
crushed to 590 micron by 0 (28 mesh by 0) using a hammer mill. In addition, a
Pittsburgh seam coal (4.9 % ash), from the U.S. Bureau of Mines experimental mine
in Pittsburgh, Pennsylvania, was ground to 74-micron (200 mesh) top size and used
in dewatering and reconstitution studies.
2.2. Reagents
The heavy crude oil (bitumen) used in this study was from Venezuela's Orinoco
Belt bitumen reserves, which had been known to exist for decades but had not been
developed due to production and handling difficulties. The reserves were tapped
when Bitumens de Orinoco S.A. developed an emulsification technique to produce a
bitumen-in-water emulsion under the trade name Orimulsion. Table 1 shows the
characteristics of this emulsion. This product and raw bitumen were obtained through
Bitor America Corporation, Boca Raton, Florida.
A cationic rapid-setting asphalt-in-water emulsion (CRS-2) provided by Russell
Standard Corporation, Mercer, Pennsylvania, was also used as a binder. Kerosene
was used as a collector for comparison purposes, and Methyl Isobutyl Carbinol
(MIBC) was used as a frother.
239
Table 1
Characteristics of Orimulsion
Typical Maximum Value
Water Content, %w/w 30.0 32.0

M e d i a n Droplet Size, microns 200 300
%Droplets 100 microns 1.5 2.5
Density (tS'^C), K g m ' ^ 1010 1013
Apparent Viscosity, m P a s
5 C (86 F),20s"' 700 1100
3 0 C ( 8 6 F), 2 0 s - ' ' 450 700
5 0 C ( 1 2 2 F), lOOs"" 300 450
7 0 C ( 1 5 8 F ) , lOOs-"" 150 250
Vanadium, ppm 300 360
Sodium, ppm 70 80
Magnesium, ppm 350 500
Flash Point, C / F 130/266 122/252(MIN)
Pour Point, C / F 0/32 5/41
Elemental Analysis, % w / w
Carbon 600 62.0
Hydrogen 7.5 7.7
Sulfur 2.7 3.0
Nitrogen 050 060
Oxygen 020 060
Ash 0.25 03
GCV, Btu/Lb 12680 11950(MIN)
GOV, MJKg''(KcalKg-'') 29.5(7046) 2 7 . 8 ( 6 6 4 0 ) (MIN)
NOV, Btu/Lb 11694 10963(MIN)
NOV, MJKg''(KcalKg"') 27.2(6497) 25.5(6091)(MIN)

240
2.3. Test Procedures for Flotation

The coal sample of 200 grams was thoroughly wetted with 400 grams of water in
a beaker by mild agitation. This slurry then was conditioned with a predetermined
amount of Orimulsion through vigorous agitation for 10 seconds in a commercial
Waring blender. The conditioned slurry was transferred to a Denver laboratory
flotation cell (4.0 L effective volume) and water was added to give a slurry of about 5
percent solids by weight. MIBC at 0.25 kg /t (0.5 lb/ton) was added and the slurry
conditioned for 2 minutes. After conditioning, air was injected and the froth was
collected for 2 minutes with the motor-driven scrapers. All the tests were conducted
under naturally occurring pH around 6.5.
When using kerosene, conditioning was performed directly in the flotation cell.
After addition of kerosene into the flotation cell, the coal slurry was conditioned for 3
minutes. MIBC at 0.25 kg/t (0.5 lb/ton) was then added and the slurry conditioned for
2 minutes. All products were filtered, dried, weighed, and analyzed. Total sulfur
analyses were performed using a LECO sulfur analyzer, and ash contents were
obtained via standard ASTM methods.
2.4. Vacuum Filtration

The laboratory vacuum filtration device used in this study was reported previously
[5,6]. Filtration rate tests were performed for some of the froth products from the
tests with Orimulsion and kerosene. For these tests, the froth collected from the
flotation cell was sent to the filtration device, and the filtration rate was measured by
recording the weight of filtrate as a function of time. The resulting filter cakes were
weighed and then oven dried. Weight losses from drying were used to determine
cake moisture.
2.5. Dust Index and Dust Reduction Efficiency

To evaluate the product dust reduction efficiency (E) due to the addition of a
binder, PETC developed a 5 minute Ro-Tap dry screening analysis method [5] to
experimentally measure the dust index (I). A dust reduction efficiency is therefore
calculated and based on the following equation.
= lo - Ii 100 (1)
lo
Where, = percent efficiency of dry cake dust reduction.

10 = dust index of cake without binder, cumulative weight percent of dry
cake finer than 100 microns after Ro-Tapping for 5 minutes.
11 = dust index of cake with binder, cumulative weight percent of dry
cake finer than 100 microns after Ro-Tapping for 5 minutes.
241
3.1. Effect of Orimulsion on Fine Coal Flotation, Dewatering and Reconstitution
3.1.1. Behavior of Orimulsion in Flotation

Table 2 compares the test results obtained with various amounts of Orimulsion and
results obtained using kerosene. The Pittsburgh No. 8 seam coal used in these tests
had a high ash content of 23 % and a high sulfur content of 6.5 %. Flotation with 0.25
kg/t (0.5 lb/ton) MIBC produced only 50.3 % froth yield (clean coal) containing 7.3 %
ash and 5.3 % total sulfur. The addition of kerosene at 1.75 kg/t (3.5 lb/ton) increased
the froth yield to 72.0 % containing 9.9 % ash and 5.7 % total sulfur. Further addition
of kerosene beyond 1.75 kg/t (3.5 lb/ton) did not increase the yield. The test results
revealed that flotation tests with Orimulsion required a much larger dosage than
flotation tests with kerosene to achieve comparable yield. However, this higher
dosage, around 20 kg/t (40 lb/ton), does not pose serious economic disadvantage
since Orimulsion costs about the same as coal on a heating basis; furthermore, this
amount is needed for the subsequent dewatering and reconstitution steps. Addition
of 2.5 kg/t (5 lb/ton) Orimulsion increased the yield to 61.1 %. As more Orimulsion
was used, the froth yield increased continuously, but the ash and sulfur content of
froth yield also increased. When 20 kg/t (40 lb/ton, about 2 %) of Orimulsion was
used, the froth yield was 72.0 % and selectivity was comparable with that observed
at a kerosene dosage of 1.75 kg/t (3.5 lb/ton). Ash content of the froth using
Orimulsion was 10.4 % compared with 9.9 % for kerosene, and sulfur contents were
5.7 % for both reagents.
Table 2
Flotation results of Pittsburgh No. 8 Seam coal (23.0 % ash and 6.5 % sulfur) at
590 microns (28 mesh) top size with 0.25 kg/t (0.5 Ib/t) MIBC.
Reagent Yield, % Ash, % Sulfur, % Combustible

Froth Tailing Froth Tailing Froth Tailing Yield, %
No Collector 50.3 49.7 7.3 39.9 5.3 7.1 61.0
Kerosene
1.75 k g / t ( 3 . 5 Ib/t) 72.0 28.0 9.9 58.5 5.7 7.7 84.8

3 . 5 0 k g / t ( 7 . 0 Ib/t) 74.3 25.7 9.9 61.8 5.7 8.2 87.2
Orimulsion
2 . 5 k g / t (5 Ib/t) 61.1 38.9 7.8 47.4 5.3 7.8 73.4
5 k g / t ( 1 0 Ib/t) 62.1 37.9 8.6 46.5 5.5 7.7 73.7
1 0 k g / t ( 2 0 Ib/t) 67.0 33.1 9.3 49.5 5.7 8.1 78.4
2 0 k g / t ( 4 0 Ib/t) 72.0 28.0 10.4 52.9 5.7 7.7 83.0
242
As shown in Table 3, the Upper Freeport seam coal possessed a high natural
hydrophobicity, producing a 65.7 % froth yield with 0.25 kg/t (0.5 lb/ton) of MIBC only.
The ash and sulfur content of the clean coal was reduced to 7.0 % and 1.1 %,
respectively, from 11.5 % ash and 1.5 % sulfur in the feed. With the addition of 0.5
kg/t (1.0 lb/ton) of kerosene, the froth yield increased considerably to 87.0 %, but the
ash and sulfur contents of the froth yield also increased considerably to 9.2 % and 1.2
%, respectively, indicating that the mineral matter in this coal was not as well liberated
as in the Pittsburgh No. 8 seam coal sample. In tests with 10 kg/t (20 lb/ton)
Orimulsion, the froth yield increased to 79.0 %, and the ash and sulfur content of the
coal increased to 8.1 % and 1.2 %, respectively. An additional doubling of the
amount of Orimulsion to 20 kg/t (40 lb/ton) did not increase the froth yield
substantially, but the ash content of the concentrate increased to 8.9 %.
Table 3
Flotation results of Upper Freeport Seam coal (11.5 % ash and 1.5 % sulfur) at 590
microns (28 mesh) top size with 0.25 kg/t (0.5 Ib/t) MIBC.
Reagent Yield, % Ash, % Sulfur, % Combustible

N o Collector 65.7 34.3 7.0 20.3 1.1 2.0 69.1
Kerosene
0 . 5 k g / t ( 1 . 0 Ib/t) 87.0 13.0 9.2 27.0 1.2 2.3 89.3
Orimulsion
1 0 k g / t ( 2 0 Ib/t) 79.0 21.0 8.1 24.3 1.2 2.2 82.1
2 0 k g / t ( 4 0 Ib/t) 81.1 18.9 8.9 22.8 1.3 2.0 83.5
The low 7.9% froth yield with 0.25 kg/t (0.5 lb/ton) MIBC, as shown in Table 4, is
indicative of the lower natural hydrophobicity of the Illinois No. 6 samples. Upon the
addition of 0.5 kg/t (1.0 lb/ton) kerosene, the floatability of this coal increased
significantly to give a 63.9 % froth yield. The selectivity was also better as the ash
content of the concentrate decreased to 8.3 % from 9.6 % with no kerosene. When
the amount of kerosene was increased to 1.0 kg/t (2.0 lb/ton), the froth yield
increased to 84.9 % with an ash content of the clean coal of 8.7 %. Test results with
Orimulsion on this Illinois No. 6 coal sample were not as good as with kerosene.
Even when 20 kg/t (40 lb/ton) of Orimulsion was used, only 65.0 % recovery was
obtained. However, the flotation selectivity was much better with Orimulsion than with
MIBC alone as indicated by both ash contents and combustible yield.
243
Table 4
Flotation results of Illinois No. 6 Seam coal (14.2 % ash and 4.9 % sulfur) at 590
microns (28 mesh) top size with 0.25 kg/t (0.5 Ib/t) MIBC.
Reagent Yield, % Ash, % Sulfur , % Combustible
No Collector 7.9 92.1 9.6 11.6 3.5 4.8 8.1
Kerosene
0 . 5 k g / t ( 1 . 0 Ib/t) 63.9 36.1 8.3 17.2 3.9 6.2 66.2
1.0 k g / t ( 2 . 0 Ib/t) 84.9 15.1 8.7 27.9 4.0 8.7 87.7
Orimulsion
1 0 k g / t ( 2 0 Ib/t) 36.3 63.7 8.1 13.3 3.8 5.3 37.6
2 0 k g / t ( 4 0 Ib/t) 65.0 35.0 8.7 16.2 4.2 5.9 67.0
Test results clearly indicate that Orimulsion is selectively adsorbed on coal and
improves the hydrophobicity of coal as kerosene does in coal flotation. However, the
adsorption of Orimulsion emulsion droplets on coal was different with different coals.
The higher Orimulsion dosage needed could be due to the following reasons: (1) the
viscosity of Orimulsion droplets may hinder the formation of water-repellent films which
enhance flotation on the surface of coal particles, (2) the hydrophobicity of Orimulsion
could be less than that of kerosene, and (3) the surfactant needed to keep the
Orimulsion stable, so that the emulsion droplets remain suspended in slurry, may
reduce the effectiveness of the emulsion in froth flotation. This phenomenon will be
discussed further in the dewatering section. More research is under way to improve
the selectivity of Orimulsion from the point of view of using a suitable emulsifier that
would improve the flotation selectivity and dewatering rate.
3.1.2. Behavior of Orimulsion in Dewatering of Flotation Concentrate

Preliminary dewatering tests by vacuum filtration were conducted on the froth
products from the flotation tests with the Pittsburgh No. 8 and the Illinois No. 6 seam
coals. Two different froth products were generated by using 20 kg/t (40 lb/ton) of
Orimulsion under vigorous agitation conditions and by using 1.75 kg/t (3.5 lb/ton) of
kerosene under mild agitation conditions. Tests were also performed with and without
Orimulsion on the raw Illinois No. 6 seam coal. Table 5 shows that the final product
cake moisture of kerosene and Orimulsion treated froth products for Pittsburgh seam
coal was 25.8 % and 30.6 %, respectively, but for Illinois No. 6 seam coai the moisture
content was the same at 28.7 % for the cakes treated by either kerosene or
Orimulsion. Figure 1 shows that the filtration rate of the Illinois No.6 seam coal was
faster with the addition of Orimulsion than without it.
244
Table 5
Cake moisture, dust Index and dust reduction efficiency of flotation products at
590 microns (28 mesh) and 21 ""C.
Cake Dust Dust
Coal MIBC Orimulsion Kerosene Moisture Index Reduction
Seam k g / t (Ib/t) k g / t (Ib/t) k g / t (Ib/t) Eff, %
Pittsburgh 0 . 2 5 (0.5) 20 (40) 0 306 5 83
Pittsburgh 0 . 2 5 (0.5) 0 1.75 (3.5) 25.8 28 3
Illinois # 6 0 0 0 26.4 28 0
Illinois # 6 0 . 2 5 (0.5) 2 0 (40) 0 28.7 15 46
Illinois # 6 0.25 ( 0 5 ) 0 1.75 (3.5) 28.7 23 18
400
240
Filtration Time, Second
Figure 1. Filtration Rate of Illinois No. 6 Seam Coal.

245
The final cake moisture content of the filter cakes was not very conclusive in this
series of tests (see Table 5). Generally, it is believed that if the finely divided emulsion
droplets remain in a dispersed stage (stable emulsion), then the froth product will be
hard to filter and will result In a higher cake moisture. On the contrary, if the emulsion
droplets form agglomerates with coal particles, the froth product will be easier to filter
and will result in a lower cake moisture and faster filtration rate. It is believed that to
be more effective, the formulation of Orimulsion needs to be modified. This modified
emulsion should have a median droplet size of around 5 microns and should be
highly hydrophobic in nature so that it would be selectively agglomerated with the coal
particles as contrasted to the mineral matter. An optimum dispersion of the emulsion
droplet size of 5 microns was reported for fine coal flotation with paraffin oil [8].
3.1.3. Behavior of Orimulsion in Reconstitution of Flotation Concentrate

The flotation concentrates generated with Orimulsion and kerosene were vacuum
filtered, thermally dried, and then Ro-tapped for 5 minutes to determine their dust
index and, therefore, the dust reduction efficiency (equation 1). As seen in Figure 2,
the resulting size distributions of filter cakes were coarser for the Orimulsion cakes for
both coals. For Pittsburgh No. 8 seam coal, the dust reduction efficiency was much
greater, about 83 % for Orimulsion as compared to 3 % for kerosene (see Table 5).
For Illinois No. 6 seam coal, the dust reduction efficiency was about 46 % for
Orimulsion as compared to 18 % for kerosene. The test results seem to indicate that
Orimulsion provides better dust reduction than kerosene.
100
Pgh-Orimulsion
10 Pgh-Kerosene
Ill-Orimulsion
l-Kerosene
I I I I 11
10 100 1000 10000
Size, microns
Figure 2. Particle size distribution of filter cakes from the froth products of Pittsburgh
and Illinois No. 6 seam coals.
246
3.2. Comparison of Orimulsion and Asphalt Emulsion in Fine Coal Dewatering

and Reconstitution Only
The temperature dependency of the viscosities of the asphalt and the bitumen
used for asphalt emulsion and Orimulsion are different, thus they could affect the in
situ cake hardening process differently, particularly in the winter season. A series of
tests was, therefore, conducted to show the effect of coal slurry temperature on cake
moisture content, cake dust index, and dust reduction efficiency for Pittsburgh seam
Bruceton mine coal of minus-74-microns particle size. All tests were performed with
high-shear blender mixing for 10 seconds with and without Orimulsion addition at 2
%. The asphalt emulsion, CRS-2, was also used for comparison.
Figure 3 shows the effect of slurry temperature on vacuum filter cake moisture
content for Pittsburgh seam Bruceton mine coal at 74 micron top size with and without
using Orimulsion and asphalt. Generally, the cake moisture contents with Orimulsion
treated cakes were about 9 percent lower than cakes without Orimulsion treatment,
and the lower slurry temperature produced higher cake moisture. For example, the
cake moisture at 7 C, 2 C, and 50^ C were 24.0 %, 21.4 %, and 17.9 % with 2 %
Orimulsion, and 32.3 %, 28.3 %, and 25.5 % without Orimulsion. For 2 % asphalt
emulsion treated cakes, moisture contents were about 4 percent lower than cakes
without asphalt emulsion treatment between 13 C to 50"" C. When the slurry
temperatures were lower than 11 C, the moisture content of asphalt treated cake was
greater than the untreated cake and it increased to 34.5 % at C. This result seems
to indicate that the lower slurry operating temperature in the winter season would not
affect the cake moisture with Orimulsion as much as it would with asphalt emulsion.
Figure 4 shows the dust reduction efficiency of dewatered cakes at different slurry
temperatures with both Orimulsion and asphalt emulsion. The data indicated that (1)
both Orimulsion and asphalt emulsion provided similar dust reduction efficiencies of
94 % and 91 % at slurry temperatures between 11"" C and 50 C, respectively; and (2)
Orimulsion continued to provide a high dust reduction efficiency of 94 % at C,
where the dust reduction efficiency of asphalt emulsion dropped drastically to 19 %.
This poor result on dust reduction between 11 C and 7 C for asphalt emulsion was
consistent with dewatering results.
Previous test data indicated that asphalt emulsion (CRS-2) is not a collector for
coal flotation. This could be because the higher viscosity of the asphalt prohibits it
from becoming an effective collector. In general, the viscosity of any binding material
seems to be a key parameter and is sometimes dependent on the process
temperature.
The performance of dewatering, reconstitution, and flotation when using Orimulsion
and asphalt emulsion seems affected by the following parameters: (1) viscosity of
water, bitumen, and asphalt, (2) surface tension of water, and (3) stability (or surface
coating) of Orimulsion and asphalt emulsion. Our future work will be conducted with
a modified emulsion which is highly hydrophobic in nature and which would selectively
agglomerate with coal particles.
247
2 %-Orimulsion
2%-Asphalt
0 % Additive
O
y
T- 1 1 1 1
^^5 10 15 20 25 30 35 40 45 50
Slurry Temperature ^
Figure 3. Effect of slurry temperature on cake dust reduction efficiency of minus 74

micron Pittsburgh seam coal with Orimulsion and asphalt.
2 % Orimulsion
2 % Asphalt
5 10 15 20 25 30 35 40 45 50
Slurry Temperature ^
Figure 4. Effect of slurry temperature on cake moisture content of minus 74 micron

Pittsburgh seam coal with and without using Orimulsion and asphalt.
248
4. CONCLUSIONS
(1) In coal flotation, Orimulsion seems to selectively adsorb onto coal and thus
improves the hydrophobicity of coal, as does kerosene.
(2) A higher dosage of Orimulsion than kerosene is required in flotation tests to
achieve comparable recovery. From a economic point of view, this higher
dosage does not pose serious problems since Orimulsion costs about the same
as coal on a heating basis. Furthermore, a higher dosage of Orimulsion is
beneficial for subsequent dewatering and reconstitution steps.
(3) Orimulsion increases filtration rate in dewatering by vacuum filtration.
(4) Orimulsion is more effective than asphalt emulsion in dewatering by vacuum
filtration, and in reconstitution at a lower slurry temperature.
(5) Orimulsion has the potential to be an effective additive for flotation, dewatering,
and reconstitution.
ACKNOWLEDGEMENT
The author wishes to acknowledge K.J. Champagne of the Coal Preparation

Division, Pittsburgh Energy Technology Center, Department of Energy, for his
conscientious experimentation.
References to any specific commercial product, process, or service is for
understanding only and does not imply endorsement or favoring by the United States
Department of Energy.
REFERENCES
1. B.K. Parekh, Proceedings, 2nd International Conference on Processing and

Utilization of High Sulfur Coals. Editors, Y.P. Chugh and R. d. Caudle, Carbondale,
Illinois, 1987.
2. G. Wasson, "Coal Dust Reduction An Evaluation of Chemical Additives and
Application Methods," Proceedings, Institute of Briquetting and Agglomeration, Vol.
20, 1987.
3. H.B. Gala, "Use of Surfactant in Fine Coal Dewatering," Ph.D. Thesis, University of
Pittsburgh. 1982.
4. W.W. Wen and A.W. Deurbrouck, "Combined Method for Simultaneously
Dewatering and Reconstitution Finely Divided Carbonaceous Material," U.S. Patent
No. 4.969.928, Nov. 13. 1990.
5. W.W. Wen. R.P. Killmeyer and A. W. Deurbrouck, "Fine Coal Reconstitution by an
In Situ Hardening Process." Proceedings of the 21st Biennial Conference of the
Institute for Briquetting and Agglomeration. Vol. 21. pp. 291-301. Nov. 1989.
6. W.W. Wen. "Simultaneous Dewatering and Reconstitution of Fine Coal,"
Proceedings of the American Institute of Chemical Engineers. 1991 Summer
National Meeting. Pittsburgh. Pennsylvania. 32 pages. August 18-21. 1991.
249
7. W.W. Wen and A.W. Deurbrouck, "A New Strategy for Fine Coal Dewatering and
Reconstitution," Fluid/Particle Separation Journal. Vol. 1, No. 2, pp. 92-96,
December 1988.
8. V.l. Klassen, I.N. Plaksine and N.S. Vlasova, "Theoretical Bases of the Action of
Reagents in Coal Flotation," Third International Coal Preparation Conference, Paper
E2, Bruxelles - Liege, June 1958.
Utilization of high sulfur coals by self-scrubbing
Robin L. Godfrey
Custom Coals Corporation
ABSTRACT
High sulfur coal states, such as Indiana, Illinois, and Ohio, are struggling with a
dilemna that has surfaced with the enactment of the 1990 Clean Air Act Amendments
(CAAA). These three states are among the top ten in the categories of coal
consumption and existing coal reserves. However, even after the high sulfur coal from
these mid-western states are cleaned in conventional coal preparation plants, it still
does not meet the emission limitation [.52 kg SOg/GJ (1.2 lbs SOg/MMBtu)] that the
CAAA mandate for the year 2000. In order to address this issue, most utilities plan
to switch to low sulfur coal from the Western U.S. and Central Appalachian region or
install scrubbers. Since coal generates almost 60 percent of the nation's electricity
and utilities consume 80 percent of the nation's coal, the choices made by the utility
companies to comply with the CAAA is of great concern to many interest groups.
Switching to low sulfur coals from outside the region puts local miners out of
work and weakens the economy in the utility's service territory. Scrubbing, which
many high sulfur state governments (namely, Illinois) advocate to preserve local
mining operations, requires a major capital expenditure by the utility. Scrubbers also
increase the operating complexity and costs of the generating station and produce
yet another environmental problem - scrubber sludge.
INTRODUCTION
Custom Coals International (CCI) possesses three cost-effective technologies

that bring most non-compliance coals east of the Mississippi River into year-2000
compliance as mandated by the CAAA. The compliance approach employed,
depends upon the characteristics of the raw coal.
Based upon the amount of organic sulfur in the coal and the ease (or difficulty)
of liberating the pyrite, three types of raw coal are differentiated as follows:
Low organic sulfur content and pyrite that liberates easily.
Moderate organic sulfur content and pyrite that liberates easily.
High organic sulfur content or the pyrite liberates with difficulty.
Depending upon the type of raw coal, the compliance approach employed for
each is described below. The beneficiated coal products that can be produced from
252
each type of raw coal above are: Carefree Coal, Self-Scrubbing Coal and Dry-
Scrubbing Coal.
1. CAREFREE COAL
Carefree Coal is a compliance product prepared by aggressive beneficiation of

non-compliance coals that have low organic sulfur and pyrite that liberates easily.
This transformation is possible because of the raw coal's make-up.
Raw coal is basically made up of three basic types of components. They are
material, pyrite and rock. Each of these three materials is found free in raw coal. But
there is a rather large portion of raw coal that is composed of two or all of these
components locked together. It is this locking that creates the array of specific
gravities characteristic of coal (refer to Figure 1).
SYMBOL MATERIAL SPECIFIC PARTICLE

GRAVITY TYPE
COAL 1.30 FREE
REFUSE 2.60 FREE
PYRITE 5.00 FREE
MIDDLING 1.55 LOCKED
MIDDLING 1.45 LOCKED
Figure 1. Types of Particles in ROM Coal
Most conventional coal cleaning disperses raw coal into two components: one
less-than and the other greater-than a pre-selected gravity. Therefore conventionally
"clean" coal contains both free and locked particles. The locked particles bring with
it sulfur (from pyrite) and ash (from rock) into the marketable "clean" coal product.
253
The refuse also contains both free and locked particles; however, the locked particles
contain organic matter that constitutes a loss of bonafide coal (heating value) and for
the producer, a loss of revenue (refer to Figure 2).
DENSE MEDIUM
SPECIFIC GRAVITY
1.50
Figure 2. Conventional Dense Medium Process
The Carefree Cleaning Process (CCP) liberates the locked particles. This is a
major factor distinguishing the Carefree process from conventional coal cleaning. The
CCP crushes coarse locked particles to produce smaller particles. Most of the smaller
particles are relatively free, depending on the type of raw coal. The principal steps
in the CCP are:
Recover a low specific gravity (1.30), coarse (plus 1/2 mm) clean coal product
(refer to Figure 3).
Reject a high specific gravity (2.00), coarse refuse (refer to Figure 3).
Crush the resulting middling product (specific gravity 1.30 by 2.00) to liberate
pyrite, other ash-forming minerals and coal (refer to Figure 4).
254
CLEAN COAL
OiNSE MEOIIlii
SPECIFIC QRAViTY
1.0
MIDDLINGS
REFUSE SPECIFIC GHAVITY
2.60
o
Figure 3. Three Product Separation
Figure 4. Liberation by Crushing/Grinding

255
Size and classify the resulting minus 1/2 mm comminuted and natural material
into three fractions: fines, ultra-fines and slimes. Discard the slimes; these
are generally high in ash, (50 percent or so) due to an abundance of clays.
Clean the fines and ultra-fines in dense medium cyclone circuits. These
circuits employ magnetite that is an order-of-magnitude smaller than
conventional magnetite and cyclones of unique design. Recover the
magnetite in circuits designed for the size of the coal and refuse particles
(refer to Figure 5).
Dewater all the clean coal fractions: coarse, fine and ultra-fine. Some thermal
drying may be required depending upon the coal.
Six-Inch Lump of
Coal
Dense Media
Suspension of 1.5
Specific Gravity
Comprised of
Sand-Sized
l\âgnetite Grains ii i
Pea-Sized Rock
Six-Inch Lump of (1.8 Sp.Gr.) Pea-Sized Coal \
Rock (1.4 Sp.Gr.) ^
Figure 5. Illustration of Sink-Float Principle
2. SELF-SCRUBBING COAL
The compliance product prepared from non-compliance coals that have moderate
organic sulfur and pyrite that liberates easily is Self-Scrubbing Coal. In this process
the sulfur is removed in two steps, one occurs in the coal preparation plant and the
other in the boiler.
256
Coals with moderate organic sulfur and pyrite that liberates easily are aggressively
beneficiated first, as described above. A high Btu recovery is maintained while at the
same time both pyrite and ash are reduced as much as possible.
A sorbent is then used to capture the sulfur dioxide produced when the organic
sulfur and residual pyrite are oxidized during combustion. Dolomite, limestone or
dolomitic limestone is the sorbent that is then agglomerated (pelletized) with the ultra-
fine fraction of clean coal.
The final clean coal product from the above process is Self-Scrubbing Coal. It is
comprised of clean coarse coal, clean fines and pellets containing ultra-fine coal and
sorbent.
There are several improvements that result from using Self-Scrubbing Coal,
especially, when compared to earlier combustion trials by others in which both the
sorbent and coal were injected together through the burner.
Less sintering occurs with low-NO^ burners, a requirement of the recent

amendments to the Clean Air Act. Sintering causes a loss of sorbent
reactivity due to a reduction in the surface area of the sorbent. Greater
sintering occurs at higher temperatures and less at lower temperatures.
Sintering is minimized by low-NO^ burners that provide an improved
time/temperature profile for SOg capture.
Slagging and fouling are reduced. The presence of ferrous iron aggravates
slagging. Removal of 85 to 95 percent of the pyrite during coal cleaning
substantially eliminates ferrous iron and therefore its fluxing action on siliceous
constituents.
Most minerals found in the mineral matter of coal are not volatile at the flame
temperatures encountered during combustion. Illite and biotite are
exceptions. These minerals form a glassy phase around 954 C (1750" F) and
1093''C (2000 F), respectively. Illite and biotite, found in the shale and clay
groups, are mostly removed by the unique desliming step, part of the
aggressive beneficiation process.
Calcium is sometimes implicated as an element that contributes to slagging.

This is true of organically bound calcium that is volatile. Calcium from
dolomite or limestone is not volatile at the temperatures encountered at
potential slagging surfaces.
The quantity of ash is not excessive. Aggressively beneficiating the coal

before introduction of the sorbent keeps ash levels near or below pre-
established levels.
Higher removals of sulfur dioxide are possible due to greater calcium-to-sulfur

stoichiometry. The aggressive beneficiation reduces sulfur substantially. For
a given quantity of sorbent, lower sulfur means greater calcium-to-sulfur
257
ratios. And, proportionately greater capture of sulfur dioxide occurs with

higher calcium-to-sulfur ratios.
Water soluble alkalies are removed by the beneficiation process, thus

reducing the potential for fouling.
Self-Scrubbing Coal attains year 2000 compliance with coals of moderate organic
sulfur and pyrite that liberates easily. No additions to or modifications of the boiler are
required with Self-Scrubbing Coal. It is received, stored, reclaimed, pulverized and
burned the same as conventionally prepared coal.
3. DRY-SCRUBBING COAL
Non-compliance coals that have difficult-to-liberate pyrite or high organic sulfur

content can be prepared into a compliance product through Dry-Scrubbing Coal.
While the Carefree and Self-Scrubbing Coal technologies can address sulfur reduction
needs for many raw coals, much of the Pittsburgh and Illinois seam coals requires
further treatment.
Substantial amounts of unused calcium oxide are present in the flyash produced
by burning the aggressively beneficiated coal to which sorbent was added. This lime
is available to capture additional sulfur dioxide, either in the duct between the air
preheater and the electrostatic precipitator or in an add-on spray dryer.
Two conditions are required for the capture of sulfur dioxide in spray dryers or in
in-duct processes. The temperature of the flue gases must be lowered to within about
-9C (15F) to 2 " C (35F) of the adiabatic saturation temperature. And, an alkaline
reagent such as lime must be present to react with the sulfur dioxide.
For high sulfur coals, the high cost of the reagent is a severe limitation to the use
of spray dryers and in-duct processes. With respect to reagent cost, however, Dry-
Scrubbing Coal has several advantages:
Less reagent is required because there is less sulfur dioxide to be removed. The
sulfur content of the flue gases before the dry processes is essentially the same
as if a low or moderate sulfur coal were burned. This is because the sulfur is
removed by aggressive cleaning and is captured in the boiler.
The unused alkali content of the flyash contains sufficient reagent to capture the
residual sulfur dioxide.
The unused alkali is present as calcium oxide, lime. It was purchased as calcium
carbonate, limestone, and converted in the boiler to the reactive oxide. On an
equal calcium basis, lime costs 2.4 times as much as limestone, assuming lime
costs $65 per ton and limestone $15.
The cost of the reagent can be considered zero in that it is part of the competitive
price paid for the coal.
258
Custom Coals is currently evaluating the economic and technical synergy between
its Dry-Scrubbing Coal and several available and emerging dry processes for
removing sulfur dioxide. Two obvious economic benefits include reduced reagent
cost and lower capital cost for the dry SOg removal processes. The latter depends
upon the extent that equipment size is proportional to the SOg removal requirement.
4. HIGH SULFUR COAL STATES AND CUSTOM COALS
Utilities need to develop compliance plans before state regulatory treatments will
be known. In some states, Public Utility Commissions (PUCs) are attempting to
address this uncertainty by modifying the traditional after-the-fact prudence review in
favor of some kind of pre-approval process. State legislatures may impose de facto
pre-approval by statutorily declaring certain compliance options and technologies to
be prudent.
Lawmakers in Indiana, Illinois, and Ohio promote the idea of preserving the coal
industry in their respective states. Indiana, for example, requires utilities to include in
all compliance plans an analysis of employment effects of the proposed change of fuel
type. Ohio law encourages the use of Ohio coal through tax breaks, low incentive
loans, easier permitting of landfills (for scrubber waste) and recovery of construction
work-in-progress costs. Illinois lawmakers have gone even further to insure the use
of in-state coal. Illinois has passed a law requiring two plants owned by Illinois Power
Co. and two plants owned by Commonwealth Edison Co. to install scrubbers as part
of their compliance strategies.
A report published by the Illinois Coal Development Board (CDB), Outlook for the
Illinois Coal Industry", conveys a solemn future for the state's coal-related industries.
The study projects that coal sales will decrease by one-third, some 20,000 jobs will
be lost and revenues to the state will fall by $50 million.
As discussed above. Custom Coals can be part of the answer to the dilemma that
these high sulfur coal states face in light of the CAAA. Custom Coals has performed
various analyses of coal from the mid-west and has proved that its technology can
bring these high sulfur coals into compliance.
As an example. Custom Coals evaluated a Lower Freeport coal from eastern Ohio.
The raw coal has 2.8 kg SOg/GJ (6.4 lbs SOg/MMBtu). The organic sulfur content is
moderate and the pyrite liberates easily. A .52 kg SOg/GJ (1.2 lbs SOg/MMBtu)
compliance Self-Scrubbing Coal can be made from this feedstock.
Through aggressive cleaning the 2.8 kg SOg/GJ (6.4 lbs SOg/MMBtu) in the raw
coal can be reduced to .91 kg SOg/GJ (2.1 lbs SOg/MMBtu). Cleaning to this level
removes 67 percent of the total sulfur in the raw coal. With Self-Scrubbing Coal, an
estimated 43 percent of the sulfur will be captured in the boiler through sulfation of the
sorbent. Predictions of the sulfur capture in the boiler are based upon data from the
literature from full-scale plant and test-boiler evaluations of SOg capture by sorbents
entering the boiler with the fuel and pilot-scale testing by Custom Coals. The final
emission limit of .52 kilograms of sulfur dioxide (1.2 pounds) comprises a total sulfur
reduction of 81 percent.
259
Analyses of the products from raw coal to Self-Scrubbing Coal are given in the
following table:
Product Ash,% kg SO2/GJ Incremental SO2 Total SO2

(lbs SO^/MMBtu) Reduction, % Reduction, %
Raw Coal 12.8 2.74 (6.35) N/A N/A
Cleaned Ooal 3.7 .90 (2.08) 67.2 67.2
Self-Scrubbing Coal 13.3 .51 (1.18) 43.3 81.4
Custom Coals technology can be used to achieve the goals of sulfur reduction
and continued use of in-state coal at costs which are substantially less than those
associated with the installation of scrubbers. Figure 6 shows the areas of Indiana,
Illinois and Ohio where raw coal feedstocks suitable for the production of Carefree
and Self-Scrubbing Coals can be found. Figure 7 graphically portrays the amounts
of coal in those states to which the CCI technology can be applied.
5. CONCLUSION
Custom Coals has a comprehensive strategy for converting high sulfur coals into
compliance coals. In addition to the environmental benefits of CCI products, it also
provides economic security and stability to communities affected by the operation of
nearby coal-burning utilities. Because these clean coal products are produced from
an electric utility's existing fuel supply, they offer a number of specific economic
advantages over other compliance strategies ~ which translates into significant
benefits for local communities.
With Custom Coals products, utilities are able to maintain their existing fuel supply
agreements, thereby preserving local mining jobs. In addition, the plants needed to
produce these clean coal products create new jobs in both construction and
operations.
Utilities can avoid the high capital cost of scrubbers and the high transportation
charges that would otherwise be added to their fuel costs in switching to low sulfur
coal. The significant cost savings represented by CCI products enable utilities to keep
rates in check, which also benefits local economies by enabling area businesses to
remain competitive.
CCI can enable coal-fired electric utilities to minimize their operating costs, remain
in compliance, and keep rates low, thereby maximizing shareholder value and allowing
utilities to continue providing clean and affordable electric power to the community.
260
Self-Scrubbing Coal
Carefree Coal
Botb
Figure 6. Feedstocks in Three States Suitable for CCI Technology
60
Northern Central Southern
Illinois Basin
Appalachia Appalachia Appalachia
^ 50-4
Figure 7. Suitable Feedstocks for CCI Technology

261
REFERENCES
1. National Coal Association, Facts About Coal (1991) 12 and 19.

2. J.K. Kindig.Ph.D., Middlings Grindings and Novel Fine-Coal Cleaning Produces
Feedstock for Self-Scrubbing Coal, International Pittsburgh Coal Conference,
Pittsburgh, PA (1991).
3. J.K. Kindig.Ph.D., Self-Scrubbing Coal an Integrated Approach to Clean Air, Coal
Prep '92 Conference, Lexington, KY (1992).
4. R.L Godfrey, Coal: Viable Fuel for The Future, Power Gen '92 Conference,
Orlando, FL (1992).
5. R.L Godfrey, Self-Scrubbing Coal, U.S. DOE First Annual Clean Coal Technology
Conference, Cleveland, OH (1992).
Chemical desulfurization of Canadian high sulfur coal with

potassiunfi permanganate
Y.A. Attia^ and A. Fung''
^The Attia Applied Sciences Incorporated, TAASI Laboratory, 1445 Summit Street,
Columbus, Ohio, 43201, U.S.A.
'^CANMET, Western Research Centre, Energy, Mines and Resources, 1 Oil Patch
Drive, P.O. Bag 1280, Devon, Alberta, Canada, TOC 1E0.
ABSTRACT
A Canadian high sulfur coal from Nova Scotia containing 8.93% sulfur and
12.08% ash was pre-cleaned by heavy liquid separation at a specific gravity of 1.33.
It was then subjected to chemical desulfurization with potassium permanganate at
room temperature and atmospheric pressure. Several process parameters were
investigated including pH, particle size, concentration of potassium permanganate,
solid content and number of chemical cleaning stages.
The pre-cleaned coal containing 4.81% sulfur and 5.62% ash, was then fed to the
chemical treatment. After three stages of chemical cleaning, the product coal
contained 2.22% sulfur and 3.48% ash, when the particle size of coal was -200 mesh
(-74 micron). Slurries of the pre-cleaned coal with -400 mesh (-37 micron) particle size
were subjected to four stages of chemical treatment. The cleaned coal contained
1.76% total sulfur and 4.86% ash. The pyritic sulfur was reduced from 1.87% to
0.06% while the organic sulfur was reduced from 2.76% to 1.71%. Thus it is possible
to reduce the total sulfur content from 8.93% to 1.76% by combined physical and
chemical techniques. The possible mechanisms involved in this process are also
discussed in this paper.
INTRODUCTION
Coal is Canada's most abundant fossil (1) fuel with 6 x 1 0 ^ tons proven reserves
and 3 x 1 0 ^ tons in deposit, which allow for more than a century supply of coal at
current production rate. Coal could be used itself as feed stock for chemical and/or
pharmaceutical industries, reductant for iron-making (using coking coal) and more
importantly for generation of electrical energy. It would be also utilized as COF (Coal
Oil Fuel). CWF (Coal Water Fuel) or CMF (Coal Methanol Fuel), etc. but its utilization
can cause a number of ecological problems such as subsidence, destruction of land
surface, acid mine drainage and air pollution. The reason for the land and air
pollution is that coal contains impurities such as sulfur and nitrogen.
264
Among the different impurities in coal, sulfur is one of the most notorious and it
causes problems in one way or another for major coal users. For example, in
metallurgical coal, sulfur increases the difficulty and the cost of making steel; in steam
coal, it contributes significantly to the wear and tear of equipment; and especially for
generation of electricity or building heating it produces sulfur dioxide emissions,
creating pollution problems and corroding boilers during combustion operation.
Sulfur exists in coal in two principal forms, organic sulfur which is chemically
bound to the coal and cannot be removed by physical methods, and inorganic sulfur,
mainly pyrite. which is not bound chemically and could be physically removed to
certain degrees from the parent coal. The extent to which sulfur content can be
reduced will depend on the nature of the sulfur form and on the particle size, size
distribution and the cleaning process. Table 1 describes the different forms of sulfur
in coal.
In practice, coal is usually cleaned at the coal mine washery to reduce its
impurities like sulfur and ash prior to transporting to the users; however, conventional
cleaning methods, i.e., physical methods by density differences or changes in surface
properties, leave a certain amount of pyritic sulfur in the coal. The organic sulfur in
the coal is basically unchanged (3). A chemical approach is, therefore, required for
the removal of organic sulfur. Previous studies on the permanganate oxidation
approach (4) using American coals, indicated that up to 48% of the organic sulfur and
76% of the total sulfur could be removed by this process.
Eastern Canadian coals (primarily in Nova Scotia) generally contain high sulfur.
This paper describes attempts to desulfurize a Nova Scotia coal under conditions of
ambient temperature and pressure.
The objective of this research was to investigate the feasibility of cleaning and
desulfurization of a Canadian High Sulfur coal by a chemical process using potassium
permanganate, after pre-treatments with physical cleaning techniques. In this work,
heavy liquid separation at specific gravity 1.33 is used to simulate physical cleaning
of coal, before the chemical treatment with potassium permanganate.
EXPERIMENTAL APPROACH
The overall experimental approach used in this laboratory investigations is shown

in Figure 1.
1. COAL SAMPLE PREPARATION
1.1. Crushing and Screening

The Nova Scotia coal which was used in this investigation was supplied by Cape
Breton Coal Research laboratory, Sydney, Nova Scotia. The coal samples were kept
in a walk-in cooler at about 4C to avoid oxidation. As shown in Fig. 1 and Table 2,
the raw coal containing 8.93% sulfur and 12.08% ash was crushed and screened to
the size range of - 6 + 1 0 0 mesh (-280 + 150 microns). The -100 mesh (-150 micron)
coal sample was discarded because of the inability of the heavy liquid separation
process to handle -100 mesh size particles. The -6 -i- 100 mesh samples were
265
Table 1. Different Forms of Sulfur in Coal
Sulfur Forms Chemmical Explanations

Formula
Pyrites and FeSg (cubic) Marcasite is less
Marcasite FeSg (orthorhomic) stable than
(main inor pyrite; upon
ganic portion) heating it is
converted to
Inorganic Sulfur pyrite
Sulfates F e S 0 4 7H20(melanterit In weathered
(small amount e) coal the sulfate
of inorganic (Na.K) F e 3 content
sulfur in .(S0j2(0H)e increases
sulfate form) (jarosite) because of
CaS04 2H2O (gyp oxidation
sum)
RSH (mercaptan or R and R' Being

thiol) alkyi or aryl
RSR' (sulfide or group
thio-ether)
Organic Sulfur RSSR' (disulfide)
Aromatic system con thiophene ring
taining thiophene ring
(5)
266
NOVA SCOT I A COAL

5=8.93 X
A5H=12.08 %
CRUSH ING
&
I S C R E E N I NG
I
-6 t 100 MESH
-100 ME5H FINES

O R G A NCI L l O UOl
SEPERAT ION S = 9 . 1 7 %
ASH=13.87 2
AT 1 . 33 S.G.
'ÂSH=5.62
GR 1ND1NG
CS INK)
'200 ME5H
KMnO ^ ROCKS, SHALES ft.

COARSE PYRITE
OX I O A T I ON
5=9.34 %
ASH= 1 4 . 9 8 %
FILTRATION
I
MULT I - S T A G E
OXIDATION - WASH I NG
I
HC I
I CL A N 1 N G
I HOT WATER
I WASHING

F 1 L T R A T 1 ON
WASTE LIQU I D
CLEAN COAL
Figure 1. Experimental Procedures.

267
retained and the + 6 mesh sample was re-crushed through stage-crushing using a
Massaw jaw crusher. This was followed by screening through a # 6 mesh screen, and
this crushing/screening procedure was repeated until all samples passed through # 6
mesh. The final -6 + 100 mesh samples contain overall 8.91 % sulfur and 11.95% ash.
1.2. Heavy Liquid Separation (Physical Pre-cleaning)

The use of a heavy liquid to separate two or more phases of specific gravities
has been reported for more than 65 years (6-8). By using a heavy-liquid separation
system to beneficate coal in the 1930s, the Dupont company (9) used a pilot plant
for cleaning anthracite at the western breaker, Shenandoah, Pennsylvania. The Otisca
process (10, 11) is a waterless, heavy liquid process using C C I 3 F . The separation
behavior in a heavy liquid is normally defined by Stoke's Law under ideal conditions:
2grH92-P^)
0.09
whereV = velocity of the separating particle (cm/sec)

r = radius of the particle (cm)
= density of the liquid
P2 = density of the particle
= viscosity of the liquid system (centipoise cP)
The ideal heavy-liquid should have the following characteristics: density is

between 1.25 and 1.70 g/cm^, unreactive with the materials to be separated, low
viscosity, low boiling point, low heat of vaporization, low flammability, low toxicity, low
corrosive properties and inexpensive.
Physical pre-cleaning was performed in this work by means of a heavy organic
liquid with 1.33 specific gravity (s.g.) using two different liquids in proportion.
In this case, liquid Varsol with 0.78 s.g. and perchlorethylene with s.g. of 1.62
were used. After heavy liquid separation, the sink portions contained coarse pyrites
and waste materials which have 9.34% sulfur and 14.98% ash. The float sample, as
well as the sink sample, were washed with acetone to eliminate any organic solvent
effects on coal surface properties. They were then dried in a specially designed
drying oven. The float sample was ground before chemical desulfurization tests and
contained 4.81% sulfur and 5.62% ash. The results are shown in Table 2.
1.3. Grinding Coal Samples after Physical Pre-cleaning

After heavy liquid separation the pre-cleaned coal samples were screened
through the +200 mesh sieve (+74 micron). The oversize samples were ground and
screened again through 200 mesh screen. This grinding/screening was repeated until
no further size reduction could be done by the grinding mill. Straub model 4e. The
rest of the +200 mesh samples were ground using wet ball-milling method. After
three rounds of ball-mill grinding, about half an hour for each round, more than 99%
268
of coal samples passed through 200 mesh screen. This was followed by drying and
mixing well for this desulfurization study.
The -400 mesh (-37 micron) pre-cleaned coal samples were prepared by using
a similar procedures, i.e. repeated ball-mill grinding and screening until more than
99% of coal samples passed through 400 mesh screen. After drying and mixing well,
all samples were stored in the walk-in cooler.
Table 2
Ash and sulfur contents of the Nova Scotia coal samples before and after heavy liquid
separation
Sample Ash % Total Sulfur Organic Sulfur Pyritic Sulfur
Raw Coal 12.08 8.93 - -
-100 Mesh
(before 13.87 9.17 - -
separation)
Sink Sample 14.98 9.34 - -
Pre-cleaned 5.62 4.81 1.86 2.75

sample
2. COAL CLEANING WITH POTASSIUM PERMANGANATE
2.1. Chemical Reagents

Analytical grade potassium permanganate (KMnOJ, hydrochloric acid (HCl) and
sodium hydroxide (NaOH) from Fisher Scientific Company, Nepean, Ontario, Canada
were used. Solutions of these chemicals were made at the required concentration by
using de-ionized water.
2.2. Variable Conditions of KMnO^ Oxidation Reaction

- Reaction at room temperature and atmospheric pressure
- Oxidation time: 1.5 hours for multi-stage oxidation reaction
1.5 hours for different pH conditions
2.0 hours for different 4 concentration
- Coal content: 10% and 25%
- pH value.O.5- 13.5
- Agitation speed:950 - 1500 rpm
- Number of oxidation steps: 1 - 4
- Permanganate concentration :2.5, 5, 10, 20, 25 and 30%
According to previous studies (12) and the experiments, sulfur removal was not very
sensitive to solution pH during the permanganate desulfurization (except close to neutral
269
conditions at which sulfur removal was found most effective). Therefore, except for the
investigations on pH effect, tests were performed without pH control.
2.3. Experimental Procedures

Ten or twenty five grams, depending on solid (coal) %, of -74 or of -37 micron pre-
cleaned coal samples were placed into a 1000 ml flat-bottom beaker containing the
required concentration of potassium permanganate (KMnOJ aqueous solution. The coal
slurry and the oxidizing reagent were mixed with a variable speed impeller, stirrer type
RZR50. After one and half hours mixing, or two hours mixing in the case of multi-stage
desulfurization, the reaction mixture was filtered under pressure using a Fischer stainless-
steel 750 ml filtering cylinder equipped with a pressure monitor. The reaction solid
mixture was washed repeatedly with 80C warm water until the pH value of the filtrate was
close to neutral.
The filter cake was transferred to a 1000 ml flat-bottom flask. 100 ml of 16% HCl
solution was poured carefully into the flask. The slurry was stirred for one hour using a
plastic-coated impeller. After HCl washing, the reaction mixture was filtered in a Bchner
funnel, and was washed repeatedly with warm (about 80C) de-ionized water until the pH
of the filtrate was close to neutral.
The filter cake was dried in a steam-drying oven overnight and was mixed very well,
ready for sulfur, ash and other tests.
2.4. Analysis
Total sulfur was determined by Leco Sulfur Determinator model SC32. Pyritic sulfur
and sulfate sulfur were determined by a combined method of ASTM chemical method
ands SC32 sulfur determinator (i.e., by measuring the total sulfur before and after
extraction of pyrite sulfur and sulfate sulfur). Organic sulfur was calculated by subtracting
the sulfate and pyritic sulfur from the total sulfur in the coal. The ash content was
analyzed by Fischer Coal Analyser.
3. EFFECT OF PERMANGANATE CONCENTRATION ON THE SULFUR REMOVAL
Chemical oxidations were carried out with pre-cleaned Nova Scotia coal sample
using different concentrations of potassium permanganate under ambient conditions of
room temperature and pressure for two hours. These oxidations were followed by 16%
HCl washing and 80C water washing for 1 hour, and half-an-hour respectively. The coal
solids contents (of both oxidation and washing steps) tested were 10% and 25%. The
results are shown in Table 3 and Figures 2, 3 and 4.
As shown in Figure 3, it appears that total sulfur decreased gradually within the
whole range of concentrations for 25% solid series (upper curves). The total sulfur
changed very little at the lower concentrations of potassium permanganate (i.e. 2.5%
4 S""/^ 4) decreased more quickly with increasing the 4 from 5%
all the way to 25%. For example, with 10% of 4, 18.2% of the total sulfur was
removed compared with 4.5% removal with 5% 4. As to the 10% solids, it appears
270
that total sulfur content dropped sharply between 0% 4 to 5% 4 and

continuously decreased down until 20% 4 . After 20% 4 total sulfur content
increased again. The reason for this increase is not clear at this time.
Table 3
Effect of 4 concentration (%) on Sulfur removal (%).
% Sulfur in Coal
10 % Solids 25% Solids

KMnO^ Total Sulfur Total ASH Solid Yield
(%) (%) Sulfur (%) (%)
(%)
0.0 5.12 5.12 5.62 100
2.5 ND 4.93 5.09 96.9

5.0 3.70 4.89 5.11 96.2
10.0 3.00 4.19 4.70 95.9
20.0 2.24 3.31 4.07 93.7
25.0 2.44 3.02 3.79 88.6
Oxidation time 2h
Agitation speed 1100-1500 rpm
Particle Size -200 MESH
Table 3 indicated a good example for the series tests of 25% solid, where ash
decreased gradually with the whole range of 4 . For example, as shown in Figure
3, ash was decreased sharply, i.e. 13.8% ash removal with the increase of potassium
contration from 10% to 20%. The overall ash removal, i.e. 5.62% ash (at 0% 4 ) *o
3.79% ash (at 25% 4 ) for 25% solids was calculated at 32.6%. Figure 4 indicated
that as 4 concentration increased the product yield decreased for the series tests
of 25% solid. But effective yield reduction did not occur until the concentration of 4
was 10% or higher.
271
2.5 5 10 20 25
CONCENTRATION OF KMn04 (%)
25 % SOLIDS 10 % SOLIDS
Figure 2. Effect of Permanganate Concentration (%) on Sulfur Removal (%).

272
2.5 5 10 20 25
25 % SOLIDS
Figure 3. Effect of Permanganate Concentration (%) on Asli Removal (%).

273
2.5 5
25 % SOLIDS CONTENT
Figure 4. Effect of Permanganate Concentration (%) on Solid Yield (%).

274
4. EFFECT OF MULTI-STAGE PERMANGANATE OXIDATION ON

DESULFURIZATION
The multi-stage permanganate oxidations were performed in order to achieve higher

level of sulfur removal. These studies involved two series of tests by using size of -200
mesh (-74 micron) coal samples for 3-stage oxidation and by using size of -400 mesh (-
37 microns) coal samples for 4-stage desulfurization. By studying these two series of
tests, the effect of number of desulfurization step and the effect particle size were
achieved. Sequential oxidation and washing approach was employed, i.e. multiple stages
of treatment with 10% 4 at 10% of solids (coal) content and a washing step using
16% HOI and then hot water (80C), following each oxidation step were performed.
Starting with 3rd stage for both testing series, ultrasonic irradiation was intermittently
applied for fifteen minutes to assist to break up the oxidation-product layer.
As shown in Table 4, 26.78% organic sulfur removal with 3.48% ash content was
obtained after three stages of treatment on -200 mesh coal, and 38.08% organic sulfur
removal with 4.86% ash content was obtained after four stages of treatment on -400 mesh
coal. While the results show that the pyritic and total sulfur were reduced by 90.14% and
53.98% respectively, after three stage oxidation for -200 mesh series and were reduced
by 97.05% and 63.36% respectively for -400 mesh series. However, if considering both
physical and chemical cleaning methods, the total sulfur decreased by 80.85%, i.e. from
8.93% to 1.76%.
From Figures 5, 6, and Table 4, the results showed the overall picture of
permanganate multi-stage oxidation: (1) Smaller size particle, i.e. -400 mesh (-37 micron)
in this report resulted in more effective desulfurization than the large size, -200 mesh (-74
micron) (2) For both -200 mesh and -400 mesh series as shown in Figure 6, the sulfur
removal in the second, the third and even the fourth steps in the case of -400 mesh
series was less than that of the first step. This may be due to the dissolution of easily
removable forms of organic sulfur leaving the more difficult forms (i.e., thiophenes)
behind.
In Table 4, the results also indicated that the ash content in the second stages (for
both -200 mesh test and -400 mesh test) were found to be higher than the corresponding
first stage. This could possible be due to incompletely washed MnOg. jarosite (KFeg
(S04)2(OH)g) and other oxidation by-product precipitates after permanganate
desulfurization reaction. These by-products may have been tightly bound on the coal
particle surface or even the pores of the coal.
In order to remove these layers so as to achieve maximum sulfur and ash removal,
ultrasonic dispersion technique was intermittently employed on and after 3rd stages for
both series of testing. The time period for ultrasonic irradiation was fifteen minutes for
each application. Results in Table 4 indicated that at 3rd stage 3.48% and 4.26% ash for
-200 mesh and -400 mesh series respectively and at 4th stage 4.86% for -400 mesh
series only. The ash contents could be maintained the same level as the 2nd stage (the
lowest for both series) after ultrasonic technique was employed.
Figure 6 indicated that for -400 mesh series, over 90% pyritic sulfur was removed
at the second stage while organic sulfur content decreased gradually with stages of
permanganate oxidation.
275
1 2 3
DESULFURIZATION STAGE
- 200 MESH - 400 MESH
Figure 5. Effect of Multi-stage Desulfurization using two different Particle Sizes,

-200 mesh and -400 mesh.
276
1 2 3
DESULFURIZATION STAGE
/ . T O T A L SULFUR % PYRITIC SULFUR - - % ORGANIC SULFUR
Figure 6. Variation of Different Sulfur forms with Permanganate Desulfurization.

277
Table 4
Effect of multi-stage desulfurization using two different sizes,
-200 mesh (-74) and -400 mesh (-37 micron).
% Sulfur in Coal
-200 mesh -400 mesh

Oxidation Organic Pyritic Total ASH Organic Pyritic Total ASH
Stage Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur
(%) (%) (%) {%) (%) (%) (%) (%)
0 2.76 1.87 4.81 5.62 2.76 1.87 4.81 5.62
1 - - 2.92 3.39 - - 2.55 4.37

2 - - 2.39 9.30 2.12 0.14 2.28 4.69
3 2.02 0.18 2.22 3.48* 1.84 0.08 1.95 4.26*
4 - - - - 1.71 0.06 1.76 4.86*
* Ultrasonic Dispersion Technique Being Applied.
Oxidation time 1.5h

Solid Percentage 10% Coal
5. PH EFFECT ON THE SULFUR REMOVAL
Without pH control, the slurry of pre-cleaned coal with 10% solids content and 10%
of potassium permanganate was 9.3. After two hours of reaction, it was found that at the
end of desulfurization reaction the solution pH was 8.2.
To study the pH effect on the sulfur removal, the pH value of the coal slurry with
10% solids and 10% potassium permanganate concentration was adjusted by using 1:1
of 50% HCl, and 0.1 NaOH. After each oxidation, the sample slurry was washed with
16% HCl and then with hot water at about 80 C for about half an hour. The results are
shown in Table 5.
As shown in Table 5, the total sulfur was higher at the acidic contition (pH 0.5-5.0)
than that at neutral and mild alkaline conditions. The lowest sulfur content could be
found near neutral condition, i.e. pH=6.5. At pH 9.5 the total sulfur content increased a
litte and became higher again at very high pH value (3.14 total sulfur at pH 13.3).
278
Table 5
Effect of inltal pH value on Residual Sulfur in Coal (%)
pH Sulfur in Coal
(%)
0.5 3.11
5.0 3.23
6.5 2.75
9.5 2.92
13.3 3
Oxidation time 1.5h
Particle size -200 mesh
4 concentration 10%
Solid Percentage 10% Coal
6. Possible Reactions in the Potassium Permanganate-Sulfur-in-coal system
Potassium permanganate is a general oxidizing agent and thus, any reaction with
lower electrochemical oxidation potential than that for potassium permanganate solution
will take place. The two-half reactions (i.e., cathodic and anodic) associated with sulfur
oxidation by potassium permanganate, as well as the overall reactions are summarized
below.
Cathodic Reactions
MnO^ + 2HÔ + 3e- = MnOî + AOH' ; E=1.23\/ (^)
'^2^4-=2^, =1.23+0.0148 log 2 - 0 . 0 5 9 1 - 0 . 0 1 4 8 log P{Hr,C) (2)
MnO^ + 8W^ + 5 e - = Mn^* + 4HÔ ; E=1.52V (add) (3)

279
Anodic Reactions
FeSg = Fe2* + 2S' + 20- ; E=0.63l/ (4)
Fe^' = Fe^* + " ; E=0.7-0.77V/
2- (6)
s- + AHô = so; + 8/y* + 6-
FeSa + aWgO = Fe2* + 2SO4" + + 14- ; E = - 0 . 3 6 2 ( 8 )
S2" + 2 = SO4 + BH* + Be- (9)
Overall Reactions (Alkaline media)
K* + SFe^* + 2SOf + SOW- = KFe^{SOÔH)ei{,Jarosite)
4Fe2* + Og + lO/VgO = 4 F e ( 0 / / ) 3 + BH* (11)
Orgr. Sulfides R^SR2=R^SOR2 (/?, anrf /?2 being alkyI or aryl groups) (12)
Orflf. Disulfides R^S^R^ = R^SO^H + R^SO^H. or HzSO^ ^^^^
Mercaptan RSH = RS^R (14)

280
OH
Thiophenes [ggQ 0^ + SO (15)
3 OH

o o
2NaOH . Na S + HO (16)
2 2
(17)
KMnO^ s one of the numerous oxidants reported (15) which can affect the conversion
of organic sulfur compounds to sulfones. Under suitable conditions, the -SOg- from
sulfone could be eliminated by base like NaOH, and the final sulfur compound, in our
case after oxidation reaction is sulfate ions
-2
'4
CONCLUSIONS
The test results lead to the following conclusions:

From previous studies (12-14) and also from the test results, potassium permanganate
appears to have a good potential as an oxidizing reagent not only for pyritic sulfur but
also for various forms of organic sulfur.
1. The permanganate oxidation of Nova Scotia coal can successively remove up to
53.99% total sulfur removal with three-stage permanganate oxidation for -200 mesh
coal slurry, and up to 63.36% total sulfur removal with four-stage oxidation
treatments for -400 mesh coal slurry can be achieved.
2. The combined method of pre-cleaning the raw Nova Scotia coal with heavy liquid
(organic liquid) gravity separation, i.e. physical cleaning method, followed by the
permanganate oxidation step, i.e. chemical cleaning, and washing step, reduced the
total sulfur content from 8.93% to 1.71%, i.e. 80.85% total sulfur removal.
3. Chemical desulfurization by using potassium permanganate is a very effective
method to removal pyritic sulfur from the Nova Scotia coal sample. A substantial
reduction of up to 96.79% of the pyritic sulfur (from 1.87 to 0.06%) has been
achieved.
4. Potassium permanganate has comparatively high potential among the oxidizing
reagents for organic sulfur removal; up to 38.08% organic sulfur removal has been
achieved for Nova Scotia coal.
281
5. By increasing the concentration of 4 concentration, the number of treatment

stages and pH control, sulfur removal is increased. Most of sulfur, especially pyritic
sulfur can be removed by a higher concentration (up to 20% for 10% solids and
20% for 25% solids) of 4 , or finer particle size (in our case, -400 mesh sample
compared to the -200 mesh sample).
6. By using ultrasonic dispersion technique (15 minutes for each application), the
oxidation products after potassium permanganate reaction were found to be
successfully removed, i.e. ash contents could be kept at lower than 5% level
regardless of the number of steps of permanganate oxidation. That is to say, this
ultrasonic method is found more useful for multi-stage oxidation and high solid
content.
7. The ash content of pre-cleaned coal was 5.62%. After one stage, it was reduced to
3.39%, i.e. 39.68% of the ash being removed. However, the ash content increased
gradually for multi-stage oxidation. This could possibly be due to the overdosage
of the oxidation, i.e. 20% or higher concentration of 4 which solubility was less
than 10% concentration at room temperature. Thus, the excess of 4 caused
increased amount of ash content, i.e. MnOg and other oxidation by-products
precipitation, as a result of oxidation reaction.
8. The permanganate can function in both alkaline (oxidation potential = 1.23 volts)
and acidic media (E = 1.52 v). According to the experiments, the best sulfur
removal was achieved when the initial pH = 7. However in our experiments, the
coal slurry of pre-cleaned coal with 10% solid content and 10% potassium
permanganate had a pH of 9.3. After two hours reaction, the pH value dropped to
8.2.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the support from Dr. H.A. Hamza and Mr.
Magdy Mikhail, Western Research Centre, CANMET, Department of Energy, Mines and
Resources Canada. We are also grateful to Cape Breton Coal Research Laboratory,
Sydney, Nova Scotia for supplying high sulfur coals to us. Also, our thanks to Mrs.
Joanne Young, Mrs. Lois Kerr, and Mr. Randal Willier for doing typings and drawings for
this paper. One of the authors (Y.A. Attia) is grateful to the Canada International
Exchange Program, Ministry of Energy, Mines and Resources for sponsoring his visit at
CANMET's Western Research Centre, Devon, Alberta.
REFERENCES
1. I. Leibson, Transport and Utilization of Coal in the Pacific Rim Countries, Pasha
Publications, Arlington, VA, USA. p25 (1986).
2. P.H. Given. FUEL. 39, (1960) and FUEL, 40, (1962).
282
3. Abdul Ali & AI, Chemical Desulphurization of High Sulphur Coals, Central Fuel
Research Institute, PO FRI-828108, Dhanbad, Bihar, India; Volume 71, # 7 ; July,
FUEL. (1992).
4. Y.A. Attia, W. Lei, and R. W. Carleton, "Removal of reaction product from chemical
oxidation of coal using potassium permanganate for desulfurization," Processing and
Utilization of High-Sulfur Coals ill, Markuszewski and Wheelock (eds.), Elsevier, pp.
391, 1990.
5. Raymond T. Greer, Coal Microstructure and Pyrite Distribution, Ames Laboratory,
U.S. Erda, Iowa State University, Ames. lA 50011; (1977).
6. J.D. Sullivan, 'Heavy liquids for mineral analysis'; U.S. Bureau of Mines; Technical
Paper, No. 381, (1927).
7. J.S. Browning, 'Heavy liquids and procedures for laboratory separation of minerals';
U.S. Bureau of Mines; Information circular No. IC8007, (1961).
8. R.B. Tippin and E.C. Tveter, 'Heavy Liquid Recovery Systems in Mineral
Beneficiation'; Trans. Soc. Min. Eng. AIME, 241, 15(1968).
9. W.B. Fouike, 'Sink and float separation commands new attention'; Eng. Min. J. 139,
33 (1938).
10. D.V. Keller Jr., C D . Smith and E.F. Burch, 'Demonstration plant test results of Otisca
processheavy liquid beneficiation of coal'; presented at Annual SME-AIME meeting;
Atlanta, GA;March (1977).
11. D.V. Keller, Jr., The Otisca Process: The Physical Separation of Coal Using a Dense
Liquid, Paper presented at Ohio University Coal Preparation Workshop, Columbus.
Ohio, O c t (1978).
12. Y.A. Attia and W.W. Lei, 'Removal of organic sulfur from high sulfur comes by mild
chemical oxidation using potassium permanganate'; 'Processing and utilization of
high sulfur coal 11; Yoginder P. Chugh and Rodney D. Glaudle, Editors, pp, 202,
(1987).
13. C.T. Rawcliffe and D.H. Rawson, 'Principles of inorganic and theoretical chemistry';
Henemann Educational Book Ltd; (1969).
14. S.C. Tsal. 'Fundamentals of Coal Beneficiation and Utilization'; Elsevier; pp. 353-369;
(1982).
15. E. Reed, 'Organic chemistry of bivalent sulfur'; Vol. II, p. 64; Chemical Publishing
Co., Inc., New York; (1968).
1993 Elsevier Science Publishers B . V . All rights reserved.
Hydrothermal Pretreatment of Coal before Molten Caustic Leaching
Syed S. Akhtar and Colin D. Chriswell
Ames Laboratory, U. S. Department of Energy

Iowa State University, Ames, Iowa 50011
ABSTRACT
A hydrothermal pretreatment of coal samples before caustic leaching results in

efficient sulfur removal using reduced amounts of caustic and to recovery of a
higher fraction of the energy content of the feed coal than caustic leaching without
the pretreatment. Pretreating an Illinois No. 6 coal with boiling water followed by a
float-sink separation using 5 0 % aqueous NaOH as the heavy medium, and then
leaching the floated coal with only the caustic adhering to the float portion (less than
1 part caustic to 1 part water to 1 part coal) at 390C for 15 minutes led to the same
residual levels of sulfur in the cleaned coal (0.5%) as was obtained performing the
float-sink procedure and leaching procedures on a non-prewashed coal using 2.4
parts caustic to 1 part coal. When prewashed Illinois No. 6 coal was leached with
lesser amounts of caustic, the energy recoveries in the cleaned coal were about 5-
10% higher than when non-prewashed coal was leached with the larger amounts of
caustic.
1. BACKGROUND
During the molten caustic leaching (MCL) of coal, caustic reacts with inorganic
species and organosulfur compounds present in coal to form water-soluble alkali
metal salts [1-4]. Subsequent washings of the resulting coal-caustic cakes with
water and dilute acid leads to recovery of a very low-sulfur, low-ash coal product
and to recovery of a spent caustic solution from which caustic for use in treating
additional coal can be recovered [5-6]. MCL conditions such as the use of 2 parts
caustic to 1 part coal, leaching temperatures of about 390C, and reaction intervals
of 2-3 hours have been shown to be effective for removing over 90% of the ash and
sulfur from coal. Despite the technical success of MCL, use of large amounts of
expensive reagents such as NaOH and severe conditions lead to high costs [7].
Previous work at the Ames Laboratory has led to more economical MCL
conditions. For example, it has been shown that for many coals, sulfur can be
removed using NaOH alone as a leachant rather than more expensive NaOH-KOH
mixtures [8]; and that leaching in two stages, 250C for 1 hour followed by 390^ C
for a few seconds, leads to as efficient of sulfur removals as leaching for several
284
hours at a high temperature [9]. And, a combination float-sink-leaching process

(FLP) developed at the Ames Laboratory requires the use of far lower amounts of
NaOH, and significantly less severe leaching conditions than used in MOL [10]. In
the FLP, 50% aqueous NaOH solutions are used as the heavy medium for float-sink
separation of coal, the float fraction and only the aqueous caustic adhering to it are
then heated to 3 9 0 ^ 0 , and as soon as that temperature is reached, the reaction is
terminated, the coal-caustic cake is washed with water, and the recovered aqueous
caustic is reused without treatment for leaching additional coal samples.
The more difficult step in the mechanism of removal of sulfur by any caustic
leaching procedure appears to be gaining access to sulfur groups. During the 2-
stage leaching procedure, improved access results from partially disrupting the coal
structure. In the companion studies to the current work [11], the literature was
evaluated in an attempt to identify potentially more economical procedures for
disrupting coal structures. Exploratory studies were performed in an effort to
determine if identified conditions or reagents actually had the potential for more
economical desulfurization of coal samples. The most economical of the identified
procedures proved to be hydrothermal pretreatment, which involves prewashing
coal with boiling water. In the current work this procedure was studied.
2. EXPERIMENTAL
2.1 Feed Coals

The properties of feed coals studied are given in Table 1. The 1186 coal was
obtained from the Monterrey Mine in southern Illinois in November of 1986. This
coal was prewashed at the mine. The IBC 101 coal was obtained from the Illinois
State Geological Survey.
Table 1
Analyses of Illinois No. 6 Feed Coal Samples (moisture-free basis)
Sulfur. % SO2 Ash Heat Moisture

Coal Total Oraanic Pyrite Sulfate Ib/MMBtu % Btu/lb %
1186 3.76 2.66 0.55 0.55 6.27 10.7 11,996 9.3
IBC 101 4.51 3.35 1.14 0.02 7.15 10.2 12,615 15.3
2.2 Float-Sink Procedure

Two similar procedures were used for performing float-sink separations. In the
first of these, 12.5 g samples of Illinois No. 6 coal were placed in centrifuge tubes,
40 ml (60 g) of 5 0 % NaOH solution was added, and the mixture was shaken until
the coal was wet with the caustic solution. Sets of four tubes were then centrifuged
at 2000 m for 10 minutes. The float portions were removed from the tube and
285
placed in an Inconel reaction crucible

(Figure 1). The liquid middle layers
Nitrogen Inlet (middlings), which contained some
Thermocouple dispersed coal, were also added to the
same crucible. A n d , the sink portions
were w a s h e d from the bottom of the
Nitrogen centrifuge tubes onto a filter paper in a
Outlet Bchner f u n n e l , w a s h e d with water,
d r i e d , w e i g h e d , and retained for
analysis. In some tests, the mixture of
coal and 5 0 % caustic in the centrifuge
tube was sonicated for 5 minutes before
centrifugation. In other instances, a
wetting agent (Mazowet DF, PPG Mazer
Chemical) was a d d e d to t h e coal in
each tube just before the caustic was
introduced. In some instances small
a l i q u o t s of t h e f l o a t e d c o a l a n d
middlings fractions were titrated
p o t e n t i o m e t r i c a l l y to d e t e r m i n e the
caustic content, and other aliquots were
Inconel
Crucible analyzed for sulfate by ion
chromatography. In the second float-
sink separation procedure, 100 g of coal
was mixed with 500 g of 5 0 % N a O H ,
and the resulting slurry was d i v i d e d
among four large centrifuge tubes. The
mixture was then separated and
Coal- processed as described above.
Caustic
2.3 Single-stage Leaching Procedure
M i x t u r e s of c o a l a n d a q u e o u s
caustic middlings were p l a c e d in an
Inconel crucible, a thermocouple was
Figure 1.
immersed into the coal-caustic mixture.
Reactor used for leaching coal.
286
a purge line was installed above the levels of coal-caustic, the crucible was sealed,
and a nitrogen purge was commenced at a flow rate of 30 ml/min at atmospheric
pressure. The nitrogen purge was maintained throughout the run. After 5 minutes
of purging, the sealed crucible was placed in a preheated vertical tube furnace. The
temperature of the coal-caustic was monitored until a temperature of 390C was
reached, and that temperature was maintained for and interval ranging from zero
minutes to 1 hour. The still-sealed crucible was then removed from the furnace and
immersed in a vat of chilled water. The temperature of the coal-caustic was
monitored until it cooled to below 50C.
2.4 Two-Stage Leaching Procedure

The same procedure was used as for single-stage leaching except that the
coal-caustic mixture was heated to 250^C, that temperature was maintained for 1
hour, the temperature was then increased to 390C, and the crucible was removed
from the reactor as soon as the coal-caustic mixture reached 390C.
2.5 Processing of Leached Coal

After the coal-caustic mixtures had cooled to below 5 0 C , the nitrogen purge
was discontinued, the crucible was opened, and the bulk of the coal-caustic cake
was removed and placed in a 1000-ml beaker. The residual coal-caustic mixture
adhering to the sides and bottom of the crucible was removed by repeated
washings with boiling water. These washings were combined with the coal-caustic
cake in the beaker. The volume of water was adjusted to about 500 ml, the
resulting slurry of coal-caustic was stirred and heated to near boiling for 5 minutes,
and it was then vacuum-filtered through Whatman No. 41 filter paper in a Bchner
funnel. The coal was washed on the filter with an additional 500 ml of boiling water.
The recovered coal was then removed from the filter, slurried with 500 ml of 10%
hydrochloric acid, and the mixture heated and stirred for 5 minutes. The acid-
washed coal was then vacuum-filtered using Whatman No. 41 filter paper and
washed on the filter with an additional 500 ml of boiling water.
2.6 Cleaned Coal Products

The cleaned coal was placed on a watch glass and dried at lOO^C overnight.
The recovered coal was then weighed and ground to <60 mesh. An aliquot was
analyzed for total sulfur using a Fisher Total Sulfur Analyzer, a second aliquot was
analyzed for heating value by the ASTM procedure using a Parr Adiabatic Bomb
Calorimeter, and a third aliquot was analyzed for ash content by the A S T M
procedure.
2.7 Sink Fractions

Sink fractions were washed from the centrifuge tubes onto a filter paper,
vacuum-filtered, washed on the filter with boiling water, dried at 1 0 0 C , and
analyzed for ash content, heating value, and total sulfur. The filtrates from some
sink fractions were analyzed for sulfate by ion chromatography.
287
2.8 Hydrothermal Pretreatment of Coal Samples

Coal samples were placed in a beaker with water and the mixture brought to a
boil for 1 h.
3.0 RESULTS AND DISCUSSION
3.1 Prewashing of Coal with Boiling Water

Experiments were performed to compare the removal of sulfur and the recovery
of coal and energy obtained from IBC 101 and 1186 coal samples with and without
prewashing with boiling water. As shown by the data in Table 2, with the 1186 coal
sulfur reductions were comparable on the prewashed coal leached with half as
much caustic, and coal and energy recoveries were consistently better. With the
IBC 101 coal, however, sulfur reductions were only slightly better on the non-
prewashed 1186 coal using 2 parts caustic to 1 part coal than on the prewashed
coal using 1 part caustic to one part coal. With the IBC 101 coal, coal and energy
recoveries were again enhanced by prewashing the coal with boiling water, but
prewashing was not able to completely overcome the effects of reduced caustic on
sulfur reductions.
Table 2
Residual sulfur, coal recovery, and heating value recovery in Illinois No. 6 coal
samples with and without prewashing with boiling water before MCL.
Prewashed Coal Non-Prewashed Coal

Recovery. % Recovery, %
S,% Coal BTU S,% Coal BTU
MCL Conditions 1:1 NaOH:Coal 2:1 NaOH:Coal
1186 Feed Coal 3.8 100 100 3.8 100 100
390C/60 min 0.8 62 71 0.6 56 65
390C/30 min 0.6 66 73
390C/15 min 0.7 66 77 0.6 56 69
390C/ 0 min 2.0 68 77 1.1 44 47
IBC 101 Feed Coal 4.5 100 100 4.5 100 100
390C/60 min 1.0 69 79 0.7 63 71
390C/30 min 0.9 70 80 0.7 63 73
390C/15 min 0.8 66 77 0.7 64 75
390C/ 0 min 1.1 73 84 1.1 64 75
2-stage 1.1 60 71 0.8 63 74
288
Additional studies were performed in which coal samples were prewashed with
boiling water and then subjected to a float-sink pretreatment using 5 0 % aqueous
caustic as the heavy medium. In these studies, shown in Table 3, prewashing the
1186 coal again led to as good of sulfur reductions using 1 part caustic to 1 part
coal as were attained without prewashing using 1.8-2.4 parts caustic to 1 part coal.
Energy and coal recoveries were markedly higher when the prewashed coal was
leached with one part caustic than when the non-prewashed coal was leached with
larger amounts of caustic. With the IBC 101 coal, the same trends are obvious.
Prewashed coal leads to just as acceptable of sulfur reductions when leached with
1 part caustic as are obtained leaching non-prewashed coal with greater amounts of
caustic, and coal and energy recoveries are better.
Table 3
Residual sulfur in Illinois No. 6 coal after float and sink of prewashed and non-
prewashed samples followed by MCL.
Prewashed Coal Non-Prewashed Coal

Recovery. % Recovery. % Recovery. %
S , % Coal BTU S . % Coal BTU S, % Coal BTU
MCL Conditions 1:1 NaOH:Coal 2.4:1 NaOH:Coal 1.8:1 NaOH:Coal
1186 Feed Coal 3.8 100 100 3.8 100 100 3.8 100 100
390C/60 min 0.2 61 75 0.2 50 55 0.5 55 64
390C/30 min 0.4 46 53 0.4 56 63
390C/15min 0.2 60 70 0.4 51 57 0.5 55 63
390C/ 0 min 0.4 66 75 0.5 49 56
IBC 101 Feed Coal 4.5 100 100 4.5 100 100 4.5 100 100
390C/60 min 0.5 65 74 0.6 51 58
390C/30 min 0.4 67 77 50 55 54 63
390C/15min 0.4 69 79 0.2 0.8
390C/ 0 min 0.4
2-stage 0.2 60 71 0.6 60 69
4.0 CONCLUSIONS
Hydrothermal pretreatment of coal, which involves only prewashing coal

samples with boiling water, before the float-sink procedure allows sulfur to be
removed efficiently using lower caustic to coal ratios.
Hydrothermal pretreatment of coal samples before the float-sink procedure

leads to a higher recovery of energy and coal than performing the same procedure
on coal samples without the pretreatment.
289
5.0 ACKNOWLEDGEMENT
This work was performed with support from the Assistant Secretary for Fossil
Energy through the Pittsburgh Energy Technology Center with Richard Read
serving as the Project Monitor. The Ames Laboratory is operated by Iowa State
University for the U. S. Department of Energy under Contract No. 7405-ENG-82.
The assistance of David Jewell and Steven Schmitt in performing this work and
h e l p f u l c o n v e r s a t i o n s with G l e n n N o r t o n and R i c h a r d M a r k u s z e w s k i are
appreciated.
LITERATURE CITED
1. R. A. M e y e r s , " G r a v i m e l t P r o c e s s A p p l i c a t i o n s a n d E c o n o m i c s , " in
Proceedings of the First Annual Pittsburgh Coal Conference. September 17-
21, Pittsburgh, PA, 381-84 (1984).
2. R. A. Meyers, W. D. Hart, J. F. Jones, L. C. McClanathan, J. L. Anastasi, and

E. M. B a r r i s h , " G r a v i m e l t P r o c e s s M o d i f i e d Circuit T e s t R e s u l t s , " in
Proceedings of the Third Annual Pittsburgh Coal Conference. September 8-12,
115-29, Pittsburgh, PA, (1986)
3. R. Markuszewski, D. R. Mroch, G. A. Norton, and W. E. Straszheim, "Coal

Desulfurization and Demineralization by Molten Caustic Mixtures," in Fossil
Fuels Utilization: Environmental Concerns. R. Markuszewski and B. D.
Blaustein, eds., American Chemical Society, Washington, D C, 42-50 (1986).
4. G. A. Norton, D. R. Mroch, C. D. Chriswell, and R. Markuszewski, "Chemical

Cleaning of Coals with High O r g a n i c Sulfur Using F u s e d C a u s t i c , " in
Processing and Utilization of High Sulfur Coals-ll. Y. P. Chugh and R. D.
Caudle, eds., Elsevier, New York, 213-23, (1987).
5. N. D. S h a h , C. D. C h r i s w e l l , a n d R. M a r k u s z e w s k i , " S e p a r a t i o n by
Countercurrent Washing of Coal-Caustic Mixtures during Chemical Coal
Cleaning," Sep. Science Technol.. 24,(1 &2), 79-95, (1989).
6. C. D. Chriswell, . D. Shah, and R. Markuszewski, "Countercurrent Washing

of Pittsburgh No. 8 Coal after Leaching with Molten Mixtures of Sodium and
Potassium Hydroxides." Sep. Science Technol.. 26,(7), 961-975, (1991).
7. D. Gray and A. E. Sawy, Chemical and Biodesulfurization Systems for

Removal of Organic Sulfur from Coal: A Critical Review. National Technical
Information Service, Contractors Report DE 90 011 259, (1990).
290
8. C. D. Chriswell, R. Markuszewski, and G. A. Norton, "Use of NaOH alone vs.

NaOH-KOH Mixtures for the Removal of Sulfur and Ash from Coal by the
Molten Caustic Leaching Process," Processing and Utilization of High Sulfur
Coals IV. P. R. D u g a n , D. R. Q u i g l e y , a n d Y. A. A t t i a , e d s , Elsevier,
Amsterdam, 385-398, (1991).
9. C. D. Chriswell and R. Markuszewski, "Improved Molten Caustic Coal Cleaning

by 2-Stage Leaching," Proceedings of the Eight Annual Pittsburgh Coal
Conference. University of Pittsburgh, Pittsburgh, PA, 305-311, (1991).
10. C. D. C h r i s w e l l , R. M a r k u s z e w s k i , and D. V. J e w e l l , " I m p r o v e d Coal

Desulfurization by a Float-Sink-Leaching Process Employing 5 0 % Aqueous
NaOH Solutions," Fuel Processing Technology. IN PRESS, (1993).
11. R. Markuszewski, C. D. Chriswell, G. A. Norton, D. V. Jewell, and S. S. Akhtar,

"Improvements in Chemical Coal Cleaning," Fossil Energy Quarterly Report to
the Pittsburgh Energy Technology Center. Ames Laboratory U.S. DOE, Iowa
State University, Ames, Iowa, November, 1991.
ORGANIC DESULFURIZATION OF ILLINOIS NO. 6 COAL
Leon M. Stock and Kuntal Chatterjee
Chemistry Division
Argonne National Laboratory
Argonne, IL 60439
INTRODUCTION
Advances in the organic desulfurization of coals depend upon the

discovery of methods for the secure definition of the sulfur forms in fossil fuel
materials as well as upon the discovery of innovative chemical desulfurization
strategies. This report summarizes our work on the utilization of selective
chemical reagents for the desulfurization of Illinois No. 6 bituminous coal.
THE SULFUR COMPOUNDS
The Argonne National Laboratory Premium sample of Illinois No. 6

bituminous coal contains 78% C (mat) with 2.0%S in organic compounds and
2.8%S in pyrite (1). Further, the pristine sample is free of elemental sulfur (2).
The organic sulfur compounds in this coal have been investigated in

several laboratories, but the recent X-ray spectroscopic studies are particularly
insightful (3,4). The XANES study at Exxon suggests that the coal contains 33%
aliphatic, 26% aromatic, and 4 1 % thiophenic organosulfur compounds (3), and
the XPS work suggests that 69% of the sulfur atoms are bonded to sp2 carbon
atoms (3). The Kentucky group also used XANES spectroscopy and found that
the sulfur in this coal was distributed in about the same way with 63% of the
sulfur bonded to sp2 carbon atoms (4). Both research teams indicate that this
pristine coal is free of elemental sulfur and of oxidized organic sulfur
compounds, such as, sulfoxides or sulfones (3,4).
Other studies of Illinois No. 6 coals have also concluded that they are
relatively rich in aliphatic, sulfidic organic compounds (5,6,7). However, it is
pertinent that the mass spectroscopic work on this coal has not provided
evidence for aliphatic sulfur compounds (8,9,10).
292
DESULFURIZATION
HYDRIDE REDUCTION.-- First, we selectively removed the pyrite by treating the

ANL premium sample (-100 mesh) with lithium aluminum hydride in
tetrahydrofuran at 67C for 24 hours (11,12,13). The product, which was recovered
after acid hydrolysis, had less than 0 . 1 % iron, and there were no pyrite reflections
in the powder diffraction X-ray spectrum (13). Furthermore, pyrite is absent in the
XANES spectrum of this material (3,4). Thus, all of the pyrite, even though some
very small particles are present (14), can be removed by this chemical method.
The material balance for sulfur is very good. This observation implies that, within
experimental error, little organic sulfur is present in polysulfides because
compounds of this class are reduced by lithium aluminum hydride (15).
SINGLE ELECTRON TRANSFER DESULFURIZATION.- Next, the pyrite-free

coal was treated with a single electron transfer reagent (SET) to selectively
react with the aromatic sulfur compounds and heterocycles (13). We used
potassium naphthalene(-l) in tetrahydrofuran at 67C for 24 hours in most
experiments. This procedure reduced the organic sulfur content by 33 to 50%
in a series of experiments under different reactions conditions.
Scope of SET Desulfurization.- The scope of single electron transfer reactions

of organic sulfur compounds is reasonably well defined. To illustrate,
dibenzothiophene can be completely converted to biphenyl. An intermediate,
2-phenylbenzenethiol, can be detected in the reaction mixture at short reaction
times showing that the reaction occurs sequentially. The reaction proceeds
smoothly in the presence of coal, but dihydro- and hexahydrobiphenyl are also
obtained. The formation of these products reflects the presence of the hydrogen
atom donor groups in coal. Aromatic thiols such as 1- and 2-naphthalenethiol
are converted to sulfur-free products under the experimental conditions. In the
presence of coal, the hydrogenation of naphthalenethiol takes place and
dihydro- and tetrahydronaphthalenethiol are formed. Di-1-naphthyl sulfide
undergoes carbon-sulfur bond cleavage to give naphthalene and, at short
reaction times,1 -naphthalenethiol.
Di-1-octyl sulfide is converted to 1-octanethiol and an array of products in

which the octyl groups are adducted to naphthalene. As expected.
293
1-nonanethiol and 1-decanethiol are recovered unchanged from the reaction

mixture. Thus, aliphatic thiols are unreactive in single electron-transfer
reactions.
These observations confirm that sp^ carbon-sulfur bonds experience

reasonably rapid cleavage. Aryl radicals are intermediates in the reactions of
diaryl sulfides and heterocyclic compounds. The aromatic thiolates that are
produced in these reactions experience further desulfurization, but the reactions
are slower than the first carbon-sulfur bond cleavage reactions of the
heterocyclic compounds and diaryl sulfides. Aryl alkyl sulfides experience
facile carbon-sulfur bond cleavage to form alkanethiols. DialkyI sulfides
decompose to form thiols, but the sp3 carbon-sulfur bonds in their anions firmly
resist cleavage and the alkanethiolates survive the reaction.
X-ray Analysis.-- The correctness of this interetation is supported by the

XANES spectrum of orginal coal, the pyrite-free coal and the product (16). As
shown in Figure 1, the single electron transfer agent reduces the signal intensity
at 2470.5ev. This signal is, of course, attributable to sulfur atoms bonded to sp2
carbon atoms in aryl sulfides and heterocyclic sulfur compounds (3,4).
BASE DESULFURIZATION.- The next experiments centered on the use of

Lochmann's base, a very reactive mixture of n-butyllithium and potassium t-
butoxide, BASE, in heptane at 98C for six hours (17). The application of this
reaction to Illinois No. 6 coal resulted in 25 to 40% desulfurization.
Scope of BASE Desulfurization.- The chemistry of base-catalyzed

desulfurization has been less completely investigated. Dibenzothiophene and
benzyl phenyl sulfide are recovered unchanged from the reaction after 6 hours
of reflux at ', but dodecyl sulfide undergoes cleavage to form dodecene and
dodecanethiol. Saturated thiols such 1-decane- and 1-nonanethiol do not
react, but naphthalenethiol undergoes quantitative desulfurization to yield
naphthalene as the principal product. Activated sulfides such as dibenzyl
sulfide undergo quantitative desulfurization to yield stilbenes and soluble
inorganic sulfides via thio-Wittig reactions (18). These results suggest that
BASE reacts preferentially with aromatic thiols and other sulfidic sulfur
compounds such as aliphatic and benzylic sulfides. Generally, thiolates are
294
formed in these cleavage reactions, they do not undergo desulfurization.

However, if the reactions yield water-soluble or volatile thiols, then
desulfurization may appear to have occurred.
X-ray Analysis.- This interetation is also supported by the XANES results

(16). The spectroscopic information displayed in Figure 2 shows that the signal
at 2469.6ev that is assigned to sulfur bonded to sp3 carbon is selectively
removed by treatment with Lochmann's base.
SINGLE ELECTRON TRANSFER AND BASE.- A sample of the pyrite-free

Illinois No. 6 coal was treated with SET and BASE and, in a separate
experiment, with BASE and SET (16,19). The results are shown in the
equations.
Pyrite-free coal
S(mf)=1.77%
SET BASE
Product (A) Product (C)

S(mf) = 1.18% S(mf) = ' .25%
BASE SET
Product (B) Product (D)

S(mf) = 0.84% S(mf) = 0.72%
The reagents act essentially independently to remove different types of

organosulfur compounds in reducing the organic sulfur content of this sample of
the Illinois coal to 0.7 to 0.8%, respectively.
ACID HYDROLYSIS. - Several lines of evidence, for example, the facility with
which hydrogen sulfide evolved during thermal reactions (20) and the
appearance of signals that could be assigned to inorganic sulfides in the
XANES spectrum suggested that the desulfurization procedure might have
been even more successful than indicated by analytical data shown for sulfur in
the chart. Accordingly, the residue from the reaction was treated with
hydrochloric acid. The sulfur content decreased to below 0.25%.
295
This observation suggests that inorganic sulfides and acid labile

compounds such as allylic sulfides are retained in the coal sample.
CONCLUSIONS
First, lithium aluminum hydride cleanly removes pyrite from the Illinois
No. 6 coal to leave the original organosulfur compounds.
Second, the SET reagent selectively removes sulfur from heterocyclic

sulfur compounds and aromatic sulfides. Lochmann's base does not remove
the sulfur from the heterocycles, but does react with sulfidic sulfur compounds
such as alkyl aromatic sulfides that are susceptible to base catalyzed
elimination reactions.
Third, the organic sulfur compounds that remain after the dual SET and
BASE treatment are dominantly aliphatic substances including alkyl and allylic
thiols.
Fourth, the sulfur compounds that remain are susceptible to thermal

decomposition and acid hydrolysis.
ACKNOWLEDGEMENT
This work was supported by the Office of Basic Energy Sciences,

Division of Chemical Sciences, U.S. Department of Energy, under contract
number W-31-109-ENG-38.
REFERENCES
1. Vorres, K. S. Users' Handbook for the Argonne Premium Coal Sample

Program, Argonne National Laboratory SANL/PCSP-89/1, October 1,
1989.
2. Duran, J. E.; Raymahasay, S.; Stock, L M. Fuel, 1985, 1167.
3. George, G. N.; Gorbaty, M. L ; Kelemen, S. R.; Sansone M. Energy &

Five/s 1991, 5, 93-97.
296
4. Huffman, G. P.; Mitra, S.; Huggins, F. E.; Shah, N.; S. Vaidya, S.; Lu, F.
Energy & Fuels, 1991, 5, 574-581.
5. Attar, A. In Analytical Methods for Coal and Coal Products] Karr, C , Ed.;
Academic Press: New York, 1979; Vol. 1.
6. Calkins, W. H. Energy & Fuels, 1987, 1, 59.
7. Palmer, S. R.; Kruge, . .; Hippo, . J.; Crelling, J. C , Proceedings:

Fourteenth Annual EPRI Conference on Fuel Science Electric Power
Research Institute: Palo Alto, CA, 1990.
8. Hughes, B. M.; Troost, J.; Liotta, R. Prepr Pap., Am. Chem. Soc, Div. Fuel
Chem., 1981, 26, 107.
9. Winans, R. E.; Neill, P. H. In Geochemistry of Sulfur in Fossil Fuels,

Orr, W. L. and White, C. M. Eds., ACS Symposium Series No. 429,
Washington, 1991.
10. Sinninghe Damst, J. S.; deLeeuw, J. N. Fuel Processing Tech., 1992,

30, 109.
11. Kuhn, J. K.; Kohlenberger, L B.; Shimp, N. F. Environ. Geol. Notes,

1973, 66.
12. Westgate, L M.; Anderson, T. F. Anal. Chem. 1982, 54, 2136.
13. Chatterjee, K.; Wolny R.; Stock, L. M. Energy & Fuels, 1990, 4, 402.
14. Vorres, K. S. Private Communication.
15. Brown, H. C ; Yoon, N. M. J. Am. Chem. Soc, 1964, 88, 1464.
16. Chatterjee, K.; Stock, L. M.; Gorbaty, M. L ; George, G. N.; Keleman, S. R.

Energy & Fuels, 1991, 5, 771.
17. Chatterjee, K.; Stock, L M. Energy & Fuels, 1991, 5, 704.
18. Wallace, T. J.; Pobiner, H.; Hofmann, J. E.; Schreisheim, A. J. Chem.

Soc, 1965, 1271.
19. Stock, L M.; Chatterjee, K. Prepr. Pap., Am. Chem. Soc, Div. Fuel
Chem.,^993,38 (2), 379,
20. Stock, L M. Unpublished results.

Low Temperature Oxidation of Sulphur
KRCliffeandMMSyed
Mechanical & Process Engineering, University of Sheffield, Mappin Street,

Sheffields! 3JD, UK
INTRODUCTION
A widely adopted method for controlling sulphur emissions from the combustion of coal
is by wet scrubbing the combustion gases so called flue gas desulphurisation (FGD). The
problem with FGD is that it does not alleviate the corrosion and fouling problems in the
boiler caused by burning high sulphur coals. Alternative methods of removing sulphur
prior to combustion have been investigated over the last two decades [1,2]. Physical
cleaning of coal to remove mineral matter by washing and gravity separation techniques is
already widely used in the coal industry. Such processes, however, will only remove the
inorganic sulphur in the coal and are not efficient if the sulphur is finely distributed
throughout the coal. The other option is to treat the coal chemically to convert the sulphur
into a soluble form which is easily removed ft-om the coal. Chemical methods have the
potential to remove all of the organic sulphur as well as the inorganic sulphur, but only the
use of molten sodium/potassium hydroxides have produced a large reduction in the organic
sulphur content of coal without completely destroying the coal matrix. The loss of heating
value of the coal and the slow rate of reaction render this process uneconomical [3,4]. The
main problem with organic sulphur removal from coal is that a significant amount of the
sulphur exists as complex thiophenes [5-7], and it is very difficult to break the thiophenic
bond without destroying the coal matrix, so it is suggested that greater emphasis should be
placed on processes which have the potential to remove rapidly all of the pyritic sulphur
and a portion of the organic sulphur.
Because of the large amounts of coal to be treated, there is a requirement that the capital
and operating costs of the treatment plant should be kept to a minimum and so the process
should meet the following criteria:
a) Operate at ambient temperatures and pressures. As coal preparation plants handle a

large throughput considerable energy savings can be made by operating under these
conditions.
b) Have a fast reaction time to minimise the residence time in the process and so reduce
the size of the reactor
Oxidants which are capable of oxidising sulphur at ambient temperatures are sodium
hypochlorite, hydrogen peroxide and potassium permanganate. All of these have been
investigated previously [8-11] but little attention has been given to kinetics of the
desulphurisation reactions. In this investigation a kinetic study of the three oxidants is
made using a British bituminous coal in which the pyritic sulphur is finely disseminated.
298
and is continued by investigating methods of limiting deposit formation on the coal particle
when using one of the oxidants, namely potassium permanganate.
MATERIALS
The coal used in these experiments was a washed sample from Prince of Wales mine,
Yorkshire. Table 1 gives an analysis of the coal. Hydrogen peroxide (30% w/v), sodium
hypochlorite, potassium permanganate and hydrochloric acid were reagent grade and were
used without ftirther purification.
Table 1
Analysis of Untreated Coal
Sample C 0 St Sp So Ash GCV
Prince of Wales 61.7 5.35 4.9 1 2.79 1.15 1.55 0.09 16.27 25.540
Sj = Total Sulphur, Sp = Pyritic Sulphur, Sq = Organic Sulphur.

Sg = Sulphate Sulphur, GCV = Gross calorific value, kJ/kg
The coal samples were crushed and ground to an average size range of 51m and a 50g
sample was weighed into a 3 litre capacity flat bottomed glass vessel fitted with a 3 blade
marine type impeller. The coal was slurried with 0.5 litre of either hydrogen peroxide
(10% w/v), sodium hypochlorite (10% w/v) or potassium permanganate (10% w/v).
After oxidation the coal slurry was filtered using a Bchner Funnel, and when using
potassium permanganate it was also washed with 14% hydrochloric acid and further
washed with water to obtain a neutral pH. Finally, the samples were dried ovemight at
75^C and then analysed. The sulphur, carbon and hydrogen contents were estimated by the
methods described in BS 1016, parts 6 and 11, while ash and calorific values (GCV) were
estimated using BS 1016, parts 3 and 5 respectively. [12] Particle size analysis was carried
out using a Malvern 2600/3600 particle size analyser VA6.
It should be noted that the organic sulphur content was not determined directly, but had
to be calculated by difference between total sulphur and inorganic sulphur, i.e. Sq = S j - Sp
-Ss.
Comparison of Oxidation capability of KMnO/j. NaOCl and H 2 Q 2

A kinetic study was carried out comparing the three oxidants potassium permanganate,
sodium hypochlorite and hydrogen peroxide. The reactions were performed for periods up
to an hour with a 10% solution of the oxidising agent. The temperature throughout the
reaction was 22^C and the results are shown in Figure 1. They demonstrate that potassium
permanganate is the most effective of the three reactants, particularly in the initial stages
before a manganese dioxide and jarosite layer formed on the coal which inhibited the
oxidation reaction. Results of potassium permanganate treated coal are given in table 2.
The formation of manganese dioxide and jarosite on the outside of the coal can be seen in
the increase in the ash content of the coal from 16.27% - 47.0% and resulted from the
Fig.l Rate of reaction of oxidation of sulphur S-
Fi(XB) P
2versustimefor KMn0 ,H 0 & NaOCl
4 2 2
299
300
decomposition of potassium permanganate and the oxidation of sulphur in the coal,

according to the following reactions:
4 ' + 2H20 + 3e' -> M n 0 2 + 4 0 H '

K+ + 3Fe3+ + 2SO42- + 6 0 H ' -> KFe3(S04)2(OH)6
Table 2
Analysis of Potassium Permanganate treated Coal
Reaction St Sp So Ss Ash GCV

Time (min)
5 2.17 0.23 1.87 0.07 14.90 24.976
15 1.78 0.22 1.49 0.07 15.08 24.262
30 1.65 0.19 1.39 0.07 14.75 24.992
60 1.52 0.15 1.30 0.07 14.38 24.998
The significance of this ash formation can be shown by applying the shrinking core
reaction model to the results for all three oxidants. In this model [13] it is visualised that
the reaction occurs first at the outer skin of the particle. The zone of the reaction then
moves into the solid and leaves behind completely converted material and inert solid. This
converted material and inert solid is the ash formed on the coal. So, at any time there
exists an unreacted cone of material which shrinks in size during the reaction. According to
this model, there are five successive steps occurring during the reaction which are:
1) Diffusion of the reactant through the film surrounding the particle to the surface of
the solid.
2) Penetration and diffusion of the reactant through the blanket of ash to the surface of
the unreacted core.
3) Reaction of the reactant and solid at this reaction surface.
4) Diffusion of the products through the ash layer back to the exterior surface of the
unreacted core.
5) Diffusion of the products through the film back into the main bulk of the fluid.
In previous work it was shown [14] that with Prince of Wales coal the main resistance
was the diffusion through the ash and for this mechanism the following equation applies:
^ = 1 - 3(1 - ^ 2(1 - XJ = P ( X J
where t = reaction time, min

= time for complete conversion of the pyrite
= ft-actional conversion of the pyrite at time t
The results are plotted in Figure 2 and show that NaOCl and H2O2 obey the model to a
reasonable degree, whereas with potassium permanganate the line through the experimental
points is considerably displaced from the origin. This shows that the initial reaction of
4 with pyrite is extremely fast, but slows down considerably due to the formation of
jarosite and manganese dioxide on the surface, so preventing the 4 from getting to
the pyrite.
301
Staged Washing using Potassium Permanganate

Attia et al [8,9] have previously shown that the use of a staged process in which the
jarosite and manganese dioxide layer was washed with 14% HCl between stages, increased
the amount of conversion. This technique was further researched by investigating the effect
of reaction time/stage and reusing the 4 in each stage. Two series of experiments
were carried out, in the first, fresh 4 was used in each stage while in the second, the
same 4 was used in each stage in a counter current manner, i.e. in the first stage the
coal was oxidised with twice used 4 solution. This oxidised coal sample was then
further oxidised with once used 4 and finally, in the third stage, it was oxidised with
fresh 4 solution. Two reaction times/stages were investigated, 5 minutes and 60
minutes, and the results appear in Figure 3. These show that the use of fresh 4 in
each stage and longer reaction time gave the highest conversion of pyrite. However, the
difference between a 5 minute and 60 minute reaction time was small and a 3 stage process
of total reaction time of 15 minutes gave nearly the same conversion as a single stage
reaction of 60 minutes duration. The use of recycled 4 show quite different results
for the 5 minute and 60 minute reaction times. In the first stage, there was a surprising
result in that a reaction time of 5 minutes gave a higher conversion than 60 minutes, this
was due to the fact that the 4 concentration in the 60 minute reaction was lower than
in the 5 minute reaction as it had already been used for 120 minutes of reaction time
compared with 10 minutes for the other solution. This demonstrated that the concentration
of 4 was important in the oxidation reaction and can be kept high by minimising the
reaction time.
Effect of Particle Size

An experiment was undertaken using 1 mm coal to investigate the effect of particle size
on the rate of reaction and as can be seen from Figure 4, the difftisional resistance offered
by the coal controlled the reaction.
Comparison with other Processes

In Figure 5 a comparison is made with the oxydesulphurisation results of Akhtar [14]
using Prince of Wales coal in a 21 stirred autoclave at 150^0, under 3.5 bar O 2 pressure and
agitated at 50Hz. The results show that in the initial stages the rate of pyritic sulphur
removal is higher using 4 . As time increases, however, the oxydesulphurisation
process has a greater rate of sulphur removed because of the lower deposit build up.
Another interesting comparison can also be made with microbial desulphurisation

methods which are competing low temperature processes. Andrews et al [15] used a
Thiohacillus bacteria in a 2001 reactor containing a coal slurry of 20% concentration and
found that a residence time of 8 days was required to remove the majority of the pyritic
sulphur. Scaling up this process to handle lOOOt/day of coal (= lOOOMW) a reactor volume
of 400,000m^ is required also there is a requirement for a large amount of air, as much as
80,000 m^/min. Using 4 , a reaction time of 15 minutes has been shown in this
paper to remove a significant amount of sulphur, which gives a reactor size of 520 m^ to
process a 1000 t/day of coal. This is a considerable reduction compared to the size of a
microbial reactor to treat a similar quantity of coal, and there is no air requirement.
Removal of Organic sulphur

Although thp experimental work concentrated on the removal of pyritic sulphur, and
organic sulphur contents were not directly determined, it was shown that up to 20% of the
organic sulphur was removed from the coal using 4 .
302
Fig.3 Three stage process. Comparison between Fig.4 Effect of particle size on removal of
fresh & recycled KMn0 4 pyritic sulphur by KMn0 4

303
100
"
L. >
o 3= >
ZZB-E
>% =3
O. CO ce
o 10 20 30 40 50 60 70
Time (min)
Fg.5 Comparison of removal of pyritic sulphur
by 4 with oxydesulphurisation
304
CONCLUSION
Potassium permanganate is a low temperature oxidant which can oxidise the pyritic
sulphur in coal more rapidly than either sodium hypochlorite or hydrogen peroxide
providing the build up of jarosite and manganese dioxide is limited. By using a 3 staged
process with a short reaction time, the effect of the formation of jarosite and manganese
dioxide on the coal can be minimised. Compared to a microbial system, the size of process
equipment will be considerably smaller, which will offset the higher cost of the reactant
4. Further work is currently being undertaken to investigate the effect of increased
shear to prevent the build up of jarosite and manganese dioxide on the coal particles.
REFERENCES
1. R A Meyer, Coal Desulphurisation, Marcel Dekker Inc, New York (1977).

2. G F Morrison, IE A Coal Research, London, Report No. ICTIS/TR15 (1981).
3. C D Chriswell, R Markuszewski, and G A Norton, in: R Dugan, D R Quigley and Y
A Attia (Eds), Processing and Utilisation of High-Sulphur Coals IV, Elsevier, New
York (1991) 385-397.
4. J L Anastasi, Barrish, et al., in: R Markuszewski and D Wheelock (Eds),
Processing and Utilisation of High-Sulphur Coals III, Elsevier, New York (1990)
371-377.
5. A Attar and F Dupris, in: Coal Structure, ACS Symp.Ser. No. 192, Ch. 16, (1981)
239-256.
6. R Garcia and S R Moinelo, " Pyrolytic Desulphurisation of some High-Sulphur
Coals", in: Energy & Fuels (1991), 5, 582-586.
7. Majchrowicz, J Yperman et al.," Characterisation of Organic Sulphur Functional
Groups in Coal by means of Temperature Programmed Reduction ", in: Fuel
Processing Technology, 15, (1987), 363-376. Elsevier Eds.
8. Y A Attia and W Lei, in: Y Chugh and R D Candler (Eds), Processing and
Utilisation of High-Sulphur Coals II, Elsevier, New York (1987), 202-212.
9. Y A Attia, W Lei and R W Cariton, in: R Markuszewski and D Wheelock (Eds),
Processing and Utilisation of High Sulphur-Coals III, Elsevier, New York (1990),
391-404.
10. D J Boron and S R Taylor, Fuel 64 (1985), 209-211.
11. Ahnonkitpanit and Prasassarakich, Fuel 68 (1989), 819-824.
12. British Standards BS1016, Part 3 (1970), Part 6 1977), Part 11 (1977).
13. O Levenspiel, Chemical Reaction Engineering 2nd Edition, J Wiley and Sons Inc.,
(1972), 360-368.
14. S S Akhtar, PhD Thesis, Chemical Cleaning of Coal to Remove Sulphur, University
of Sheffield, UK (1989).
15. G F Andrews, R Dugan and C J Stevens, in: R Dugan, D R Quigley and Y A
Attia (Eds), Processing and Utilisation of High-Sulphur Coals IV, Elsevier, New York
(1991) 515-531.
Molten-Caustic Leaching ( M C L ) Process Integration
Michael A. Nowak* and Robert A. Meyers''
*U.S. Department of Energy, Pittsburgh Energy Technology Center, P.O. Box 10940,
Pittsburgh, PA 15236
''Robert Meyers, Applied Technology Division, TRW Space and Electronics Group,
One Space Park, Redondo Beach, CA 90278
Abstract
The MCL process, a chemical coal cleaning method that employs molten sodium hydroxide
to remove 90% of the sulfur and ash from coal, is discussed. The construction and operation
of a 2.5 g/s (20 Ib/hr) continuous integrated cleaning circuit is described. The circuit is
capable of producing a very low sulfur (0.4%) product with a low (2.5%) to very low (0.5%)
ash content. Because of improvements made in the process design, the cost of producing
MCL product fuel has dropped from $88/ton ($97/Mg) to $59/ton ($65/Mg). Combustion tests
on the product fuel suggest that it may be successfully burned in a pulverized-coal-fired
boiler, but deposition and NO^ emissions may present problems.
1. Introduction
With the support of the U.S. Department of Energy (DOE), TRW has been developing the
Molten-Caustic Leaching (MCL) process since 1980, when laboratory batch tests began. In
1983, TRW constructed a 0.12-0.62 g/s (1-5 Ib/hr) semicontinuous reactor to conduct process
parameter studies. In 1986, TRW was awarded a contract to design, construct, and operate
a continuous circuit (up to 2.5 g/s or 20 Ib/hr) to generate the data necessary to assess the
technical and economic feasibility of the MCL process. This paper describes the results of
integrated circuit tests conducted in 1991 and 1992 and auxiliary activities related to the
development of the MCL process.
The MCL process is a chemical coal cleaning process capable of reducing the sulfur content
of coal by 90% while simultaneously reducing the ash content to below 1%. The process is
remarkable in its ability to remove organic sulfur as well as inorganic (pyritic) sulfur.
The MCL process test circuit (Fig. 1) consists of a hopper feeding a rotary kiln in which one
weight of coal is treated with two weights of molten sodium hydroxide at a temperature of
approximately 400C for one to two hours. The kiln discharges into a dissolver tank. The
306
WATER
REGENERATOR LIME
EVAPORATOR
V S) REACTED
REGENERATED ' CAUSTIC
DRY CAUSTIC
CAUSTIC
2^
it Ca. Si. AI. S
m m
COUNTERCURRENT
KILN REACTOR WATER WASH
FEED
COAL
WATER ACID
TREATMENT
ACID/WATER
WASH
WATER
-
f
WATER ^
Ca. Fe. Na. . SO4
GRAVIMELT
COAL
Figure 1. Schematic of t h e Molten-Caustic Leaching Process

A d a p t e d from R e f e r e n c e 6
307
resulting 35-50% aqueous caustic/coal slurry enters a countercurrent water wash train
consisting of seven stages, the first two stages using vacuum filters and the final five stages
employing centrifuges. At each stage, the coal is washed with approximately 4.0 weights of
water. The resulting filtrate (caustic concentrate) is sent to the mineral matter removal and
regeneration sections.
The process design has the coal cake exiting the water wash section and entering a second
wash train where the cake is contacted with dilute sulfuric acid used to remove residual alkali
and iron compounds. The product then undergoes three stages of water washing.
After centrifuging, the resulting clean coal contains 50% moisture. The MCL product can
be dried or used to produce a coal-water mixture. The chemistries of the various process
components have been described in detail (1).
2. Process Unit Optimization and Integration
After assembly of the major process components, each component was tested to optimize the
system operating parameters. Earlier efforts focused on off-line parametric testing of the
circuit components to assess the effect of various operating parameters on plant performance.
The parameters examined were kiln temperature, coal/caustic ratio, kiln residence time,
caustic quality, dissolver tank temperature, water wash temperature, wash water-to-coal ratios,
and repulping tank residence times. The effectiveness of a number of components was
assessed. These components included acid waste stream treatment, acid wash train, and the
caustic regeneration section.
Initially, forty-four non-integrated tests were conducted using Pittsburgh No. 8 coal and ten
tests were conducted using Kentucky No. 9 coal. The feed coal size was minus 14 mesh
(smaller than 1.40 mm) in all but five tests, for which it was minus 6 mesh (smaller than 3.35
mm). The caustic/coal ratio was varied between 1.0 and 3.0. The kiln was operated at
temperatures ranging from 370 to 438C and kiln residence times of 1.5 to 3.0 hours.
Nitrogen gas was used to sweep the kiln. The wash train employed approximately 10 weights
of water per weight of coal in the caustic wash and the acid wash sections.
The results of these initial tests demonstrated that product coal could be produced with no
reduction in calorific content, nominal voltiles loss, minimum carbonate formation, and low
water retention. The kiln usually operated continuously for 5 days at a time, achieving total
sulfur reductions of 90% and organic sulfur reductions ranging from 57 to 90%. A number
of important objectives were met, including production of 1359 kg (3000 lbs) of product coal
having ash and sulfur contents ranging from 0.4 to 1.9% and 0.1 to 2.4%, respectively, and
heat contents ranging from 29,308 to 33,146 kJ/kg (12,600 to 14,250 Btu/lb). However,
equipment operating failures prevented integrated operation for extended periods of time.
Also, it was determined that fines production is largely a result of the post-kiln processing
steps.
308
To enable integration, the following modifications were made to the circuit: a breaker bar was
installed to prevent kiln discharge from hanging up and blocking flow from the kiln; an
additional scrubber was installed on the kiln vent; the slurry tank level controllers were
modified to improve their reliability; the reliability of the vacuum filters in the water wash
section was improved by increasing the velocity of the feed and recycle lines, which prevented
plugging of the lines and filter feed pan; band heaters and insulation in the wash section were
upgraded to maintain wash temperature; more efficient impellers in the slurry tanks were
installed to maintain better suspension of solids; an improved antifoam injection system was
installed in the wash sections; and the insulation in the evaporator section was upgraded.
The key operating parameters for the integrated test run were a 1.25 g/s (10 Ib/hr) coal feed
rate, 2.5:1 caustic-to-coal ratio, 390-410C internal kiln temperature (skin temperatures 405-
435C), 2-hour kiln residence time, and 10:1 wash water-to-coal ratio. In addition, laboratory
testing indicated that by eliminating the acid wash and providing additional water washing,
a product coal with slightly higher ash content but not higher sulfur or sodium contents could
be produced at some cost savings. The effect of wash water pH on nal ash, sodium, and
sulfur contents was examined. The coal selected for testing was a Pittsburgh No. 8 coal
containing 2.8% sulfur (ROM) corresponding to 1.93 kg SOj/GJ (4.5 lb SOj/MM Btu). The
coal was washed and crushed to minus 14 mesh (smaller than 1.40 MM). The coal fed to the
kiln contained less than 2% moisture, had a heating value of 32,578 kJ/kg (14,006 Btu/lb),
contained 7.6% ash and had a total sulfur content of 1.93% (dry basis). Sulfur forms analysis
indicated the coal contained 0.62% pyritic sulfur, 0.01% sulfatic sulfur, and 1.30% organic
sulfur.
3. Results of the Integrated Circuit Test
The results of the integrated test are presented in Table 1. The target product sulfur level was
achieved when the kiln skin temperature was raised to 425 C (internal temperature of 400""C).
Approximately 272 kg (600 lb) of product coal was collected from the circuit and additional
samples of kiln discharge were also collected.
The average sulfur content of the product generated under these conditions was 0.32% (0.19
kg SO2/GJ or 0.45 lb SO2/MM Btu). The acidity of the acid wash section was varied from
pH 5 at the start of the test, to pH 10 when sulfuric acid addition was tumed off, and then
lowered to between 1 and 2 when acid addition was resumed. At the end of the test, the acid
addition was tumed off and the pH of the acid wash section was allowed to equilibrate at pH
10. At wash pHs of 5, 1 to 2, and 10, the resulting MCL product had average ash contents
of less than 1.7%, less than 0.5%, and less than 3.5%, respectively. The average ash content
of MCL product was slightly higher than anticipated (3.39%) because clearing a plug in the
caustic regeneration section (flaker) inadvertently piped sodium hydroxide back to the
deionized water holding tank, so that the acid wash section was using dilute alkali instead of
deionized water. Later tests demonstrated the average ash content could be lowered by an
additional 0.5% with additional water washing.
309
Table 1
Analysis of MCL Product from Continuous Integrated Operation
Acid Wash pH No. of Samples' Product Sulfur, % Product Ash, %
5* 17 0.48 1.61
5 2 0.47 1.96
10 3 0.30 3.25
1-2 2 0.43 0.45
10 36 0.31 3.39
a. Integrated circuit product samples were collected at approximately 2-hour intervals.
b. Kiln skin temperature was 425C. For all other samples, kiln skin temperature was
435C.
Table 2
Effect of Carbonated Water Washing on Ash Derived from MCL Product
Weight % of MCL
Product, Water Wash
Weight % of MCL Followed by
Weight % of Product, Water Carbonated Water
Constituent Starting Coal Wash Only Wash
Ash 7.24 2.56 1.67

Silicon Dioxide 3.42 0.31 0.22
Aluminum Oxide 1.77 0.16 0.10
Ferric Oxide 1.16 0.37 0.32
Titanium Oxide 0.09 0.03 0.02
Calcium Oxide 0.39 0.40 0.33
Magnesium Oxide 0.07 0.04 0.03
Sodium Oxide 0.04 0.60 0.10
Potasssium Oxide 0.11 0.04 0.01
Sulfite 0.22 0.65 0.52
310
The test successfully demonstrated full integration of the MCL circuit, including the use of
recycled caustic and complete recirculation of process water. Caustic recycle in the circuit
required 12 hours from end to end. Recycled caustic was used continuously for two periods
of 60 and 48 hours, respectively, representing nine recycles of sodium hydroxide. Generally,
the integrated circuit ran smoothly and integration of the process unit operations was
successfully demonstrated. Further characterization of the MCL product is ongoing at PETC.
4. Potential Improvements to MCL
Although integration of the plant had been achieved, unit operations had not necessarily been
operating at their optimum throughput. Additional off-line testing indicated that with properly
sized equipment, lower wash water-to-coal ratios (5:1) could be employed while still
producing products with satisfactory moisture contents and at acceptable throughputs.
In subsequent tests, TRW determined that washing with carbonated water can have a
beneficial effect on the product quality if washing with sulfuric acid is eliminated. The
example in Table 2 indicates that washing with carbonated water effects a moderate reduction
in the ash content of a water-only washed MCL product, while the alkali content is reduced
substantially.
5. MCL Product Combustion Characteristics
Initial combustion tests (3) on MCL samples suggested that, due to lower volatile matter
content of the product coal relative to the parent coal, ignition of the MCL product may be
more difficult. However, pilot-scale combustion tests indicated that once ignition takes place,
a stable flame could probably be maintained. Sulfur emissions from the treated coals
(Pittsburgh No. 8 and Kentucky No. 11) were 85 to 95% lower than for the parent coals.
emissions were higher for the product coals relative to the parent coals. Chemical
analysis predicted that these coals would have a low-to-medium slagging propensity, which
was verified by combustion tests. Fouling is more difficult to predict but the product alkali
content suggested the product coals would have medium-high and low-medium fouling
tendencies, respectively, for the Pittsburgh No. 8 and Kentucky No. 9 coals. However, the
ash depositional characteristics were deemed likely to be offset by the low ash content.
Subsequent additional combustion tests (4) have been conducted under the sponsorship of the
Department of Energy. Preliminary findings indicate that the product's volatile matter
consists of low-heating-value gases, and the ignition characteristics of the MCL product
appear to be acceptable. Mid-range char reactivity was not greatly affected by the MCL
treatment. Although slagging deposit growth was slower, slagging deposits may be stronger
for the product relative to the parent coal. The investigation agreed with the earlier study that
found resulting ash particles to be finer than those from the parent coals. The potential for
high-temperature fouling appeared to be greatly promoted because of substantial production
of alkali-containing submicron ash. Results of emissions levels were mixed, but staged
311
combustion may provide satisfactory emissions. The conclusions of the study

recommended additional investigations concerning ash deposition, dependence of NO^
formation on combustion conditions, and carbon utilization efficiency (burnout) and its impact
on fly ash utilization. Further combustion characterization of MCL product coal is being
discussed.
6. MCL Econoniic Evaluation
An engineering and economic assessment of the Molten-Caustic Leaching process was

undertaken by DOE (5). The initial design case for the assessment assumed the operating
conditions to be those of the MCL bench-scale test conditions as they existed in 1987. This
and subsequent design cases are listed in Tables 3 , 4 , and 5. The subsequent design cases are
based on engineering data derived from the MCL testing program and operating parameters
which have been assessed as those likely to be achieved at full scale. The 1992 and
Optimized design cases have eliminated the use of acid washes. At this stage, the design cost
estimates are assumed to be accurate to plus or minus 25%.
For a 105 kg/s (10,000 tpd) optimistic-design plant, the capital cost is estimated at $339 MM,
allowing 10% for engineering fee and 10% contingency. The largest cost associated with
producing MCL coal, however, is for the raw materials and fuel coal consumptions. The
largest cost items are associated with the coal/caustic reaction section. Lime consumption,
solid waste disposal and fuel coal represent 60% of the total annual operating and maintenance
costs. The makeup cost of alkali is lowered by improving washing and filtration efficiencies.
The use of NaOH instead of a mixture of NaOH and KOH lowers the raw material costs and
reduces solid waste disposal costs and lime consumption.
The cost of producing MCL coal has dropped from $97/Mg ($88/ton) for the 1987 design case
to $65/Mg ($59/ton) for the 1992 design and could be further reduced to $56/Mg ($51/ton)
if the optimistic design case is realized. Economy of scale is estimated to reduce MCL
production costs 37% by increasing the plant size from 105 kg/s (10,000 tpd) to 315 kg/s
(30,000 tpd). These costs do not assume any byproduct credits nor the potential to sell SO2
emission allowances. The delivered cost includes return on equity of 15%.
Identified as key elements in realizing the optimizing design case are improvements in the kiln
design to increase the heat transfer from the kiln to the caustic/coal mixture and reduce the
caustic/coal ratio, kiln temperature and kiln residence time; optimization of kiln conditions
to minimize formation of humics and carbonate; and identication of kiln conditions that
minimize voltiles loss. The ash and moisture content of the feed coal may have significant
impact on the kiln operating conditions and process economics.
Table 3
MCL Process Plant Design Bases
-
w
tv
Desi~n Case: 1987 1989 1990 1992 Ootimized

Parameter
Coal Feed Pgh. No.8 Pgh. No.8 Pgh. No.8 Pgh. No.8 Pgh. No.8
Caustic KOH/NaOH NaOH NaOH NaOH NaOH
Caustic/Coal Ratio 2.5 2.0 2.0 2.0 1.0
Reaction Temperature, C 390 410 444 444 410
Kiln Residence Time, hr 2.5 2.5 2.0 2.0 1.0
Coal Converted to Humate, % 2.0 2.0 1.0 1.0 1.0
Conversion to Carbonate, % 5.0 2.0 1.0 1.0 1.0
Water/Coal Ratio in Caustic Wash 4.0 4.0 2.5 2.5 2.5
Cake Liquid, % in Caustic Wash Cake 2.0 2.0 1.0 1.0 1.0
Water/Coal Ratio in Mineral Wash 3.0 2.0 2.0 2.0 2.0
Cake Liquid, % in Mineral Wash 2.0 1.0 1.0 1.0 1.0
Water/Coal Ratio in Acid Wash 3.0 2.5 2.0 2.0 2.0
Cake Liquid, % in Acid Wash Cake 2.0 1.0 1.0 1.0 1.0
Water/Coal Ratio in Product Wash 3.0 2.5 2.0 2.0 2.0
Cake Liquid, % in Product Wash Cake 2.0 1.0 1.0 1.0 1.0
Excess Lime in Mineral Recovery, %
Feed Coal Ash, %
25
11.5
15
11.5
0
11.5
11.5
11.5
Feed Coal Sulfur, % 4.27 4.27 4.27 4.27 4.27
Feed Coal Heating Value, kJ/kg 30,275 30,275 30,275 30,275 30,275
(Btu/lb) (13,016) (13,016) (13,016) (13,016) (13,016)
Feed Coal Sodium Content, ppm 500 500 500 500 500
MCL Product Ash, % 1.15 0.58 0.11 0.11 0.11
MCL Product Sulfur, % 0.42 0.42 0.42 0.42 0.42
MCL Product Heating Value, kJ/kg 33,441 31,878 30,664 30,664 31,878
(Btu/lb) (14,377) (13,705) (13,183) (13,183) (13,705)
MCL Product Sodium Content, ppm 500 500 500 500 500
Table 4
Energy Balances for MCL Design Cases
Design Case: 1987 1989 1990 1992 Optimized
Reactor Heating Coal, kJ/s 40 42 46 46 13
(MMBtu/hr) (137) (145) (157) (157) (145)
Evaporator Heat Coal, kJ/s 968 885 746 708 523
(MMBtu/hr) (3,131) (2,863) (2,415) (2,415) (1,786)
Recycle Furnace Coal, kJ/s 61 60 76 76 30
(MMBtu/hr) (207) (206) (259) (259) (102)
Feed Coal, kJ/s 2720 2720 2720 2720 2720
(MMBtu/hr) (9,281) (9,281) (9,282) (9,282) (9,282)
Electricity, kJ/s 17 17 17 10 10
(MMBtu/hr) (58) (58) (58) (35) (35)
Total Energy In, kJ/s 3755 3679 3567 3560 3326

(MMBtu/hr) (12,814) (12,553) (12,171) (12,148) (11,350)
Total Energy Out
as MCL Product, kJ/s 2857 2740 2641 2669 2775
(MMBtu/hr) (9,750) (9,351) (9,016) (9,106) (9,467)
Overall Energy Efficiency, % 76.1 74.5 74.1 74.9 83.4
-
w
w
-
w
~
Table 5
Material Balances for MCL Design Cases
Stream 1987 1989 1990 1992 Optimized
Feed Coal, kg/s 105 105 105 105 105
(ton/hr) (417) (417) (417) (417) (417)
Process Water, kg/s 826 774 540 540 540
(ton/hr) . (3,277) (3,072) (2,144) (2,144) (2,144)
Caustic, kg/s 1.0 1.0 0.94 0.94 0.94
(ton/hr) (3.9) (4.0) (3.7) (3.7) (3.8)
Lime, kg/s 29 29 24 18 19
(ton/hr) (117) (117) (96) (72) (74)
Product Coal, kg/s 90 89 90 90 90
(ton/hr) (356) (355) (358) (358) (358)
Solid Waste, kg/s 167 114 94 81 81
(ton/he) (664) (454) (371) (322) (323)
Liquid Waste, kg/s 712 712 495 495 494
(ton/hr) (2,827) (2,825) (1,963) (1,963) (1,960)
Fuel Coal, kg/s 38 35 31 31 19
(ton/hr) (152) (140) (124) (124) (74)
Coal Yield, % = product coal +
(feed coal + process fuel coal) x
100 62.5 63.8 66.2 66.2 72.9
315
7. Summary
A continuous, integrated Molten-Caustic Leaching circuit has been constructed and

successfully operated. The circuit is capable of producing a very low sulfur (0.4%) product
with a low (2.5%) to very low (0.5%) ash content. Because of improvements made in the
process design, the cost of producing MCL product fuel has dropped from $88/ton ($97/Mg)
to $59/ton ($65/Mg). Further improvements in the process are considered likely. The cost
of producing MCL product is projected to drop to $51/ton ($56/Mg) as those improvements
are realized. Combustion tests on the product fuel suggest that it may be successfully burned
in a pulverized-coal-fired boiler, but deposition and NO^ emissions may present problems.
References
1. H.B. Gala, R.D. Srivastava, K.H. Rhee, and R.E. Hucko, Coal Preparation. 7(1-2),
1989.
2. Molten-Caustic Leaching (Gravimelt) System Integration Project, Final Report,

Contract No. DE-AC22-86PC91257.
3. T.S. Mcllvried, S.M. Smouse, and J.M. Ekmann, "Evaluation of Combustion

Performance of Molten-Caustic-Leached Coals," in Processing and Utilization of High
Sulfur Coals III. R. Markuszewski and T.D. Wheelock, eds., Elsevier, Amsterdam,
1990.
4. P. Goldberg, U.S. Department of Energy, manuscript in preparation.
5. E.I. Wan, SAIC, "Technical and Economic Updates of the Molten-Caustic Leaching
Process," prepared for the U.S. Department of Energy, Pittsburgh Energy Technology
Center, manuscript in review.
6. J.L. Anastasi, E.M. Banish, W.B. Coleman, W.D. Hart, J.F. Jones, L.
Ledgerwood, L.C. McClanathan, R.A. Meyers, C.C. Shih, and W.B. Turner,
"Molten-Caustic Leaching (Gravimelt Process) Integrated Test Circuit Operation
Results", in Processing and Utilization of High Sulfur Coals III. R. Markuszewski and
T.D. Wheelock, eds., Elsevier, 1990, Amsterdam.
Chemical desulfurization o f coal using microwave irradiation
J i a n - k a n g Yang and Si-feng Chen

East China University of Chemical Technology, Shanghai 200237, P.R. China
Abstract
Coal was slurried with acids or alcohol and irradiated with 2.45 G H z
microwave in a tuned waveguide applicator, The coal slurry continuously pas
sed through the quartz tube which cut across the waveguide.
The factors affecting the desulfurization process were investigated.
Results indicated that the total sulfur removal from coal could be 5 5 - 7 0 %
(about 90%inorganic and 2 0 - 3 0 % organic).
1. INTRODUCTION
High sulfur coal pollutes the environment when it is used for power, gas
and coking. It accounts for a large proportion of coal resources in our country.
So exploring for a feasible method of coal desulfurization, both technically and
ecconomically, is of immediate significance.
High sulfur coal in Southwest China contains 3 - 5 % of sulfur by mass, of
which approximately 5 0 - 8 0 % is pyritic, 25-60%o is organic, and a small
amount is sulfatic for unweathered coal. Pyritic sulfur can be cleaned rather
effectively by physical cleaning method, such as gravitational float sink tech
niques; whereas organic sulfur requires a more sophisticated method to break
chemical bonds.It is required that organic sulfur be removed to some extent in
order to meet with the compliance of coal in use.
Much attention has recently been paid to the removal of organic sulfur,
due to growing research interest in clean coal technology as well as tougher reg
ulation imposed by the Environmental Protection Agency.However, the molec
ular identification of organic sulfur in coal has not yet been well documented.
Whenever a chemical process is used, the selectivity of the process or the
process medium becomes one of the focal points. Due to the heterogeneity and
complexity of coal structure, it seems impossible to think of any chemical ex-
318
traction process that has a 100% selectivity toward organic sulfur removal. If a
process extracts hydrocarbon and carbonaceous materials easier than
organosulfur compounds from the coal,it will cause the coal to lose at least
some of its original heating value, Therefore, efforts have been made to develop
extraction processes that have high selectivity toward organic sulfur
removal. Such processes are important not only for commercial clean coal
development but also for the scientific investigation of organic sulfur in coal.
The synergistic supercritical extraction process belongs to this category.
The supercritical extraction process has been successfully used in various
chemical and food industries. This process, with various solvents, has been ap
plied to coal in order to reduce the sulfur content.The synergistic supercritical
extraction process involving mixtures of solvents was developed by Lee et al.
The research on microwave enhanced chemical cleaning of coal using caus
tics had been investigated by researchers at GE(General Electric CO.). The re
sults demonstrated that microwave irradiation of caustic-treated coal,followed
by water and acid wash, produced a low sulfur,low ash product, G E researchers
tested this process under a great variety of reactive conditions but some of them
were not well controlled. The Ames Laboratory^'^^^designed and developed an
Experimental Microwave Applicator System(EMAS).The applicator was a res
onant cavity.It was used to obtain the maximum electric field intensity in the
coal and coal components for promoting desulfurization.
The results of our investigation^%n coal treated with waste lye and multi
ple microwave exposures showed that up to 85% of the total sulfur and
5 0 - 6 0 % of the organic sulfur were removed, but the coking properties of coal
were reduced.
This paper attempts to demonstrate the potential for removing sulfur from
Southwest China coal using acids, alcohol as leachant to make slurry for
desulfurization through microwave applicator.
2. E X P E R I M E N T A L
2.1 Coal sample analysis

The test has studied three coal samples from Southwest China. Their
proximate, ultimate, sulfur form analyses are given in Table 1,2 and 3.
319
Table 1
Proximate analysis of coal(dry basis)
Coal Type Volatile Matter% Ash% Fixed Carbon %
Yutianbo 15.83 22.58 61.53

Yanshitai 23.65 29.6 46.75
Pingbazi 18.79 16.57 64.63
Table 2
Coal Type C% H% 0% N% S%
Yutianbo 67.13 3.93 1.27 1.68 3.89

Yanshitai 57.87 4.69 1.01 1.98 5.21
Pingbazi 75.92 4.33 0.82 2.10 4.41
Table 3
Forms of
Yutianbo Yanshitai Pingbazi
Sulfur
Pyritic 3.11 4.48 3.61

Sulfur%
Sulfate / / /
Sulfur%
Organic 1.88 2.89 2.40
Sulfur%
Total 4.99 7.37 6.01
Sulfur%
2.2 Experimental procedures

Yutianbo, Yanshitai, Pingbazi coal (Sichuan Province ) were ground to
nearly 200 mesh in size, aqueous sulfuric acid, acetic acid, or methanol were ad
ded to make slurry. Then, the slurry was passed through the quartz tube which
was inserted in the waveguide applicator, using varying leachant compositions
and different cavities.
The treated coal slurry was then filtered through filters, using Bchner
320
funnel and under vaccum. The filtered solids were washed consecutively with
100ml boiling water (per each gram of coal), hot 10% H C l , and again with boil
ing water. The coal was subsequently dried for 1 hour at about 1 lO'C.
2.3 Applicator
Quartz tube
Quartz tube
Waveguide
Shorting
Dlunger
Waveguide
W-1 Applicator
W-2 Applicator
Fig.l Schematic diagram of appHcator
Slurry inlel
Applicator
Microwave Circular iDireclional couplen Tuner
generator
Slurry outlet
Fig.2 A systematic diagram illustrating

the chemical coal cleaning process
3. R E S U L T S AND DISCUSSION
Two sets of experiments were carried out in W - 1 , a n d w - 2 microwave

applicators with coal slurry made of coal and sulfuric acid -water,acetic acid
-water, or methanol - w a t e r mixtures. The results were as follows:
Table 4 shows the information regarding the forms of sulfur and the
321
desulfurization results of the Yutianbo, Yanshitai, Pingbazi coal and

H 2 S O 4 - H 2 O , HAC-H2O, C H 3 O H - H 2 O . The experiments were carried out in
W - 1 applicator.
Table 5 shows the forms of sulfur and the desulfurization results carried
out in W - 2 applicator.
Table 4
Coal desulfurization in W - 1 Microwave Applicator
1 Total S Pyritic S Organic S
Leachant ! Coal Type Reduction Reduction Reduction
%(d.a.f.) %(d.a f.) %(d.a.f.)
1
HjSO^-HjO i Yutianbo 51.71 80.1 4.8
1:6 1 Yanshitai 65.26 99.8 11.8
1 Pingbazi 72.04 100 30
HAc-HjO Yutianbo 51.71 73.95 14.4
1:6 1 Yanshitai 57.26 80.1 21.8
Pingbazi 57.57 73.1 34.2
CH3OH-H2O Yutianbo 44.29 55.0 26.6
5:2 1 Yanshitai 56.99 78.3 23.9
1 Pingbazi 56.57 69.3 37.5
Table 5
Coal desulfurization in W - 2 Microwave applicator
Total S Pyritic S Organic S
Leachant Coal Type Reduction Reduction Reduction
%(d.a.f.) %(d.a f.) %(d.a.f.)
H2SO4-H2O Yutianbo 38.08 59.8 2.1

1:6 Yanshitai 45.86 71.0 6.6
Pingbazi 61.73 96.4 2.9
HAc-HjO Yutianbo 35.87 49.2 13.3
1:6 Yanshitai 43.83 53.6 28.4
Pingbazi 56.24 86.4 8.8
CH3OH-H2O Yutianbo 20.24 15.1 28.7
5:2 Yanshitai 52.65 67.0 30.1
Pingbazi 60.40 66.2 51.3
The above results obviously showed that acetic acid and methanol under
microwave irradiation still worked very much like organic solvent and more
322
organosulfur compounds were removed. However, the organic sulfur was not
very sensitive to the H2SO4-H2O mixture, but the reductionof pyritic sulfur was
most effective with the H2SO4-H2O mixture.
It seems the W - 1 applicator was used to obtain the maximum electric in
tensity in the cavity region but the electric intensity may not be uniform. Table
5 indicates that the reduction of organic sulfur of the coal in W - 2 applicator
was slightly better than W - 1 , but its reductions of total sulfur and pyritic sulfur
were poor. Therefore, it is necessary for us to design and construct a new kind
of applicator.
4. C O N C L U S I O N S
1. Microwave irradiation of Sichuan Province coal for effectively re

moving sulfur, including organic sulfur, has been studied. Experimental results
demonstrate that the reduction of total sulfur was 5 5 - 7 0 % (about 75-90%)
inorganic and 20-30%) organic sulfur).
2. Additional work is required to optimize process parameters, and to un
derstand more fully the role that microwave plays in the desulfurization reac
tions
3. The experiments need to be scaled up to obtain additional information.
At the same time, economic factors should be taken into consideration.
REFERENCES
1. A.G.Starbuck, U.S.Patent 4,213, 793 1980

2. Sunggyu Lee et al. Fuel 68 1210-1213 1989
3. P.D.Zavitsanos,et al "Coal Desulfurization by a Microwave Process"DOE
Contract N o . D E - A C 22 - 8 0 PC 30142 1980-1982
4. C.K.Richardson, et al "Chemical Cleaning of llUnois No.6 Coal Using a
Microwave / Caustic Treatment " Proc.3rd Annual Pittsbugh Coal Confer
ence 1986 PP 130-141
5. G.E.Fanslow, et al "Microwave Heating of Coal and C o a l / C a u s t i c Mix
tures", J.Microwave Power and Electromagn. Energy 23(4) 211-217 (1989)
6. J.K.Yang, et al "Coal Desulfurization by Microwave and its Relation to
Sample Dielectric Property " Huadong Huagong Xueyuan Xuebao 14(6)
713-718(1988)
Biodepyritization of Pittsburgh Seam Coal:

Mechanism and Implications for Process Design
T. R. Clark^ and G. J. Olson^
^Coal Preparation Division, Pittsburgh Energy Technology Center,

Pittsburgh, PA 15236*
^Little Bear Laboratories, Inc., P.O.B. 1434, Red Lodge, MT 59068
Abstract
Laboratory studies on bacterial desulfurization of Pittsburgh seam coal are
being conducted to determine the mechanisms of biodepyritization and the
resulting implications for design of microbial processes for depyritization of coal.
We are currently comparing leach rates of Pittsburgh No. 8 (150 - 600 ium) coal by
ferric ions in columns under sterile, anoxic conditions with leach rates of coal
inoculated with ThiobacHlus ferrooxidans under aerobic conditions. In addition,
shake flask studies are in progress to determine if finely ground coal (75 - 150 jum)
is depyritized by T. ferrooxidans and Leptospirillum ferrooxidans at similar rates. If
the ferric ion mechanism dominates in coal biodepyritization, depyritization of coal
fines in slurry ponds could be based on ferric ion leaching. In this system, soluble
Fe(lll) ion would percolate through the slurry to oxidize pyritic sulfur and, in turn, be
reduced to Fe(ll). Regeneration of the Fe(lll) oxidant from Fe(ll) could occur in a
rotating biological contactor or other bioreactor as a loop in a recycle stream. This
design would eliminate the need for costly aeration of the bulk coal slurry.
1. Introduction
Acidophilic iron-oxidizing bacteria, such as ThiobacHlus ferrooxidans and

Leptospirillum ferrooxidans, can depyritize coal. Microbial pyrite oxidation is
generally believed to follow two routes. The "indirect" route involves oxidation of
pyritic sulfur by ferric ions, producing sulfate; The oxygen in sulfate is derived
largely from water, and the pyritic iron passes into solution unoxidized. Ferrous
iron is oxidized to ferric ions by the bacteria, a process which occurs up to 10
times slower abiotically (Singer and Stumm, 1970). In this indirect route, the
organisms generate the Fe(lll) oxidant but do not directly oxidize pyritic sulfur.
* This research was supported in part by an appointment of T.R.C. to the U.S. Department of Energy Fossil Energy
Postgraduate Research Training Program administered by the Oak Ridge Institute for Science and Education, Oak Ridge,
Tennessee.
324
The "direct" route of microbial pyrite oxidation has been defined as a process
whereby microorganisms attach to the surface of pyrite and enzymatically oxidize
sulfur (Ehrlich, 1990). Cell-sized holes or depressions on the pyrite surface, as
visualized by electron microscopy, are often cited as evidence of direct attack
(Bennett and Tributsch, 1978). However, given the propensity of microorganisms
to attach to surfaces, such depressions could also be produced by the indirect
mechanism that involves Fe(lli) oxidation of pyritic sulfur.
Although Fe(lll) has been shown to completely oxidize pyritic sulfur to sulfate
(Boogerd et al., 1991), direct microbial attack on pyrite is claimed to be necessary
to prevent accumulation of partly oxidized sulfur species (e.g., elemental sulfur) on
pyrite surfaces (Beyer ei a/., 1987; Merrettig ei a/., 1989). Additionally, the rate of
direct microbial oxidation of pyrite is suggested to dominate over the indirect rate,
except at elevated temperatures (Boogerd ei a/., 1991). Consequently, bioreactors
for microbial coal depyritization are designed to aerate coal-water slurries and
permit the direct oxidation of pyrite. Such studies include a recently described 200
L trough reactor (Andrews et al., 1991) and 50 kg/hr pilot plant employing a series
of Pachuca-type reactors (Rossi, 1992). These designs require expensive aeration
of large volumes of coal slurries, typically containing less than 20% solids. We
have evidence that biodepyritization of 0.6 6 mm Pittsburgh No. 8 coal, cleaned
in a preparation plant, is dominated by indirect (ferric ion) bioleaching, suggesting
less expensive designs may be effective for microbial desulfurization of finely
disseminated pyrite.
Column studies showed that L. ferrooxidans, which oxidizes Fe(ll) to Fe(lll)
but cannot oxidize sulfur directly, removed pyritic sulfur from coal as effectively as
iron- and sulfur-oxidizing T. ferrooxidans or a consortium of acid mine water
microorganisms. Elemental sulfur accumulation was negligible in all leach columns
(Olson, 1993). Both L. ferrooxidans and T. ferrooxidans in shake flasks depyritized
finely ground coal to a comparable degree without accumulation of elemental
sulfur. The coal was also leached effectively in columns by various concentrations
of Fe(III) in sterile, oxygen-depleted spent medium without accumulation of
elemental sulfur. Together, these results suggest that nonaerated treatment
strategies may be effective for microbial desulfurization of this coal.
2. Materials and Methods
2.1. Cells.
T. ferrooxidans (ATCC 13661) and L ferrooxidans (R. Blake, Meharry Medical
College) were grown on 9K medium using ferrous sulfate as an energy source
(Silverman and Lundgren, 1959). Cells were harvested by centrifugation, washed,
and resuspended in 1/10 strength 9K salts. Cell counts were done using a Petroff-
Hausser chamber with phase contrast microscopy.
2.2. Coal.
Coal, which had been cleaned by jigging, was obtained from the North
American Mine in Belmont, Ohio (analysis, Table 1). The coal was sieved to
325
fractions of 150 - 600 /um (leach columns) or 7 5 - 150 jum (shake flasks). The coal
was sterilized by heating to 100C for 30 min in a vacuum oven on each of three
successive days.
Table 1
Analysis of Pittsburgh No. 8 Coal'
Component Percent**
Carbon 72.6
Hydrogen 5.0
Nitrogen 1.3
Oxygen (IND) 6.2
Sulfur 4.8
Ash 10.1
Forms of Sulfur:
pyritic 2.1
organic 2.7
sulfate 0.02
elemental <0.01
' composite analysis from values for a 0.6 to 6.3 mm size fraction
provided in Olson, 1993.
^ moisture-free basis
2.3. Column studies.

Leach columns (25 108 mm) were fashioned from plastic syringe barrels (60
cc). Sterile coal (15-43 g) was added to the columns, which were leached once-
through with deaerated, spent, and diluted 9K iron medium. The spent medium
was generated by bacterial oxidation of ferrous iron in 9K medium. Cells were
removed by centrifugation and the resulting solution sterilized by two consecutive
titrations through 0.22 jum filters. The spent medium was diluted for individual
experiments with sterile 0.011 H2SO4 and deaerated by continuous sparging of
the reservoir with N2. Continuous flow (2-3 ml/hr) through the columns was
maintained by a peristaltic pump. Unlike the larger glass columns used by Olson
(1993), the headspace in each of these columns was displaced with leach solution
to minimize the possibility of oxygen entering the column. The columns drained
through outlet tubing directly into 125-ml conical flasks.
A similar system was devised for flooded columns that received an aerated
leach solution (dilute 9K salts + ferrous sulfate). An initial inoculum of 0.4-1.0
10^ . ferrooxidans cells was added directly to the column at the start of the leach
cycle. Samples were collected on a daily basis and the concentration and
speciation of iron determined following centrifugation of the sample at 14,000 g
for 3 min.
326
The influence of particle size on the difference between the leach rates of 7.
ferrooxidans and L ferrooxidans was also determined. Shake flasks (250-ml
Erienmeyer) contained 8 g of coal (75 - 150 jum), 100 ml of leach solution, and
inoculated flasks had an initial cell concentration of 1.6 10 cells/ml. The leach
solution consisted of 9K salts (minus iron) (Silverman and Lundgren, 1959) diluted
to 1/10 strength in 0.01 sulfuric acid. Shake flasks were maintained at 29C and
175 rpm in an incubator-shaker (New Brunswick Scientific).
Coal was recovered by gravity filtration through a coarse paper at the end of
the experiments, rinsed with deionized water, and dried in a vacuum oven at 95-
100C. Coals were analyzed according to ASTM methods (ASTM, 1991). Soluble
iron was determined by the o-phenanthroline colorimetric method (ASTM, 986).
Elemental sulfur was determined by high-pressure liquid chromatography following
extraction with tetrachloroethylene (TCE), as described by Buchanan and Warfel
(1990), except that the sample was not heated during the TCE extraction process
but was shaken for 1 hr at room temperature.
3. Results and Discussion
Leach column results (Olson, 1993) have shown that L. ferrooxidans

depyritizes 0.6 6 mm Pittsburgh No. 8 coal as rapidly as did T. ferrooxidans or a
consortium of acid mine water bacteria. After 2.5 months of leaching, coal
depyritization was 16% in the presence of . ferrooxidans, 7% with the acid mine
water consortium, and 13-24% (two separate experiments) by L ferrooxidans.
Elemental sulfur content of the coals was never greater than 0.05%.
In the currrent study, T. ferrooxidans leached iron from 75-150 jum coal about
50% faster than did L ferrooxidans (Figure 1). However, L. ferrooxidans was
days
Figure 1. Kinetics of iron leaching from 75-150 um Pittsburgh No. 8 coal in shake
flasks by T. ferrooxidans (}), L ferrooxidans ( ), and an uninoculated
control ().
327
unable to maintain the Fe(lll)/Fe(ll) ratio at as high a level as T. ferrooxidans,

perhaps accounting for the lower leaching rate. In this connection, L. ferrooxidans
has been reported to effectively oxidize Fe(ll) at low concentrations but has a lower
maximum rate of Fe(ll) oxidation than T. ferrooxidans (Morris et al., 1988). Analysis
of the coal after 17 days showed that 79.5% and 71.0% of pyritic sulfur had been
leached from coal treated with T. ferrooxidans and L ferrooxidans, respectively,
while 14.8% was leached from an uninoculated control. As with the coal in the
large leach columns, accumulation of elemental sulfur was minimal and did not
exceed 0.004% in an uninoculated control, nor in coal treated with either T.
ferrooxidans or L. ferrooxidans.
The once-through leach columns were devised to study oxidation rates in
systems where a leach solution containing a relatively constant Fe (111) concentration
would percolate through a wetted solid, as would be characteristic of coal in a
slurry pond. In the first experiment (Table 2), iron in the leach solution was
reduced completely to Fe(ll), indicating that the observed rate of depyritization may
have represented an underestimate of the maximum potential rate. In a second
experiment, a higher concentration of Fe(lll) was used and the iron in the leach
solution remained 80% Fe(lll) after passing through the solids in the column,
indicating that excess oxidant was available.
Table 2
Indirect Leaching of Pittsburgh Coal by Fe(ili) in Deaerated, Continuous
Flow Leach Columns
EXP 1" EXP 2"
Temp. C (s.d.) 20.5 (+1.4) 20.1 (+1.6)

Total Sulfur 4.05 4.19
Pyritic-S 1.51 1.55
Sulfate-S 0.08 0.02
Organic-S 2.46 2.62
Elemental-S 0.01 0.02
%Depyritization 27 22
" Exp. 1: 43 g coal, 508 mg/1 Fe(lll) in leach solution, t = 21 days

^ Exp. 2: 15 g coal, 1330 mg/1 Fe(lll) in leach solution, t = 8 days
The finding that coal from the two columns was depyritized to a similar
extent under disparate conditions is secondary to the main finding that little
elemental sulfur accumulated under either set of conditions. Also, the organic
sulfur values did not increase, suggesting that jarosite precipitation had not
occurred. Experiments involving leaching over an extended period of time are now
in progress.
328
Unfortunately, cell activity in the inoculated columns (as determined by iron

speciation) was less than optimal in the onc^-through system and a direct
comparison to the indirect Fe(lll) leaching columns was not made. These studies
are also continuing because we are confident that cell washout was not
responsible for the poor activity observed.
If oxidation by Fe(lll) is the dominant mechanism of depyritization of Pittsburgh
seam coal, then coal can be processed without aeration of the bulk material. The
solution could be percolated through a coal slurry, where aeration is restricted to a
relatively small volume side reactor and Fe(ll) is oxidized to Fe(lil) by acidophilic
bacteria during recycle. Olem and Unz (1977) showed that a rotating biological
contactor (RBC) populated by Fe-oxidizing thiobacilli could be effective in oxidizing
iron in acid mine drainage waters. Lazaroff and Dugan (1991) proposed later that
a similar strategy could be employed as part of a coal depyritization system to
reoxidize Fe(ll) in a leach solution which circulates beween the RBC and a bed of
crushed coal populated by iron and sulfur oxidizing thiobacilli.
We suggest that a separate bioreactor might be applied to depyritization of
coal fines in slurry ponds (Figure 2). This treatment scheme departs from the
proposal of Lazaroff and Dugan (1991) since oxidation in the slurry pond would
depend entirely on Fe(lll). A biological component to the slurry pond would not be
necessary since accumulation of elemental sulfur does not appear to be
problematic during Fe(lll)-mediated pyrite oxidation in Pittsburgh coal.
LIME
DISPOSAL ^ 1
I SLURRY
IRON AND POND
SULFATE
PRECIPITATES
Fedll)
Fe(II)-i.(III)
Fe(U)
ROTATING
BIOLOGICAL
CONTACTOR
Figure 2. RBC and slurry pond circuit for microbial depyritization.
329
4. Summary
Fundamental studies in the laboratory, using T. ferrooxidans and L
ferrooxidans, have provided strong evidence that finely disseminated pyritic sulfur in
Pittsburgh coal can be effectively oxidized by Fe(lll) without resulting in an
accumulation of elemental sulfur. The oxidation of pyrite within slurry ponds offers
a direct application for an Fe(lll) dominated system. Slurry pond depyritization by
Fe(lll), incorporating a bioreactor in the recycle stream to reoxidize Fe(ll),
represents an economical approach to recovering a high Btu product.
Acknowledgment
Our thanks to M. Schoffstall and D. Fauth who provided technical assistance

and to R. Rohrer for conducting elemental sulfur analyses.
References
American Society for Testing and Materials, 1986. Standard test methods for iron
in water, designation D-1068-84. Annual Book of ASTM Standards, Vol. 11.01,
ASTM, Philadelphia, Pennsylvania.
American Society for Testing and Materials, 1991. Standard test method for
forms of sulfur in coal, designation D-2492-84. Annual Book of ASTM
Standards, Vol. 5.05, ASTM, Philadelphia, Pennsylvania.
Andrews, G.F., P.R. Dugan, and C.J. Stevens. 1991. A large laboratory scale
demonstration of bacterial coal depyritization. In: Proceedings of ttie Second
International Symposium on ttie Biological Processing of Coal, EPRI GS-7482,
Electric Power Research Institute, Palo Alto, California, pp. 3-1 to 3-14.
Bennett, J.C. and H. Tributsch. 1978. Bacterial leaching patterns of pyrite

crystal surfaces. Journal of Bacteriology 310-317.
Beyer, M., H.G. Ebner, . Assenmacher, and J. Frigge. 1987. Elemental

sulfur in microbiologically desulphurized coals. Fuel 66: 551-555.
Boogerd, F.C., C. van den Beemd, T. Stoelwinder, P. Bos, and J.G. Kuenen.
1991. Relative contributions of biological and chemical reactions to the overall
rate of pyrite oxidation at temperatures between 30C and 70C. Biotechnology
and Bioengineering 38: 109-115.
Buchanan, D.H. and L.C. Warfel. 1990. Perchloroethylene extraction of

sulfur and sulfur compounds from coal. American Chemical Society,
Division of Fuel Chemistry Preprints 35(2): 516-522.
330
Ehrlich, H.L 1990. Biogenesis and biodegradation of sulfide minerals on the

earth's surface. In: Geomicrobiology, Revised and Expanded, 2nd ed. Marcel
Dekker, Inc., New York, pp. 514-547.
Lazaroff, N. and P.R. Dugan. 1991. The precipitation and removal of

Fe(lll) sulfates from bacterial leachates of pyritic coals. In: P.R.
Dugan, D.R. Quigley, and Y. A. Attia, eds. Processing and Utilization of High-
Sulfur Coals IV. Elsevier Science Publishers, New York, pp. 155-183.
Merrettig, U., P. Wlotzka, and U. Onken. 1989. The removal of pyritic

sulphur from coal by Leptospirillum-Wke bacteria. Applied
Microbiology and Biotechnology 3 1 : 626-628.
Norris, P.R., D.W. Barr, and D. Hinsin. 1988. Iron and mineral oxidation by
acidophilic bacteria: affinities for iron and attachment to pyrite. In: P.R. Norris
and D.P. Kelly, eds. Biohydrometallurgy. Proceedings of the International
Symposium, Wan/vick, 1987. Science and Technology Letters, Kew Surrey,
Great Britain, pp. 43-59.
Olem, H. and R.F. Unz. 1977. Acid mine drainage treatment with rotating
biological contactors. Biotechnology and Bioengineering ^9\ 475-491.
Olson, G.J. 1993. Biodesulfurization of coal containing finely

disseminated pyrite: evidence for an indirect mechanism of bioleaching.
International Biohydrometallurgy Symposium, Jackson Hole, Wyoming (to be
held Aug. 22-25, 1993).
Rossi, G. 1992. Coal depyritization: achievements and problems.

Presented at the Third International Symposium on the Biological
Processing of Coal, EPRI/USDOE, Clean^âter Beach, Florida.
Silverman, M.P. and D.G. Lundgren. 1959. Studies on the

chemoautotrophic iron bacterium Ferrobacillus ferrooxidans 1. An
improved medium and a harvesting procedure for securing high cell
yields. Journal of Bacteriology 59: 642-647.
Singer, P.C. and W. Stumm. 1970. Acidic mine drainage: the rate-determining
step. Sc/ence 167: 1121-1123.
Isolation and Kinetic Analyses of Bacterial Strains Which Desulfurize Model

Compounds Characteristic of Coal
Ping Wang"^, Arthur E. Humphrey* and Steven Krawiec
Department of Molecular Biology and Center for Molecular Bioscience and

Biotechnology, Lehigh University, Bethlehem, Pennsylvania, U.S.A.
Gram positive, aerobic, non-acid fast, non-endospore forming, largely monomohic

rods which convert dibenzothiophene (DBT) or dibenzosulfone (DBTO2) to 2-hydroxybiphenyl
(OH-BP) were isolated from soil samples. The identity of the product has been established
by fluorometry, colorimetry, UV analysis, HPLC, and mass spectrometry. The
desulfurization activity of bacteria (presumptively identified as Rhodococcus erythropolis and
having a stable DbtS"*" phenotype) has been characterized. With DBTO2 as a sole sulfur
source, strain Nl-36 has a maximum specific growth rate ( ^ of 0.235 hr^ (corresponding
to a minimum generation time 2.95 hours). The saturation constant (KJ for DBTO2 was
estimated as 0.39 ; the yield (Y^J is 9 mg of biomass / of DBTO2. OH-BP is not a
carbon source for the isolates nor is the carbon frame of OH-BP altered by the organisms.
Batch and fed-batch cultures created with five percent inocula of Nl-36 into media having
DBT or DBTO2 as sole sulfur source have an exponential growth phase which lasts for
approximately 40 hours; DBT (or DBTO2) rapidly disappears, and OH-BP accumulates to
concentrations of 40 in cultures with DBT and 70 with DBTO2. The DbtS""
phenotype is inducible by DBT or DBTO2 and is repressed by SO4". The desulfurization
substrates, DBT and DBTO2, at concentrations up to 200 do not inhibit growth whereas
the product, OH-BP, inhibits growth at 50 . Preliminary data show that the desulfurization
activity occur on the surface of Nl-36 cells.
1. INTRODUCTION
Studies of the microbial removal of organic sulfur from coal have occurred worldwide.
During the past several years, the microbial desulfurization of compounds characteristic of
fossil fuels has advanced from an intriguing hypothesis to an established laboratory
phenomenon. Organisms exhibiting the "4S" (sulfoxide, sulfone, sulfonate and the released
sulfate) pathway are said to have a DbtS"*" phenotype (1). Bacteria with metabolic activities
*: present address: Biotechnology Institute, 316 Wartik Lab, The Pennsylvania State University,
State College, PA 16802 Tel. 814-863-8524
+ : Corresponding author
This work was supported by U.S. Department of Energy, contract number DE-AC22-89PC89903.
332
to desulfurize DBT via "4S" pathway (and other pathways) have been isolated and recently
described (2,3,4,5,6,7).
Beginning with coal contaminated soil samples, we have isolated Gram positive, aerobic,
non-acid fast, non-endospore forming, largely monomorphic rods which convert
dibenzothiophene (DBT) or dibenzosulfone (DBTO2) to 2-hydroxybiphenyl (OH-BP). The
identity of the product has been established by fluorometry, colorimetry, UV analysis, HPLC,
and mass spectrometry. On the basis of constituent fatty acids and the ability to oxidize a
variety of organic molecules, the strains (Nl-36, N l - 4 3 , Qla-22) were identified
presumptively as Rhodococcus erythropolis (8).
The published knowledge about the desulfurization phenotype is largely qualitative; the
kinetic data gathered in this study establish microbial desulfurization of selected thiophenes
as a quantitative phenomenon. These quantitative data are important for biologists to
enumerate a complete inventory of metabolic activities. The most fundamental value of the
kinetic analyses is that a phenotype of some soil isolates becomes more thoroughly described.
The practical value is that the data can serve as the basis for engineering designs of
bioreactors for growth of the microorganisms and for the desulfurization process.
In this report, we describe the kinetic analyses of oxidation and desulfurization of DBT and
DBTO2 in the following conditions: in batch cultures, in continuous cultures, and in the
presence of potential inhibitors. In addition, we comment on the regulation of the phenotype
and the location of the activity in cells.
2. MATERIALS AND METHODS
The screening, isolation, and identification of strains, the demonstration of the

desulfurization product and the methods for measuring enzyme activities are described
elsewhere (8,9).
The studies of continuous culture and some of the batch cultures were performed in a
BioFlo C30 reactor (New Brunswick Scientific, Inc.) with a working volume of 355 ml.
Some batch cultures were also run in a New Brunswick Scientific Inc. computer-controlled
BioFlo III reactor. The working volume of the vessel was 1.5 liter. The growth limiting
nutrient for the continuous cultures was sulfur; this element was present in the medium in the
form of DBTO2 at a concentration of 50 . The DBTO2 was found precipitated from the
medium in a nutrient reservoir in an initial run. Stirring and mild heating of the substrate
reservoir appeared to alleviate this problem. No visible precipitation was evident and analyses
show that DBTO2 concentration stayed constant through a seven day period. For the
experiments shown in this report, the substrate reservoir (10 liter medium in a glass carboy)
was always stirred and mildly heated.
The dilution rate (D, in reciprocal hours) for continuous cultures was calculated by dividing
the nutrient flow rate (in ml/hour) by the total working volume of the reactor (in ml). Steady
states were obtained by running four working volumes of medium through the reactor at the
same dilution rate. Samples were taken when steady states were established for each D.
Biomass, substrate and product concentrations were measured.
A high performance liquid Chromatograph equipped with a Brownlee column (Spheri-5,
RP-18, 5 micron, 100 4.6 mm) with 50% acetonitrile as mobil phase (flow rate: 1.6
ml/min.) was used for quantitative assay of the "4S" compounds. An Ingold pH probe, a
333
Fisher Accumt pH meter (model 805MP), a Galvanic dissolved oxygen (DO) probe and an
ABEC DO meter (model DD A100) were used to monitor and control broth pH and DO
concentration of cultures "on-line" during fermentations.
Liquid cultures on a platform shaker were shaken at 200 rpm at room temperature ( - 2 5 ' '
C). The standard conditions for kinetic analyses carried out in bioreactors were: pH = 6.0;
temperature = 30 C; agitation = 300 m ; aeration = 1 . 5 w m . Exponentially growing N l -
36 cultures (in DBT or DBTO2 medium; O.D. at 660 nm equal to approximately 1.0) were
used as inocula (5%). In the media for continuous cultures, 6.0 g/1 of glucose were used,
while 3.0 g/1 were used for other cultures. Variations from these conditions will be indicated
where applicable. NaOH (2%, w/v) for both batch and continuous cultures and 3% HCl for
batch cultures were used to maintain the desired pH.
Antifoam (0.02%, v/v) was included in the media for all the batch and fed-batch cultures
in the bioreactors to exclude the foam which sometimes contributes to contamination. For fed-
batch cultures, glucose solutions were injected into the reactors (3.0 g/1) at the late exponential
phase. (Measurement of glucose shows that at that time almost all the glucose originally
added was consumed).
In the experiment pertaining to carbon source, Nl-36 was inoculated into media with no
carbon source, with 35.0 OH-BP, with 0 . 1 % EtOH + 35.0 OH-BP, or with 1.0%
EtOH -h 35.0 OH-BP. The same media without inoculation were set in parallel as
controls. Growth was monitored for seven days.
Nine media were prepared for the inhibition experiment. The media were S-free medium
plus the following: 1) 50.0 DBT, 2) 100.0 DBT, 3) 200.0 DBT, 4) 50.0
DBT02, 5) 100.0 DBTO2, 6) 200.0 DBTO2, 7) 20.0 MgS04, 8) 50.0 OH-BP
+ 20.0 MgS04, 9) 100.0 OH-BP + 20.0 MgS04. The final concentration of
ethanol in all 9 media was 1.0 %.
3 . RESULTS AND DISCUSSION
3 . 1 . Batch and Fed-batch Cultures

A total of seven batch and fed-batch cultures were analyzed to establish the kinetics of
growth and desulfurization of Nl-36. Two experiments had 100.0 of DBT as sole sulfur
source and five had 100.0 of DBTO2 as sole sulfur source. One DBT culture was a
typical batch culture without pH control; the second was a fed-batch culture with pH control.
Both were performed in the BioFlo C30 reactor; Figures 1 and 2 show the time courses for
the two cultures, respectively. For the DBTO2 cultures, three representative runs (Figures 3,
4, and 5) are shown here; (the other two were duplicate experiments and gave similar results).
Data in Figure 3 shown here were obtained from a typical batch culture; the other two sets
of data (Figures 4 and 5) are both from fed-batch cultures. The last experiment had pH
control, the others did not. The optical densities (at 660 nm) and the pH as well as the
concentrations of dissolved oxygen, glucose, DBT, DBTO2, and OH-BP were monitored for
the cultures.
Several aspects of the data from these five cultures merit note. In all instances, a high
yield of cells (3-8x10^ cells/ml) was achieved. Also, stationary phase was rapidly achieved;
in particular, using a 5% inoculum, stationary phase typically occurred after approximately
forty hours of growth. The concentration of DBT or DBTO2 rapidly diminished. OH-BP
334
Figure 1. Batch Culture with DBT as Sulfur Source Figure 2. Fed-Batch Culture with DBT as Sulfur Source
upper panel, cell growth, pH and DO upper panel, cell growth, pH and DO
lower panel, substrate and product concentrations lower panel, substrates and product concentrations
Figure 3. Batch Culture with DBT0 as Sulfur Source Figure
2 4. Fed-Batch Culture with DBTO as Sulfur Source
2
(in BioFlo HI) (in BioFlo C30)

upper panel, cell growth, pH and DO upper panel, cell growth, pH and DO
lower panel, substrate and product concentrations lower panel, substrates and product concentrations
335
336
10000 r100
-90
-80
1000
X
1 -70
LJ
X 6
)
L- -60 O
U
100 Q
-50
-40
-30
0 20 40 60 80 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0
Time (hr)
Glucose OH-BP DBT02

added
0 20 80 100120140
Time (hr)
Figure 5. Fed-Batch Culture with DBTOj as Sulfur Source (in BioFlo III)
upper panel, cell growth, pH and OD; lower panel, substrates and product concentrations
production lagged behind growth. The extent of DBT or DBTO2 utilization was high and the
production of OH-BP was greater when DBTO2 was the substrate as compared with DBT.
The yield of OH-BP peaked at a time approximately equivalent to the transition from late
exponential phase to stationary phase, where OH-BP concentrations were approximately 40
for DBT cultures and 50 - 70 for DBTO2 cultures. In multiple batch cultures
maintained for > 200 hours, production of OH-BP was highest during exponential phase; it
was higher with DBTO2 than with DBT. During growth of the cultures without pH control,
the pH of the media dropped, a condition commonly seen with batch cultures. The decline
in pH did not interfere with the production or continued presence of OH-BP.
From all the batch and fed-batch cultures shown here, it is noted that after the highest
concentrations of the desulfurization product, OH-BP, were achieved, the concentrations
subsequently decreased to approximately 7 0 - 7 5 % of the maximum yield. The possibility that
337
the OH-BP was used as carbon source after glucose levels became low was tested by adding
glucose during cultivation (see fed-batch cultures in Figures 2, 4 and 5). The glucose was
added to determine if the presence of glucose would offset the decline in OH-BP which was
observed in the latter half of incubation. When batch and fed-batch cultures are compared,
the data show that the addition of glucose did not stop the decline of OH-BP level.
OH-BP as potential carbon source or as potential inhibitor for cell growth was further
tested to analyze the reason for the decline of OH-BP. First, Nl-36 was streaked on agar
surfaces of plates containing (i) no carbon source, (ii) OH-BP or glucose or ethanol as sole
carbon source, (iii) ethanol with each of the other carbon sources, and (iv) all three
compounds together. No growth was seen with no carbon source or OH-BP as the carbon
source. Glucose supported growth after four days. Ethanol alone or with either or both of
the other carbon sources supported visible growth after two days of incubation. Results for
the liquid culture experiments show that OH-BP alone does not support growth, which agrees
with the solid surface cultures (8,9). The OH-BP concentrations in inoculated media and in
uninoculated controls indicate that the OH-BP introduced into the medium was not consumed
(see Table 1). Thus, the decline of OH-BP was not because of its consumption as a carbon
source.
Table 1. OH-BP Concentration in Media at Seven Days of Incubation
Medium Inoculated Uninoculated
OH-BP 28.38 32.87

OH-BP -1- 0.1%EtOH 32.36 31.17
OH-BP + 1.0%EtOH 31.72 31.78
The data show that in both inoculated and uninoculated media, the concentrations of OH-
BP decreased to equivalent extents after seven days of incubation. This excludes the
possibility that OH-BP was consumed by cells as a carbon source, and raises the possibility
that OH-BP is abiotically removed (for example, by evaporation, or more likely, sublimation)
from the media.
The possibility that DBT, DBTO2 and OH-BP are inhibitors of growth of Nl-36 was tested.
The results (Figure 6 and 7) show that concentrations of up to 200.0 , DBT and DBTO2
do not inhibit the growth of Nl-36. OH-BP shows some inhibition at concentrations of 50.0
and 100.0 (see Figure 8). As the concentration of OH-BP increased in the medium (from
0 to 100.0 ), the rate of growth decreased during exponential growth.
OH-BP is a primary product of the desulfurization process for the soil isolates. The
concentration of OH-BP diminishes during the stationary phase of batch cultures. OH-BP does
not support growth when present as sole carbon-source. Further, higher concentrations of
OH-BP inhibit growth. Thus, the diminished concentration of OH-BP may be adaptive;
detoxification, for example, might be achieved through degradation or conversion of the
compound. Sublimation, or evaporation, may be additional factors contributing to the decline
of OH-BP.
Experimental data show that pH = 6.0 and = 30 C (the condition we used for
continuous and most of the batch cultures) were optimal for desulfurization activity (8).
338
Figure 6. Effect of DBT Concentrations on Cell Growth. Figure 7. Effect of DBTO2 Concentrations on Cell Growth.
upper panel, DBT concentrations and biomass upper panel, DBT0 concentrations and biomass
2
lower panel, DBTO and OH-BP concentrations lower panel, DBT0 and OH-BP concentrations
2
339
1000
100
CL
m
I
X
o
15 20
Time (hr)
- D.W.(OH-BP 100)
D.W.(OH-BP 0 ) - D.W.(OH-BP 5 0 )
OH-BP ( 5 0 uM) - OH-BP ( 1 0 0 uM)
Figure 8. Effect of OH-BP Concentrations on Cell Growth.
3.2. Continuous Cultures

Some data, such as the maximum specific growth rate and biomass yield from certain
substrates are more rapidly obtained in continuous cultures than in batch cultures. The
maximum specific growth rate ( ^ ^ a x ) of Nl-36 was obtained in continuous culture by using
a wash-out technique. In this technique, steady state is established and then the dilution rate
is abruptly increased to a value well above ^^. The specific conditions chosen for the
experiments described here were such that steady state was achieved at dilution rate (D) 0.193
hr^ (since preliminary data indicated that ^^^ is approximately 0.2 hr ^ D = = 0.193 hr^
is close to but less than the ^ ) . Then, D was suddenly increased to 0.399 h r S a m p l e s
were taken and biomass was measured at the initial steady state and at 0.5 to 3 hours interval
during wash-out. Cells achieved maximum growth at ^^ after approximately 10 hours of
wash-out.
The saturation constant K, was calculated by Monod relationship (10) with known ^^,
and S (instantaneous or steady-state substrate concentration). The yield coefficient, /g, was
calculated from known biomass (x) and substrate concentrations (S).
Figure 9 presents the data from the wash-out experiment. The dilution rate was changed
at time zero. The differences between the slope of the wash-out curve and the dilution rate
is the specific growth rate () at any time point. The curve shows that increased with time,
and after approximately 10 hours of wash-out, stabilized at ^^ Using the following
equation:
(1)
at
The maximum specific growth rate of Nl-36 in the experimental condition is obtained: 0.235
reciprocal hour (i.e., ^=0.235 h r ^ .
340
O
Umax= D - ( - - ^ - ^ ) = 0.235 / hr
dt
-0.5
-1

c -1.5
-I
-2
u = D = 0.193 / hr
-2.5
-3-6 -4 -2 0 2 4 6 8 10 12
Time ( h r )
Figure 9 Wash-out Curve for ^,^^.
Mmax can be converted to a minimum doubUng time, tjîn (which is the same as generation
time G) from the following equation:
(2)
From which, at = 2xo at t = tj,

12 . ln2
^ ^d,min" (3)
The minimum doubling time (or generation time) obtained in this way for Nl-36 is 2.95
hours.
Dilution rates were set at different levels for the continuous culture. At each steady state,
samples were taken and biomass as well as substrate (DBTO2) and product (OH-BP)
concentrations were measured (see Figure 10).
The yield coefficient was obtained by extending the biomass curve to the Y axis. A value
of 450 mg biomass was obtained in this way. This value was then divided by the amount of
substrate consumed. That is,
^x/s
(4)
So- S
It is assumed that S = 0, since almost no detectable substrate was observed in the culture
when a low dilution rate was used. From this Y^, = 9 mg / was obtained (at So = 50
). The theoretical curve shown in Figure 10 is the curve calculated with single substrate
limitation and assuming constant yield, Y^/,. The experimental data are different from the
theoretical data indicating that there might be more than one substrates which was limited at
341
m
I
X
6
CN
O
m
Q
0.04 0.08 0.12 0.16 0.2

Specific Growth Rate (1 / h r )
- Biomass (X) DBT02 - OH-BP Theoretic X
Figure 10. Biomass Dry Weight, Substrate and Product Concentrations.
higher growth rates and/or there might be some repression or inhibition effects at higher
dilution rates.
The K, was calculated from the data shown in Figure 10. Since is known, can be
calculated from the following equation.
(5)
This equation can be converted to:
K=Sx ( - ^- 1 ) (6)
A value of was obtained as 0.39 for DBTO2 by averaging several experimental

points at high dilution rates where substrate concentrations could be detected (see Table 2).
Table 2. Calculation of Saturation Constant
0.193 2.01 0.435

0.225 7.57 0.336
0.232 31.1 0.402
Average 0.39+0.05
342
3.3. Regulation
In order to examine whether or not the desulfurization activity is inducible by one or more
of the substrates, and whether or not one of the end products, the SO4" ion, represses or
inhibits the activity, the cells were grown in presence or absence of DBT or DBTO2 and in
presence or absence of MgS04. Culture suspensions were sampled and used to measure the
desulfurization activities on DBT or DBTOj.
The data are highly suggestive (and the implications are very important). The data (see
reference 8) indicated that: i) DBT and DBTO2 disappear under all conditions tested, ii) the
product OH-BP forms only in the absence of MgS04, and iii) DBT is possibly oxidized to
DBTO2 in the presence of MgS04. These data indicate that desulfurization of DBT or DBTO2
is repressed (or inhibited) by SO4" but that disappearance of DBT or DBTO2 is not affected.
The disappearance of the substrates (DBT and DBTO2) may be a physiological or physical
process, i.e., it may not be an enzymatic process. An example of a non-enzymatic process
is association of a substrate with a carrier.
The role of SO4" in repression of the gene expression or inhibition of the enzyme activity
was determined by the following experiment. Two-day-old Nl-36 cultures growing in either
DBTO2 medium or DBTO2 plus MgS04 medium were washed and resuspended in buffer.
Desulfurization activities were measured for the suspension from the DBTO2 culture in the
presence and absence of MgS04, and for the suspension from the DBTO2 plus MgS04 culture
in the absence of additional MgS04. The data show that when MgS04 was included in the
culture medium, there was no desulfurization activity detected. When MgS04 was later added
to the assay system, desulfurization activity was almost the same as occurred without addition
of MgS04. Thus, SO4" ion affects DbtS gene expression but not enzyme activities (8). The
repression by sulfate means that biotechnological application of cell-based bacterial
desulfurization will require concomitant removal of sulfate.
3.4. Site of Activity

When cells were broken, components separated, and the activities of the fractions
measured, the activity was higher in the surface components (cell wall and membrane) than
in the cytoplasmic fractions (preliminary data, see reference 8). The observation that activity
resides on the cell surface indicates that the biological mediator of desulfurization is particulate
rather than soluble. The biotechnological implementation of microbial desulfurization may be
achieved with a cell fraction rather than whole cells; hence, the undesirable effect from sulfate
can be avoided by working with a sub-cellular component (as in a fluidized bed).
3.5. Conclusions
OH-BP is not a carbon source for the isolated and characterized organism; thus, the carbon
frame of OH-BP is not further consumed by the organism, leaving it as an end product of the
pathway. The strain has great potential for large scale desulfurization of coal because the
phenotype is stable, the desulfurization process excises only the sulfur atom from the carbon
frame without breaking any of the carbon-carbon bonds, and as preliminary data on coal
suggested (8). With the isolated organism, the process may remove the organic sulfur from
coal without reducing the energy value of coal.
The data presented in this report extend the knowledge of sulfur-limited growth of a
Rhodococcus sp. from batch cultures to fed-batch and continuous cultures. The hypothesis of
bacterial desulfurization of organic sulfur compounds in coal has been transformed to an
343
established phenomenon by isolation and characterization of certain bacterial strains. Features

of the phenotype of the responsible bacteria are being extensively quantified. Furthermore,
the behavior of the organisms in a variety of growth settings are being understood. The data
constitute "base-line" measurement for the consumption of DBT and DBTO2 and the
appearance and effect of OH-BP. These measurements will be an invaluable reference when
assessing the effectiveness of bacteria in desulfurizing coal and other fossil fuels.
REFERENCES
1. Krawiec, S. In G. E. Pierce, Ed., Developments in Indust. Microbiol., Society Indust.

Microbiol. (1990) 31:103-114.
2. Kilbane , J. J. Proceedings 7th Annual Coal Prep., Utiliza., and Environ. Ctrl Contract.
Conf., U.S. DOE, Pittsburgh Energy Technol. Cntr, PA. (1991) 375-381.
3. Omori, T., L. Monna, Y. Saiki and T. Kodama. Appl. Environ. Microbiol. (1992)
58(3):911-915.
4. Afferden, M. van, S. Schacht, and J. Klein. Arch. Microbiol. (1990) 153(4):324.
5. Dahlberg, . D. 3rd International Symp. on the Biol. Proc. of Coal. Section 1 (1992) 10.
6. Ochman, M., B.Klubek, J.Boydstun, D.Clark and S.Nabe. Microbios, (1990) 63:79-91.
7. Gallagher, J. R., E. S. Olson and D. C. Stanley, FEMS Microbiol. Letters, (1993)
107:31-36.
8. Wang, P., Ph.D. dissertation. Dept. Mol. Biol., Lehigh Univ., Bethlehem, Pa. (1992)
9. Wang, P. and S. Krawiec, manuscript in submission, (1993).
10. Monod, J., Recherches sur le croissance des cultures bacteriennes, 2nd ed. Hermann,
Paris, (1942)
Characterization o f Fluidized Bed Combustion F l y Ashes Produced f r o m H i g h

Sulfur Coals.
Syed S. Akhtar and Scott M. Schlorholtz
Materials Analysis and Research Laboratory, Department of Civil and Construction

Engineering, 46 Town Engineering Building, Iowa State University, Ames, Iowa 50011.
ABSTRACT
An investigation of five different fly ashes produced by the fluidized-bed combustion of

various high and low sulfur coals is reported. The objective of the study was to provide
information concerning the properties that might affect their utilization. X-ray fluorescence
spectrometry was used to determine the elemental composition of the various samples. The
crystalline composition was determined by X-ray diffraction. Scanning electron microscopy
was used to study the morphology of fly ashes. Other tests that were conducted included
particle size determination, temperature rise with water, loss on ignition, and density.
1. INTRODUCTION
Fluidized bed combustion (FBC) has emerged as a viable option for burning high sulfur
coals. In the last decade FBC power and heat generation stations have become attractive
because of their reduced production of SO2 and NO^ as compared to pulverized coal
combustion power plants. This is due to the addition of sorbents which remove SO2 and the
lower operating temperatures than temperatures in conventional pulverized coal combustion
boilers. FBC temperatures are also below the point at which nitrous oxides are formed.
Fluidized bed boilers are broadly categorized as atmospheric fluidized bed combustion
plants (AFBC) or pressurized fluidized bed combustion plants (PFBC). The waste generated
by the FBC systems depends on the type of the combustion system. During the last decade
research efforts have been redirected towards the PFBC system. The PFBC technology
offers many key advantages compared to more conventional coal based technologies. These
include improved plant efficiency, lower capital cost, reduced space requirement, and
reduced emission of SO2, NO^, and CO2.
The drawback of the FBC system is that while reducing air pollution, greater quantities
of solid wastes are produced compared to conventional coal combustion systems. The major
objective of this investigation was to conduct a thorough investigation of the fundamental
characteristics of different atmospheric and pressurized fluidized bed combustion fly ashes.
Knowledge of the physical and chemical characteristics of these wastes will allow one to
make more reliable decisions concerning the use (or disposal) of the various combustion
by-products produced by these power plants.
346
2. MATERIALS
Samples from five different fluidized bed combustion units were investigated. Sample
no. 1 was obtained from the Iowa State University power plant. This is a circulating
fluidized bed boiler operated at atmospheric pressure. The plant bums about 400-500
tons/day of high sulfur Iowa coal. Limestone is used as a sorbent and about 110-125
tons/day of by-product is produced.
Sample no. 2 was obtained from an industrial circulating fluidized bed combustion power
plant. The plant mainly burns western coal (Wyoming coal from Rochelle mine) but also
uses some Iowa coal. About 2000 tons/day of coal is burned, this produces about 400
tons/day of by-product.
Sample no. 3 was collected from the University of Iowa power plant, Iowa City. This
is an atmospheric fluidized bed combustion plant which mainly burns about 200 tons/day of
Kentucky coal. Limestone is used as a sorbent and by-product production is about 60-65
tons/day.
Samples no. 4 and 5 were obtained from the Karhula pressurized circulating fluidized bed
(PFBC) testing facility in Karhula, Finland. This integrated pressurized fluidized bed
combustion unit of 10 MWt capacity operated at 232 psia pressure and 880C with a fuel
feed rate of 7.2 tons/hr. Ninety percent sulfur removal was achieved at a Ca/S molar ratio
of 1.1 for high sulfur coals while the low sulfur coals required a Ca/S molar ratio of about
1.4 [1]. The samples investigated in this study were obtained from the combustion of a
western sub-bituminous and a midwestem bituminous coal. Limestone was used as a
sorbent for both coals. Table 1 presents the analysis of the type of coals used to produce
the fly ashes investigated in this study.
Table 1
Analysis of the coal types used in different FBC plants.
Iowa Wyoming Coal Wyoming Coal Illinois Kentucky
Coal (Rawhide) (Rochelle) #6 Coal Coal
Moisture % 18.72 31.00 30.90 12.70 6.35

Ash % 11.70 6.80 4.70 9.60 10.38
Carbon % 53.95 69.50 48.03 61.81 72.18
Hydrogen % 3.98 4.90 3.40 4.19 4.99
Nitrogen % 1.24 1.10 0.73 1.04 1.48
Sulfur % 3.80 0.50 0.40 3.70 1.47
Oxygen % 6.61 17.20 11.89 7.60 19.88
H.V. Btu/lb 9858 7760 8300 11100 12144
347
3. EXPERIMENTAL METHODS
X-ray analytical techniques were used in this study to determine both the bulk chemical
composition and the mineralogy of the various samples.
X-ray diffraction (XRD) was used to determine the crystalline components present in the
samples. A Siemens D-500 diffractometer was used throughout this study. The
diffractometer was fully computer controlled via an LC-500 interface and a PDF 11/23
microcomputer. A copper X-ray tube was used for all analyses. Monochromatic (or nearly
so) radiation was obtained via a diffracted beam monochromater and electronic
discrimination. The diffractometer was equipped with medium resolution slits and it was
operated in step scan mode.
Samples were prepared for XRD and trace element analysis by grinding a 30 gram
portion of a given sample to a fine particle size using a shatter box. XRD specimens were
prepared using a front-loading technique.
X-ray fluorescence spectrometry (XRF) was used to quantify the major, minor and
selected trace elements present in the FBC ash samples. A Siemens SRS-200 sequential
X-ray spectrometer was used throughout this study. The spectrometer was fully computer
controlled via an LC-200 interface and an IBM compatible microcomputer. The following
major and minor elements were measured in this study: Si, Al, Fe, S, Ca, Mg, , , Na,
Ti, Sr, and Ba. XRF assays were converted to oxide format (i.e.. Si is reported as SO2,
etc.) so that the values could be compared with the results obtained from XRD. The
following trace elements were measured in this study: Cd, CI, Cr, Cu, , Ni, Pb, and Zn.
Samples were prepared for XRF analysis (major and minor elements only) by igniting
a 2 grams portion of sample at 900 to 950C for 1 hour and then cooling the ignited sample
to room temperature and weighing it to determine its loss on ignition. XRF specimens were
prepared by fusing a 1:5 mixture of ignited sample and spectroflux 105 [Johnson-Matthey]
in a Pt-Au crucible at 100020C. This method of specimen preparation was employed to
minimize interelement effects and eliminate mineralogical effects. Also, the method was
employed because no suitable FBC ash standard reference materials (SRM's) were available
for calibration. Hence, the fused disc technique allowed for quick and reliable calibration
using a minimum number of standards. Also, the concentration of specific elements (S in
this instance) could be increased as needed using only reagent grade compounds.
Trace element specimens were prepared by pouring 3.0 grams of each sample into
disposable sample cups. The ends of the sample cups were closed with 4.0 m thick
prolene. Three trace element standards were made by blending spectroscopically pure
calcium carbonate with three different standard reference materials. This was done to adjust
the mass absorption coefficient of the three standards so that they more closely simulated the
mass absorption coefficients of the FBC ash samples. Hence, the calculations used to
estimate the concentration of trace elements in the FBC ash samples were drastically
simplified.
Morphology of the various samples was investigated using a Jeol JSM 840A scanning
electron microscope (SEM). The SEM was equipped with a Kevex Delta V energy
dispersive X-ray analyzer and a Kevex Quantum (light element) detector.
348
The particle size distribution of the various samples was measured using a sonic sifter.
A sonic sifter uses waves of sonic frequency to agitate particles on specially designed sieves;
and thus, produces relatively fast and accurate separation of particles of different sizes.
However the method is based on purely physical separation techniques and cannot distinguish
true particles from agglomerated particles. Hence, the test results obtained on FBC ash
samples, since they are an air sensitive material that may agglomerate quickly under
changing laboratory condition, should be viewed on a relative basis, rather than an absolute
size distribution measurement.
Temperature rise of a FBC ash-water mixture was measured using a method similar to
that described in ASTM C UO, sections 35 through 39 [2]. However, the procedure was
simplified to allow for hand agitation rather than the mechanical stirring method listed in the
specification.
The density of the FBC ash samples was measured using a Quantachrome gas
pycnometer. Ultra pure helium or nitrogen was used as the purge gas.
4 . 1 . CHEMISTRY
Chemical compositions of all the FBC ash samples that were investigated are summarized
in Table 2. In general, all FBC ash samples were mainly composed of Si, Ca, S, and Al.
However,the quantities of Si and Ca vary considerably between AFBC samples and PFBC
samples. With the exception of sample #4, the PFBC samples are generally deficient in Ca
and Fe, and enriched in Si and Al. The reason for PFBC samples being low in Ca is mainly
due to a lower calcium based sorbent requirement. For PFBC, in order to achieve 90% SO2
removal, a Ca/S molar ratio of approximately 1.1 is required for high sulfur coals whereas
for AFBC, this ratio is above 2.5 [1,3].
A lower limestone requirement for PFBC results in by-products which contain
proportionally more coal-derived constituents with correspondingly higher silica and alumina
and lower calcium content. For the sample #4, a high calcium western sub-bituminous coal
was used. A high inherent calcium content of the coal, along with the added limestone as
sorbent, resulted in a high calcium content in the fly ash. However, in contrast to the AFBC
ashes, the calcium in this PFBC ash was bound in different crystalline states and was not
available as free calcium (CaO). This was confirmed by the temperature rise test with water
on this fly ash. Chemical assays of FBC ash samples were in good agreement with the
results from the XRD study.
The results of the trace element study are listed in Table 3. All concentrations are
reported in g/g (parts per million, ppm). CI and Mn were by far the most variable trace
elements measured in the FBC ash samples. The remaining trace elements typically
remained less than 100 ppm throughout the study.
349
Table 2
Results of elemental analysis on the five FBC ash samples
Oxides % Sample #1 Sample #2 Sample #3 Sample #4 Sample #5

(AFBC) (AFBC) (AFBC) (PFBC) (PFBC)
SO2 28.1 22.5 17.1 26.9 41.3

AIP3 6.2 8.2 7.0 9.7 9.6
FeÔ, 14.9 8.9 7.4 4.2 3.4
SO3 13.4 17.7 10.6 12.4 13.2
CaO 29.7 35.2 33.3 37.7 21.8
MgO 0.7 5.0 2.2 4.0 4.6
P2O5 0.2 0.4 0.8 0.4 0.4
KjO 0.6 0.6 0.9 0.6 0.9
NajO 0.2 0.1 0.8 <0.2
TO2 0.3 0.5 0.4 0.7 0.5
SrO 0.04 0.1 0.0 0.2 0.1
BaO 0.03 0.2 0.3 0.1
L.O.I. 7.28 1.96 19.8 2.54 4.05
Table 3
Results of the trace elements study.
Element Sample #2 Sample #3 Sample #4 Sample #5

(AFBC) (AFBC) (PFBC) (PFBC)
Cd N/M <5 <5 <5

CI 400 800 50 150
Cr N/M 36 30 140
Cu 45 N/M 105 90
N/M 890 170 280
Ni 50 42 30 120
Pb 75 147 30 35
Zn 70 169 95 80
N/M = not measured

350
4.2. MINERALOGY
The results of the X-ray diffraction study are summarized in Table 4. The mineralogy
of the samples obtained from atmospheric fluidized bed combustion plants was dominated
by only four compounds. The four compounds (minerals) were: (1) Anhydrite, CaS04; (2)
Lime, CaO; (3) low-Quartz, SO2; and (4) Hematite, Anhydrite was the most
abundant mineral present in all these samples. Lime and quartz were the second and third
most abundant minerals, closely followed by hematite. A small amount of calcite (CaCOa)
and periclase (MgO) were also commonly observed in the diffractograms. One of the
samples also contained the two major peaks for portlandite, (Ca(0H)2). Minor constituents
remain unidentified in several of the diffractograms.
Table 4
Crystalline components present in the five FBC ash samples.
Mineral Chemical Sample Sample Sample Sample Sample

Name Formula #1 #2 #3 #4 #5
Anhydrite CaS04
Quartz low SO2 m
Wollastonite CaSiOa N/D N/D N/D m
Gehlenite Ca2Al2Si07 N/D N/D N/D ?M 7
Calcite CaCOa m m m m m
Gypsum CaS04.2H20 N/D N/D N/D m N/D
Hematite 623 - -
Lime CaO - -
Portlandite Ca(0H)2 m - - - -
Periclase MgO m m - - -
= major,
m = minor,
N/D = not detected,
? = questionable due to line overlap.
Atmospheric fluidized bed combustion plants are operated at a temperature range of

850-900C for optimum sulfur capture [4]. Since these temperatures are well below the
melting point of the inorganic constituents, no glass phase was readily apparent in any of the
diffractograms. This is in contrast to the glassy nature of the fly ash produced in pulverized
coal burning power plants.
The mineralogy of the PFBC ash samples was found quite different from that of the
atmospheric fluidized bed combustion plants. The major crystalline phases that were
identified for these samples included: (1) Anhydrite, CaS04; (2) Wollastonite, C a S i O j ; (3)
Gehlenite, C a 2 A l 2 S i 0 7 ; and (4) low-Quartz, SO2. Minor amounts of calcite and gypsum
were also tentatively identified in the PFBC ash samples.
351
The reason for such differences in the mineralogy of the PFBC ashes to the AFBC ashes
is due to the different nature of the chemical reaction that takes place in PFBC system. In
AFBC's, limestone is first calcined to CaO before it reacts with SO2 to form calcium sulfate.
The sulfation reaction is prevented from going to completion by the relatively impervious
layer of calcium sulfate that forms around the unreacted particles of calcium oxide. This
layer impedes the diffusion of SO2 to the unreacted core of the particles. Under PFBC
conditions, the chemical reactions are quite different. The high partial pressure of CO2 in
the combustion chamber inhibits the calcination reaction from proceeding. The calcium
carbonate is converted directly to calcium sulfate without an intermediate step by the
following reaction:
CaCOa + SO2 + I / 2 O 2 CaS04 + CO2 (1)
CO2 is expelled from the individual particles of limestone in parallel with the diffusion of
SO2 and O2 into the particle. This reaction mechanism maintains the porous nature of the
particles and the sulfation reaction proceeds further towards completion than in the case of
AFBC's. Also the limestone that is present in the combustion bed, when in excess of that
needed for reaction 1, can combine with silica by the following reaction [5]:
CaCOj + SO2 - CaSiOs + CO2 (2)
This is a solid-solid reaction, occurring while both of the reactants are in solid form. It
is dependant on several factors, primarily the abundance of reactants, partial pressure of CO2
and temperature. Previous researchers have reported that calcium from the bed reacts with
quartz and clay minerals to produce crystalline calcium silicate and calcium aluminosilicate
minerals [6,7,8].
4.3. M O R P H O L O G Y AND SURFACE CHARACTERISTICS

All fluidized bed combustion residue materials are expected to be a heterogenous mixture
of:
1- coal-related inorganic matter;
2- uncombusted coal particles;
3- limestone in various stages of calcination and sulfation; and
4- residual sand from the start up bed.
Examination of the FBC ash samples under an optical microscope revealed the presence
of variable color and morphology in the particles. For AFBC ash samples three types of
particles were easily distinguishable;
(a) Black irregularly shaped particles assigned as incompletely burned coal;
(b) Irregularly shaped particles, grey in color.; and
(c) Light-colored particles with a brownish coating.
In contrast, the PFBC ash samples contained a much smaller number of black particles.
These samples showed more irregularly shaped particles with colors that ranged from dark
brown to golden. Reddish colored particles were also frequently observed in these samples.
352
All these samples were then examined under a scanning electron microscope (SEM).
SEM micrographs are presented in Figures 1-10. This investigation revealed that for both
AFBC and PFBC ash samples, at least two different types of particles were present;
(a) smaller, irregularly shaped particles with very rough texture (see figures 2,4,6,8 and 9).
Type (b) particles were large with relatively smooth surfaces (see figures. 1,3,5,7 and 10).
The chemistry of type (a) particles indicated that the AFBC ash samples were mainly
composed of Ca, Si, Al, S, Fe and Mg. For PFBC ash samples, however, Si, Al, and S
were predominant with smaller amounts of Ca and Mg. Type (a) particles were clearly of
aluminosilicate origin. These were presumed to have originated from coal associated mineral
matter. These results are in good agreement with the XRF results which indicated that
PFBC ash samples were rich in Si and Al.
Type (b) particles contained significant amounts of Ca, indicating them to be spent
limestone. These particles were substantially sulfated as they also showed a high amount of
S in the EDS analysis. For the AFBC ash samples, an important observation was that the
surface of these particles was relatively smooth with some cracks on the surface. However,
at certain points the surface became very porous. It has been previously reported that,
although thermodynamically favorable, sulfation of calcined limestone is impeded by CaS04
that blocks most of the pores after about 35 % of the limestone has been reacted [9].
Figures 3 and 5 show such particles. These figures illustrate the formation of relatively
non-porous regions as well as porous regions in the sorbent particles. Figures 7 and 10
show the sorbent based particles of the PFBC ash samples. Both particles showed more
surface texture as compared to AFBC sorbent ash particles. These particles seemed to be
the agglomerates of the crystalline and recrystallized minerals with the limestone sorbent
particles. The chemistry of these particles revealed a predominant amount of Si and the
presence of along with some Na, Mg and Al. These particles may have been
recrystallized resulting from calcium-abundant compositions reacting with quartz and the
aluminosilicate bonding material.
4.4. PHYSICAL PROPERTIES

Physical properties of the fluidized bed combustion fly ashes have a direct influence on
their utilization behavior as engineering materials or when disposed of. The results of the
physical properties of all the samples are summarized in Tables 5 and 6. All the samples
exhibited similar trends, with a predominance of fine size particles. There was, however,
a fairly wide range of particle sizes between different sources of the FBC ash samples. The
particle size of the samples is influenced to a greater extent by the particle size distribution
of the bed sorbent, fluidizing and conveyance gas velocities, type of coal and the degree to
which coal was crushed prior to burning [10]. The variability of the various particle size
fractions tended to increase with decreasing particle size. A greater proportion of the AFBC
materials contain fine size particles as compared to PFBC materials. The reason for this
difference is probably due to a higher temperature in the PFBC boiler which results in the
partial melting and agglomeration of fine particles. Samples no. 1 and 3 have high loss on
ignition and their particle size distribution revealed a significant amount of black particles
of unbumt carbon distributed almost uniformly in all size fractions.
353
Figure 1. Scanning Electron Micrograph of sample # 1 .
Figure 2. Scanning Electron Micrograph of sample # 1 .

354
Figure 3. Scanning Electron Micrograph of sample #2.

355

356

357

358
Table 5
Results of the particle size analysis of five FBC ash samples.
% Passing
Particle Size Sample #1 Sample #2 Sample #3 Sample #4 Sample #5

210 microns 99.08 95.94 97.60 98.8 93.6

149 microns 98.51 88.07 95.58 90.9 86.8
106 microns 96.24 79.00 90.22 73.3 76.7
74 microns 90.01 68.43 78.33 50.1 60.5
53 microns 80.52 60.43 64.60 35.2 48.7
37 microns 66.54 46.95 46.11 16.7 34.0
Table 6
Results of other physical tests of five FBC ash samples.
Test Sample #1 Sample #2 Sample #3 Sample #4 Sample #5

Density (g/cm^) 2.85 2.98 3.49 2.75 2.87
Temp. Rise (C) 4.60 6.0 10.0 <0.5 0.6
The density of a fly ash reflects partly the chemical composition and morphology, and
partly the operating conditions of the power plant. The density of all the FBC ash samples
was tested with the values ranging from 2.75 to 3.50. This variation in the density results
of five FBC ash samples is due to a variation in CaO content of the samples. The presence
of variable amount of carbonaceous matter and a greater variability in iron oxide content also
could contribute to a greater variability in the density.
Since the majority of these samples contained CaO and CaS04, they reacted vigorously
with water:
CaO + H2O Ca(0H)2 (3)
CaS04 4- 2 H 2 O CaS04.2H20 (4)
Both reactions are exothermic ( = 1140 kJ/kg and = 126 kJ/kg, for reactions 3
and 4, respectively) and the hydration of calcium sulfate results in the formation of a
cemented mass. Thus, if high calcium residues from AFBC are treated with water during
handling or disposal, temperature rise and a possible solidification of the material is to be
359
expected. The temperature rise test was utilized to assess the reactive calcium content of the
various samples of FBC ash. The temperature rise results indicated the presence of free lime
in the AFBC samples and very little lime in the PFBC ash samples. This verifies the
completion of chemical reaction of calcium carbonate to calcium sulfate for PFBC process.
5. CONCLUSIONS
Physical, chemical and physico-chemical properties of five different fly ashes produced
by three atmospheric fluidized bed combustion plants and a pressurized circulating fluidized
bed combustion unit have been investigated. On the basis of the results, the following
conclusions can be made.
Ashes formed in the combustion of coal with added limestone in fluidized bed combustion
units are very complex and heterogeneous in nature. These ashes vary widely in their
composition and structure. These ashes can also be considered as chemically reactive
crystalline solids. This is in contrast to fly ash that is normally obtained from conventional
pulverized coal power plant which is predominantly composed of glassy materials.
The mineralogy of PFBC ashes was quite different from that of the AFBC ashes. PFBC
ashes showed the presence of calcium silicate. It appears that the elevated pressure altered
the phase equilibrium conditions in the boiler and forced the anhydrite reaction to
completion. The remaining calcium bearing materials then combined with silica to form
calcium silicate.
With exception of sample #4, the PFBC fly ashes are generally deficient in Ca and Fe,
and enriched in Si and Al as compared to AFBC ashes. The PFBC combustion process
leaves very little reactive lime (CaO) around, hence, PFBC ashes are not very reactive with
water and they do not evolve much heat when combined with water. AFBC ashes, on the
other hand, contain a significant amount of reactive lime which results in an exothermic
reaction when mixed with water.
The morphology of these samples showed a high degree of inhomogeneity. The two
principal species were the fine, irregularly shaped particles originating from coal related
minerals and the relatively large, smooth particles of spent sorbent.
It appears that the AFBC ashes have considerable potential for being utilized as a
stabilizing agent in several different fields of engineering. The formation of calcium silicate
in the PFBC ashes does suggest the potential for the formation of higher calcium silicates,
compounds that may function as hydraulic cement. Whether or not this would occur at
practical power plant operating conditions is currently not known.
6. ACKNOWLEDGEMENTS
The authors acknowledge the assistance from Steve Ambrose of Midwest Power, Des
Moines, for providing some technical information to this paper. The authors would also like
to thank Jerry Amenson for helping in the SEM investigation of the test samples.
360
REFERENCES
1. Proval, S. and Dryden, R. "Pilot plant test results and demonstration of the Ahlstrom
Pyroflow pressurized circulating fluidized bed technology." EPRI Utility Conference on
the Application of fluidized-bed combustion for power generation, Cambridge, MA, Sept.
1992.
2. American Society of Testing Materials, 1992 Annual Book of ASTM Standards, Vol.
4.01, (ASTM, Philadelphia, PA, 1992.)
3. Utilization Potential of Advanced SO2 Control By-Products. EPRI CS-5269, Project

2708-1, Interim Report Prepared by ICF Northwest, Richland, Washington, June 1987.
4. Berry, E.E. and Anthony, E. J. "Properties and environmental considerations related to

AFBC solid residues." Fly Ash and Coal Conversion By-Products: Characterization,
Utilization and Disposal III, (G.J. McCarthy, F.P. Glasser, D.M. Roy and S. Diamond
eds.) Materials Research Society Symposium Proceedings, 86 (1986) 49-58.
5. Deer, W. ., Howie, R. ., and Zussman, J. "An introduction to the rock forming

minerals." Longman Group Limited, London, 11th edition, 1978.
6. Mazza, M. H., Green, D. ., Parris, M. W. and Newton, G. J. "Mineral

Characterization of fluidized bed combustion aerosol ash-Montana Rosebud
sub-bituminous coal." U.S. Dept. of Energy Morgantown Research Center Report
MERC/TPR-78/1, Morgantown, (1978) 1-20.
7. Zygarlicke, C. J., Steadman, E. N. and Benson, S. A. Prog. Energy Combustion Sei.,

16 (1990) 193.
8. Dawson, M. R. and Brown, R. C. "Bed materials cohesion and loss of fluidization

during fluidized bed combustion of midwestern coal." Fuel, 71 (1992) 585-592.
9. Berry, E. E., Hemmings, R. T., Cornelius, B. J. and Anthony, E. J. "Sulphur oxidation

states in residues from a small-scale circulating fluidized bed combustor." Fly Ash and
Coal Conversion By-Products: Characterization, Utilization and Disposal V, (R.T.
Hemmings, E.E Berry, G.J. McCarthy, and F.P. Glasser eds.) Materials Research
Society Symposium Proceedings, 136 (1988) 9-22.
10. Tung, S-E., and Williams, G. C , "Atmospheric fluidized-bed combustion: A technical

source book." Final report, sponsored by U.S. Dept. of Energy, Morgantown Energy
Technology Center, DOE/MC/14536-2544(DE88001042), 1987.
Assessment of pressurized fluidized-bed combustion

power plants using high sulfur coal
J.M. Wheeldon,^ S.G. Drenker,^ G. S. Booras^ and R. R. McKinsey^
Êlectric Power Research Institute, 3412 Hillview Ave., Palo Alto, OA 94303
^Bechtel Group, Inc., 50 Beale St., San Francisco, OA 94119
1. ABSTRACT
Results of an EPRI engineering and economic study confirm that pressurized

fluidized bed combustion (PFBC) power plants have lower capital costs than other
advanced fossil technologies. The operating costs are shown to be sensitive to coal
properties, particularly the sulfur content. Lower sulfur content coals result in lower
sorbent and ash disposal costs and a correspondingly lower cost of electricity. These
sensitivity studies indicate that for medium to low sulfur coals the levelized cost of
electricity from PFBC power plants is lower than from integrated gasification combined
cycle (IGCC) plants.
Even though a low sulfur coal potentially offers the lowest cost of electricity, if it
has to be transported any distance it may be more economic to use a local high
sulfur coal. To test this hypothesis, costing were carried out for a utility-scale bubbling
PFBC power plant located somewhere in the tri-state region of Kentucky, Illinois and
Indiana. The cost of electricity was determined for a local high sulfur bituminous coal
and three low sulfur coals, two Appalachian bituminous coals, and a Wyoming sub-
bituminous coal. The resulting costs of electricity were very similar. The closer the
plant is to the low sulfur coal producing regions the less economically attractive will
be the high sulfur coal. Means of making the high sulfur coal more competitive are
discussed.
2. INTRODUCTION
Coal-fired PFBC power plants offer several advantages over conventional power
generation techniques including lower capital costs, reductions in the cost of
electricity, superior environmental performance, and improvements in generating
efficiency of at least 12%. These advantages have prompted considerable research
and development effort to produce a power generating system with high availability
362
and reliability, and the thermal, environmental and economic performance criteria
required by utilities. In the past two years four combined cycle bubbling PFBC
demonstration units have commenced operation (1). They have nominal outputs of
80-MWe and are located in Spain and the USA with two in Sweden. A fifth unit is
under construction in Japan (2). All the units are designed using ABB-Carbon
technology. The success these demonstration units have enjoyed has resulted in three
separate design studies for 320-MWe plants, one in Japan and two in the USA (3).
Prompted by the potential of bubbling PFBC technology, and encouraged by the
results of the Demonstration Program, EPRI has been engaged in studies to assess
the economic and environmental performance of coal-fired PFBC power plants for
application by US utilities. These studies have been performed by Bechtel with the
assistance of ASEA-Babcock, now incorporated into Babcock and Wilcox, and ABB-
Carbon. The results confirm that the capital cost of a 350-MWe PFBC plant is lower
than for other advanced fossil power plants of similar size (4). They also reveal that
for a constant coal price, the economics are favored by low sulfur coals. See Figure
1. The higher the coal sulfur content the higher are the limestone and ash flow rates.
In addition to increasing the operating cost, this increases the size of the solids
handling equipment and increases plant capital costs. These factors result in an
increased cost of electricity.
49
s
4

36-
1 2 3
Coal sulfur content,%
Figure 1. Effect of coal sulfur content on cost of electricity for bituminous coals.
The variation in cost of electricity with coal sulfur content for similar sized PFBC
and IGCC power plants was compared. The IGCC plant uses a highly integrated,
oxygen blown, entrained-flow gasifier (5). Although distinct technologies, both plants
are at similar degrees of advancement so the comparison is considered valid. Design
363
details for the two plants are presented in Table 1. The differential cost of electricity
is presented in Figure 2 where it is shown that the economics favor PFBC for coals
with less than 3 to 4% sulfur. The prime reason for this trend is that as sulfur content
falls so the amount of limestone fed to, and ash removed from, the PFBC falls with
reductions in heat rate, total capital requirement and operating costs. For the IGCC
plant, the reduced sulfur content leads to reduced revenue from by-product sulfur
sales with only minor reductions in total capital requirement. The net effect is an
increase in the cost of electricity with reduced sulfur content coals, the reverse of the
effect with PFBC plants. If the Ca/S molar ratio for 95% retention can be reduced then
the differential costs will increase in favor of PFBC, shifting the curve to the right and
raising the critical coal sulfur content. Work continues to verify these cost data.T h e
studies show coal-fired PFBC power plant technology to be a highly cost effective
option for power generation expansion, especially for low sulfur content coals.
However, for plants distant from sources of low sulfur coal it may be more economic
to use local high sulfur coal. This paper discusses the work carried out to investigate
this hypothesis. Process performance, plant capital costs, coal costs including
transportation, and the cost of electricity have been prepared for four coals to be
burned at a 360-MWe PFBC power plant in a Midwest high sulfur coal mining area.
3. DESCRIPTION OF 360-MWe PLANT
Coal is received by rail via 100-car trains. After removal of tramp iron and other
foreign material, the coal is fed into the preparation system. There it is ground to the
required size distribution and mixed with water to form the paste, containing 25%
moisture, that is injected into the boiler. Limestone for sulfur capture is assumed to
be available locally and delivered to the site by truck. It too is ground to the required
size distribution but remains dry and is fed to the boiler pneumatically using a lock
hopper system.
The boiler, primary and secondary flue gas cyclones, and some ash cooling
systems are installed within a vessel operating at pressures up to 235 psia (16.2 bar).
Also included are the ash reinjection vessels that store bed material at operating
temperature. These allow the rapid lowering and raising of bed level required to
facilitate load control. The combustion air enters the boiler through a sparger-type
distributor. The cleaned flue gas streams recombine after the cyclones and pass to
the gas turbine down the center of a coaxial pipe. In the absence of a suitable plant
layout diagram for the 360-MWe plant, a systems schematic for American Electric
Power's 75-MWe Demonstration PFBC plant is presented in Figure 3 (6).
Fluidized beds in general have low inherent NO^ emissions because of the low
combustion temperatures. Inherent values are typically around 0.2 Ibs/MBtu. Data from
the Demonstration Program indicates that by simply introducing ammonia into the
freeboard NO^ emissions can be reduced by 75% down to 0.05 Ibs/MBtu (7). The cost
of installing and operating such reduction equipment improves environmental
performance for negligible increase in the plant capital and operating costs.
364
Table 1
Design details used in economic comparison of PFBC and IGCC plants
PFBC IGCC
N e t output, M W e 360 500

N e t heat rate, B t u / k W h 8180 8050
Plant configuration 1 combustor 2 gasifiers (1)
1 gas turbine 2 g a s turbines
1 steam turbine 2 steam turbines
Gas turbine type Ruggedized ABB GE7F
inlet temperature, F 1550 2300
Steam turbine type ABB advanced GE standard
main steam pressure, psia 3600 1450
main steam temperature, F 1075 1000
reheat steam temperature, F 1075 1000
Sulfiir removal, % 95 99
N O x emissions, Ibs/MBtu 0.05 (2) 0.06 (3)
Sulfiir sale credit, $ / t o n - 80
A s h disposal cost, $ / t o n 10.5 10.5
(1) Highly integrated design. Air for o x y g e n plant taken ft-om gas
turbine air compressor. O x y g e n purity 95%.
(2) With ammonia injection in combustor ft-eeboard.
(3) With fiiel gas saturation and nitrogen recycle ft-om o x y g e n plant.
IGCC FAVORED
OA
PFBC F A V O R E D
80% capacity
0-4-J factor
^-5 1 '
0 2 3
Coal sulfur content, %
Figure 2. Difference in cost of electricity with coal sulfur content for similar sized PFBC
and IGCC power plants.
365
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r
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S~7 Pee
d Hopoe
r
^ 1 Cfushe
r
Q Rejec
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. C WP ~ ^^ Bel
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r and
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Rojcrl
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Figure 3. System's schematic for AEP's 75-MWe PFBC Demonstration Plant (Taken
from reference 6).
The gas turbine is a modified version of ABB-Carbon's GT140 which drives the
air compressor and generates around 66 MWe. The compressed air is delivered to
the combustor vessel through the annular portion of the coaxial pipe, passing
countercurrent to the flue gas. This arrangement eliminates the need for a refractory-
lined pipe and so precludes the possibility of refractory passing to. and damaging, the
gas turbine. The gas leaving the turbine is at 763T (406"C) and passes to a three-
stage economizer to help heat the boiler feed water. The remaining particulates in the
cooled flue gas are removed in a bag house prior to stack discharge.
Ash leaves the process in two main streams; the cyclone ash and the bed ash.
Cyclone ash is continuously discharged by the cyclones. All the ash collected by the
primary cyclones is combined and partially cooled by combustion air in indirect heat
exchangers. The ash collected by the secondary cyclones is similarly cooled. The two
ash streams are then combined and further cooled, also indirectly, by boiler feed
water, after which they are depressurized through a proprietary device. Finally the ash
stream is stored in its own silo prior to disposal. The bed ash is directly cooled in a
region below the sparger distributor by a portion of the incoming combustion air.
It is then removed intermittently from the combustor through a lock hopper
system and conveyed to its own storage silo prior to disposal.
The boiler is a once-through Benson-type with reheat. To reduce the heat rate
and the plant capital cost, on a $/kW basis, a high temperature supercritical steam
cycle was included in the design. This raises the net output from ABB-Carbon's
nominal 320 MWe to 360 MWe. The steam turbine used is one of a new generation
of advanced steam turbines commercially available in Europe. Inlet steam conditions
366
are 3626 psia/1075T/1075T (250 bar/579'C/579'C). Because of various design

refinements, such as improved steam seals, it is claimed that they have a higher
turbine efficiency. Several 70-MWe versions of this design have been sold and are
operating in Europe. Designs for larger sized turbines are available but as yet none
have been manufactured (8). The steam turbine compatible with a nominal 360-MWe
power plant will generate around 280 MWe. The steam is exhausted to the surface
condenser at 1.85 inches of mercury (0.063 bar). Further, the turbine is designed to
allow uncontrolled steam extractions for condensate and boiler feed water heating, for
driving the boiler feed water pumps and for deaeration.
Other balance of plant systems are of conventional design except for the water
treatment system where an additional step has been included to achieve the higher
water quality required for a once-through boiler. The combustor vessel is enclosed
only from the level of the coal and limestone feed points down. Above this level
protection is not considered necessary as there are no moving parts and routine
maintenance of a mature plant should require only limited access.
4. ACCEPTABILITY OF SUPERCRITICAL STEAM CYCLES
Problems with the first generation of supercritical steam plants have discouraged
many US utilities from including them in their plans for new power plants. Utility
concerns and the way they are being addressed are presented as follows (9);
a unique form of stress-corrosion cracking of the waterwall tubes in the

vicinity of the firebox. This has largely been resolved in pulverized coal (PC)
plants with the advent of improved materials. It is unlikely to occur in a
fluidized bed boiler because the lower combustion temperatures result in
lower outer metal temperatures.
increased turbine blade erosion by iron oxide particles from the inside of the
boiler tubes. Higher steam temperatures accelerate formation of the oxide
which begins to exfoliate sooner than in lower temperature applications.
Recent development work has shown that erosion damage can be limited in
three ways; thorough chemical cleaning of the boiler tubes approximately
every 5 years; the application of plasma spray coatings to the blades; and
selection of boiler tube materials which produce lower amounts of more
tenacious oxide.
cycling duty limitations because of long startup times and limited turndown
capability. These problems have been largely overcome through
development work in Europe and Japan where higher energy costs have
placed a premium on higher efficiency power generation systems.
367
the efficiency of the high pressure turbine stages were often lower than
expected. Improved blade design and manufacturing procedures have
resulted in higher and more accurate projections for turbine performance.
From this short discussion it is apparent that advances have been made to
overcome the shortcomings of the first generation of supercritical boilers. New
designs are greatly improved and PC units are already operating reliably and
efficiently in Europe and Japan. There is no reason why these new supercritical
turbines cannot be used with confidence in conjunction with bubbling PFBC power
plants.
5. STUDY CRITERIA
The general premise of the cases examined is that the designs are based on a
grass-roots, base-loaded facility, using ABB-Carbon's combined-cycle, bubbling PFBC
technology. Other criteria include the following:-
The site is level and located in the tri-state region of Kentucky, Illinois and
Indiana within a 50 mile radius of Evansville, a high sulfur bituminous coal
mining region containing many coal-fired power plants. The detailed plant
costing used in previous studies were based on a site in Kenosha, Wisconsin
and this data base is used for the present study. Although climatically
different regions, they are both Mid-West locations and the plant capital costs
are expected to be very similar.
The sorbent used is limestone.
Sulfur retention performance is based on 95% capture.
Ammonia is injected ahead of the cyclones to reduce NO^ emissions.
Plant designs are based on a mature technology.
Equipment sizing and sparing are based on an equivalent availability of 80%.
Equipment is designed for a 30 year plant life.
Ash is disposed off-site according to non-hazardous waste disposal

guidelines.
All coal is delivered to the site by rail as not all plants will have access to the
Ohio River.
368
The cost estimating approach used is consistent with an EPRI Class II

Preliminary Estimate, as defined in the Technical Assessment Guide (TAG)
(10).
6. RESULTS OF STUDY
A local high sulfur bituminous coal mined in the tri-state area was selected as the
base coal for economic evaluation of the PFBC power plant. Three cost-competitive
low sulfur coals were selected for comparison. They were as follows; a subbituminous
coal from Campbell County, Wyoming; and two Central Appalachian bituminous coals,
one from Perry County, Kentucky and the other from Buchanan County, Virginia. All
four coals selected come from seams with abundant reserves. Typical coal
composition data are presented in Table 2. The sulfur contents vary from 0.4 to 3.3%,
and so fall within the range found to be most economic for PFBC power plants.
Table 2
Coal composition data
Coal Local high E. Kentucky W. Virgiia Wyoming

sulfur coal sub-bitum.
Composition, wt. %
Moisture 9.2 6.8 5.8 30.2
Carbon 67.2 69.6 73.9 48.2
Hydrogen 4.4 4.7 4.8 3.3
Nitrogen 1.4 1.4 1.5 0.7
Sulfur 3.3 1.3 0.7 0.4
Oxygen 5.9 6.4 6.3 11.9
Ash 8.6 9.8 7.1 5.3
Higher heating value, Btu/lb 12800 12500 13100 8340
6.1. Delivered cost of coals

Table 3 presents estimated costs for the four coals delivered to the power plant.
The free-on-board (FOB) cost at the mine is a representative value taken from an EPRI
data base (11). Naturally there is spread around these costs as well as variations with
sulfur content, the costs in each mining location trending down with increasing sulfur
content. The Wyoming sub-bituminous coal has by far the lowest FOB cost because
of the high productivity, low cost operations possible from the surface mining of thick
seams, some almost 100 feet thick. The rail costs are also estimated using the EPRI
369
Table 3
Cost data for coals delivered by rail to vacinity of Evansville
Coal Local high E. Kentucky W. Virginia Western

Rail transport distance, miles 50 240 390 1210
Prices, Dec.1992, $/ton (*)

FOB at mine 22.75 26.55 28.72 4.24
Transportation 4.23 8.33 11.57 17.81
Delivered 26.98 34.88 40.29 22.05
Delivered, in $/MBtu 1.08 1.40 1.54 1.32
(*) Taken from EPRI data base (11)
data base. The transportation cost for the three bituminous coals is around 2 mills/ton-
mile and it is possible to use the same rail company from mine to power plant (12).
The rail companies transporting coal from Wyoming coal charge only around 1
mill/ton-mile. The lower cost arises from high productivity and the heavy investment
made in upgrading track and rolling stock (13). These low cost rail companies do not
reach all the way into the region around Evansville so it will be necessary to transfer
the loaded rail cars over to the higher cost local companies for final delivery to the
power plant. This increase is included in the estimated transportation cost for the sub-
bituminous coal presented in Table 3. This combination of low cost mining and
transportation results in the sub-bituminous coal having the lowest delivered cost, in
$/ton, of all four coals. This is remarkable considering that the transport distance is
over 1200 miles. However, when expressed in terms of $/MBtu, because of its higher
heating value, the high sulfur coal has the lowest cost. The West Virginia coal, which
has the lowest sulfur content, is the highest cost fuel because of its high FOB price
and the long distance traveled.
6.2. Process performance

The process performance data are summarized in Table 4. Compared to the high
sulfur coal, the low sulfur coals have lower limestone demand, ash discharge rates
and SOg emissions. The net power output is similar for all four coals but because of
its higher moisture content the heat rate for the sub-bituminous coal is greater than
the others. Because of this adverse effect, rather than adding further moisture to
produce a coal feed paste it was elected to feed the sub-bituminous coal dry using
a lock hopper system. The cost of this design change has been included in the capital
and operating cost estimates.
370
Table 4
PFBC process performance summary for the four coals
Coal Local high Kentucky W. Virginia Western

Coal, tons/day (as received) 2840 2710 2710 4380

MBtu/hr 2960 2990 2990 3040
Limestone, tons/day 890 280 150 85
Ash discharge, tons/day 1030 580 360 340

S 0 2 , Ibs/MBtu 0.26 0.10 0.05 0.04
NOx, Ibs/MBtu 0.05 0.05 0.05 0.05
Power generated, MWe

Gas turbine 67.8 65.4 66.0 69.4
Steam turbine 298.8 303.0 304.8 295.9
Total 366.6 368.4 370.8 365.3
Auxiliary power, MWe 8.1 7.4 7.2 7.4

Net power to grid, MWe 358.5 361.0 363.6 357.9
Heat rate, Btu/kWh (HHV) 8260 8280 8230 8510

Cycle efficiency, % (HHV)41 3 412 41.5 40.1
6.3. Total capital requirements

The costing are presented in Table 5. The majority of the boiler island equipment
and some of the balance of plant equipment was costed individually. Where costs
were not available, estimates were made by factoring actual equipment costs for the
80-MWe units constructed for the Demonstration Program. To allow for any increased
uncertainty in the costs of the 360-MWe plant, project and process contingencies have
been increased where appropriate. Where necessary, costs have been escalated at
3.2% per annum to bring them to a common basis of December, 1992. The total
capital requirement values are considered to be accurate to better than 20%.
Included in the costing is an allowance for funds used during construction
(AFUDC). which is calculated as a proportion of the total plant cost. The construction
time for a 360-MWe PFBC is 29 months. A PC plant of similar size would require a
construction time of 36 months. The shorter construction period for the PFBC plant
results in an AFUDC factor 30% lower than for the PC plant.
The total capital requirement is highest for the high sulfur coal case because the
higher limestone and ash flow rates increase the size of the solids handling
equipment. Conversely the total capital requirement is lowest for the West Virginian
coal which has the lowest sulfur content. The difference in the two costs is only
around 3%. The dry feed lock hopper system elevates the costs for the subbituminous
371
Table 5
PFBC capital cost data for the four coals
Coal Local high E. Kentucky W. Virginia Wyoming

Boiler island 142.4 139.4 139.0 139.9

Balance of plant 143.6 139.5 138.5 144.0
Indirect field costs 39.8 38.8 38.6 39.6
Home office engineering 31.0 30.3 30.1 30.8
Contingencies 63.1 61.6 61.3 62.4
Total plant cost 419.9 409.6 407.5 416.7
AFUDC (1) 32.3 31.5 31.4 32.1

Owner's costs 21.8 20.2 19.8 20
Total capital requirement 474.0 461.3 458.7 468.8
Generating capacity, MWe 358.5 361.0 363.6 357.8

Total capital req'ment, $ / k W 1322 1278 1261 1310
Costs in $millions except where indicated

(1) Allowance for funds used during construction
coal plant. Because the power outputs are so similar the trend of the normalized total
capital requirement, in $/kW, is similar to the absolute values.
The Demonstration program discussed earlier has shown PFBC technology to
be fuel flexible and capable of burning a range of coals. Consequently, a plant
designed for operation with high sulfur coal could easily transfer over to low sulfur
coal if circumstances demanded it. The reverse switch would not be so easily
achieved unless the limestone and ash handling equipment had been designed to
cope with increased solids flow rates. The range of excess solids handling capacity
could be limited if the alternative to the low sulfur coal was to be a low sulfur/high
sulfur coal blend. Incorporating such flexibility into the basic design gives the utility the
capability to take advantage of low cost fuel options as they arise, regardless of coal
sulfur content. According to the cost data presented in Table 5, the capital cost
increase to achieve this flexibility is not prohibitive.
6.4. Cost of electricity

These costs are developed according to TAG guidelines and include the
performance and cost data presented in Tables 3, 4 and 5. An 80% capacity factor
is used, all costs are for December, 1992 and start-up is in 2000. The data are
presented in Table 6 where the cost of electricity (GOE) is shown to be similar for all
372
Table 6
Cost of electricity for the four coals
Coal Local high E.Kentucky W.Virginia Wyoming

Capital charge 20.0 19.3 19.1 19.8

O&M with consumables 6.1 6.0 5.9 6.1
Coal (costs as per Table 3) 8.9 11.6 12.7 11.2
Limestone ($12.5/ton) 1.1 0.4 0.2 0.2
Ash disposal ($10.5/ton) 1.4 0.8 0.5 0.5
Levelized cost of electricity 37.5 38.1 38.4 37.8
Costs in m i l l s / k W h escalated to December, 1992.

80% capacity factor with start-up in 2000.
four coals. The lowest COE is for the local high sulfur coal but not by as much as
might have been anticipated from its much lower delivered cost. The fuel cost
advantage is eroded by the higher costs for capital, limestone and ash disposal. All
of these higher costs arise because of the higher coal sulfur content.
From this information it is concluded that a bubbling PFBC power plant located
within a 50 mile radius around Evansville, Indiana, can burn high sulfur coal to
generate electricity at a price competitive with that generated from low sulfur coal. For
plants outside of this radius economic circumstances will change with low sulfur coal
becoming progressively more competitive as the site gets closer to the mine.
7. FURTHER FACTORS AFFECTING THE COST OF ELECTRICITY
This section discusses ceaain aspects which may improve or lessen the
competitiveness of high sulfur coal compared to the low sulfur coal options.
7.1. Externality charges

Some regulatory bodies are currently considering whether industry should bear
the cost of any detrimental effects their processes have on the environment and the
public social well-being. Such charges, known as externalities, could be assessed on
unregulated emissions as well as on any residual regulated emissions leaving control
technology equipment. Whether such charges will be imposed and what their values
should be has not been decided at the federal level but some states have proposed
values to be used for evaluating new energy resource decisions. Values to be used
in Massachusetts are presented in Table 7 (14).
373
Table 7
Externality charges used in resource assessment in Massachusetts
Emission species Externality charge

$/ton
S02 1,700
NOx 7,200
C02 24
Suspended solids 4,400
N20 4,400
CO 960
CH4 240
Volatile organics 5,900
These charges vary considerably between states. For example, the charges used
in California for SO^ and NO^ are $18.300/ton and $24,500/ton, respectively. Further,
some states are considering an ash disposal charge due to diminishing landfill
locations. With respect to PFBC operation the emission levels for the first four species
in Table 7, SOg, NO^, COg and suspended solids, are well characterized. The NgO and
CO are not fully characterized but preliminary measurements indicate that values for
both are below 10 ppmv. As yet there are no published data for CH4 and volatile
organics.
The values for the first four emission species have been used to calculate by how
much they effect the COE values presented in Table 6. The results are presented in
Table 8. On average the externality charges raise the cost of electricity by 23
mills/kWh, or 61%. Although the costs for the four coals are still similar, their relative
rankings have changed. The costs have risen more for the local high sulfur coal,
because of the higher SOg in the flue gas, and for the sub-bituminous coal because
of the higher COg level arising from the higher heat rate.
Although the externalities do not significantly influence the relative cost of
electricity for the four coals, the charges do adversely affect the general
competitiveness of coal relative to natural gas. With natural gas there will be little SOg
and no suspended solids in the flue gas, so externality charges would be assessed
on only NO^ and COg, for which the charges are 2.0 and 10.5 mills/kWh, respectively.
This is a total externality charge of 12.5 mills/kWh, 10.5 mills/kWh less than the
average value of 23 mills/kWh for the four coals. The major contributor to this cost
differential is the externality charge levied on CO2.
374
Table 8
How cost of electricity is affected by externality charges as assessed in Massachusetts
Coal Local high E. Kentucky W. Virginia Wyoming

COE from Table 5 37.5 38.1 38.4 37.8
Externality charges
S02 1.8 0.7 0.4 0.3
NOx 1.5 1.5 1.5 1.5
C02 19.8 20.3 20.4 21.6
Suspended solids 0.2 0.2 0.2 0.2
Revised COE 60.8 60.8 60.9 61.4
All costs in mills/kWh escalated to December, 1992.

80% capacity factor with start-up in 2000.
7.2. Ash utilization and disposal

To reduce the impact of ash disposal on the cost of electricity, EPRI is to fund
work to identify uses for the ash along with its associated value and extent of
utilization. From Table 6, the cost of ash disposal for the local high sulfur coal is 1.4
mills/kWh, 3.7% of the total cost. These figures indicate that for this coal there is good
potential for cost reductions if the ash can be marketed. The potential for cost
reductions with the lower sulfur coals is much lower, for example for the
subbituminous coal the ash disposal cost is 0.5 mills/kWh, 1.3% of the total cost. If an
externality charge were assessed on the ash, the financial incentive to utilize the ash
would be increased.
The physical and chemical properties of PFBC ash differ from those of AFBC
ash. In an AFBC, the limestone completely calcines resulting in a large amount of free
lime in the ash. In a PFBC, the higher partial pressure of COg inhibits calcination and
this results in less than 1 % of free lime in the ash. The lower free lime makes cement
products made from PFBC ash less prone to the secondary reactions and cracking
that has plagued AFBC cement products (15). This is expected to make PFBC ash
a more valuable by-product than AFBC ash. Often dolomite, which has a high
magnesium content, is used as the sulfur sorbent. Magnesium oxide promotes
secondary reactions in cements and this would limit the utilization of ash from PFBC
plants using dolomite.
There will still be a need to dispose of ash, so cheaper means of disposal need
to be pursued. One possibility is to include disposal of ash at the mine site in any coal
375
purchase agreement. Such an agreement will be to the benefit of the local high sulfur
coal because the distances traveled and the rail costs incurred will be lower than for
the low sulfur coals.
7.3. Improved sorbent utilization

EPRI is working with the developers of circulating PFBC power plants (16,17) to
establish whether this technology can reduce limestone demand and so lower capital
and operating costs. Reduced limestone demand also results in reduced ash disposal
costs. Ca/S molar ratios of around 1.3 are being claimed for sulfur retentions in
excess of 95%. The circulating PFBC also has the potential to reduce plant capital
costs but this would be the case regardless of coal type and so will not influence the
relative costs of electricity.
From Table 6, the effect of raw limestone and the disposal of ash upon the cost
of electricity for the high sulfur coal is shown to be 2.1 mills/kWh, 5.6% of the total
cost. Reducing the Ca/S molar ratio from 2.55 to 1.3 will reduce the limestone and ash
flows and lower the cost of electricity by 1.0 mill/kWh, 2.7% of the total cost. For the
low sulfur coal the combined reductions are only 0.3 mills/kWh and 0.8%, respectively.
Again, if an externality charge were assessed on the ash, the financial incentive to
lower limestone demand would be increased.
7.4. Raw material and transportation cost variations

The data presented in Tables 4, 6 and 8 show that PFBC technology is capable
of producing electricity at a price competitive with low sulfur coal and with excellent
environmental performance. Several cost factors can influence the process economics
resulting in one coal being favored over another.
Increased coal sulfur content. If the high sulfur coal sulfur content was to
increase to 4.0%, the increased limestone and ash flows would result in a increased
capital and operating costs and increase the cost of electricity by 0.8 mills/kWh. To
keep the cost of electricity the same the coal cost would have to fall to $0.98/MBtu,
or $20.70/ton, to compensate. A site specific study would have to be carried out to
establish the maximum coal sulfur content that could be burned before the use of a
low sulfur coal became more economically attractive.
Decreased limestone and ash disposal costs. As high sulfur coals use more
limestone and produce more ash for disposal the cost of electricity is more sensitive
to variations in the associated prices. For example, the cost of limestone used in the
study is $12.5/ton. If the cost was $8.5/ton there would be a 0.4 mills/kWh decrease
in the cost of electricity for the high sulfur coal but less than 0.1 mill/kWh for the sub-
bituminous coal.
Reduced cost for low sulfur coal. As utilities implement their strategies to comply
with the terms of the 1990 Clean Air Act Amendment the demand for low sulfur coal
is expected to increase to the detriment of high sulfur coal. Demand for Eastern low
sulfur coal is expected to increase by around 45 million tons/annum by 2000 while the
376
demand for Western coal is expected to increase by between 65 and 150 million
tons/annum by 2000 (18). With this market trend high sulfur coal will remain cost
competitive as its FOB cost is likely to decrease relative to that of low sulfur coal.
This increased demand for low sulfur coal probably will saturate existing rail
corridors requiring increased rail investment. Provided that this is done judiciously rail
costs are not expected to rise and indeed may fall as productivity is increased and
unprofitable routes are closed. The potential for rail cost reductions is greatest in the
Eastern region where costs are higher. However, as the rail cost only constitutes 30%
of the delivered cost for coal, a 10% reduction would only lower the cost of West
Virginian coal by $0.04/MBtu to $1.50/MBtu which would reduce the cost of electricity
by 0.4 mills/kWh to 38.0 mills/kWh which is still above the 37.5 mills/kWh for the high
sulfur coal. Because of the long distances traveled the rail cost constitutes 80% of the
delivered cost for the Wyoming coal. Here a 10*^0 reduction would lower the coal
cost by $1.78/MBtu to $20.27/MBtu which would reduce the cost of electricity by 0.9
mills/kWh to 36.9 mills/kWh which is only marginally lower than the 37.5 mills/kWh for
the high sulfur coal.
Concluding comments. On the basis of these calculations PFBC power plants

built in the region around Evansville are expected to produce electricity more
economically when fired on local high sulfur coals in preference to low sulfur coals
delivered by rail. However, as the plant location moves closer to the source of the low
sulfur coal, the high sulfur coal will become less competitive as its transportation cost
increases compared to that of the low sulfur coal. For this reason high sulfur coal
plants built at, or close to, the periphery of the high sulfur coal fields are more likely
to burn low sulfur coals, either from the Western or Eastern coal fields. Waterways
usually offer the lowest transportation costs and so reduce the delivered cost of the
coal. As the Ohio River runs through the tri-state region, Western sub-bituminous coal
may be more economically attractive than local high sulfur coal for riverside plants
located within the 50 mile region around Evansville and beyond.
8. CONCLUSIONS
1. The cost of electricity generated by a bubbling PFBC power plant has been
calculated for four coals delivered by rail to a site within a 50 mile radius of
Evansville, Indiana. The coals were; a local high sulfur bituminous; two central
Appalachian low sulfur bituminous; and a low sulfur Wyoming sub-bituminous.
2. The delivered cost for each coal was calculated which included estimating the
transportation costs. Despite being transported over 1200 miles the sub
bituminous coal was the cheapest in $/ton. However, when expressed in $/MBtu,
because of its higher heating value, the local high sulfur coal was the cheapest.
The low sulfur Appalachian coals were the most expensive.
3. The total capital requirement was determined for each coal. Because of the
greater flow rates of limestone and ash the high sulfur coal-fired plant had the
377
highest cost but it was only 3% higher than the lowest cost plant which burned
the low sulfur Appalachian coal.
4. The costs of electricity for each coal were very similar. The lower delivered cost
advantage of the local high sulfur coal was eroded by the higher costs for
capital, limestone and ash disposal.
5. The costs of electricity for each coal still remained similar when externality
charges, as applied in Massachusetts, were assessed on SOg, NO,^, COg and
suspended particulates. The costs were, however, higher on average by 23
mills/kWh, 61%. Externalities for natural gas amount only to 12.5 mills/kWh, 10.5
mills/kWh lower than for the four coals. This differential adversely affects the
general competitiveness of coal relative to natural gas.
6. The delivered cost of low sulfur coal relative to high sulfur coal is not expected
to fall so the future cost of electricity from PFBC plants fired with high sulfur coal
will remain competitive. Nevertheless, it is essential to control feedstock costs,
both coal and limestone.
7. Means of reducing the cost of electricity from high sulfur coal-fired plants are
discussed. These include; utilizing the ash as a building material; investigating
alternative means of ash disposal; and improved limestone utilization, possibly
by burning the coal in a circulating PFBC power plant.
8. Although it is clear that high sulfur coal is competitive in the region around
Evansville, it is likely to become less competitive as the power plant location
moves closer to the source of low sulfur coal. This results in an increase in the
transportation cost of the high sulfur coal raising its delivered price relative to that
of low sulfur coal.
REFERENCES
1. Anderson, J. 5. and Jansson, 5. ., "Commissioning experience from three PFBC

plants", Proc. 11th International FBC Conference, Montreal, April, 1991, Vol. 2, pp
787 to 794.
2. Fujita, M., "Outline of Wakamatsu PFBC project". Conference Proceedings of
"Application of fluidized-bed combustion for power generation", Boston,
September, 1992, EPRI PR-101816, April, 1993.
3. Private communication. F. S. Kinsinger, Babcock and Wilcox, to J. M. Wheeldon,
EPRI, August, 1992.
4. Wheeldon, J. M. et al, "Cost and performance improvements in utility-scale
bubbling PFBC power plants", Proc. 12th International PFBC Conference, San
Diego, May, 1993. To be published by ASME.
5. van Liere, J., Willeboer. W. and Zon, G. D., " Dutch IGCC developments 1992:
Demkolec plant status, Demoprogram and R&D work", 11th Conference on
Gasification Plants, San Francisco, October, 1992. To be published by EPRI.
6. Whitney, S., "PFBC applications in utility systems", Power-Gen '92, Orlando,
November, 1992.
378
7. Dahl, . and Nordin, S., "Experience from the first year of commercial operation
of the Vrtan PFBC plant". See Reference 2.
8. Private communication. S. A. Jansson, ABB-Carbon, to R. R. McKinsey, Bechtel,
April, 1992.
9. "Assessment of supercritical power plant performance", EPRI CS-4968,
December, 1986.
10. "EPRI Technical Assessment Guide", EPRI P-6587-L. Vol. 1, Rev. 6, September,
1989.
11. Private communication. J. Piatt, EPRI, to J. M. Wheeldon, EPRI, February, 1993.
12. "Coal transportation risks for fuel switching decisions", EPRI IE-7118, Volume 2:
Eastern rail/river network, January, 1992.
13. Ibid. Volume 1: Powder River basin and inland waterways, September, 1991.
14. Smock, R. W., "Externalities bias planning against fossil-fired generation", Power
Engineering, July, 1992, 11.
15. Bland, A. E. et al, "Production of no-cement concretes utilizing FBC waste and
power plant flyash", Proc. 9th International FBC Conference, Boston, May 1987,
Vol. 2, pp 947 to 953.
16. Rehwinkel, ., von Wedel, G. and Kitchen, W. ., "Deutsche-Babcock circulating
PFBC experience and the outlook for market applications of the technology". See
Reference 2.
17. Provol, S. J. and Dryden, R. J., "Pilot plant test results and demonstration of the
Ahlstrom Pyropower pressurized CFB technology", ibid.
18. "Utility coal markets under acid rain legislation", EPRI IE-7110, June, 1991.
B A S I C PARAMETERS OF SULFUR CAPTURE BY SORBENTS

DURING COMBUSTION OF HIGH SULFUR COAL PELLETS
M. S . Ahmed 1 , a n d Y. A. Attia 2.
1 . U n i v e r s i t y of Suez Canal, Department of Metallurgical Eng.,

C o l l e g e o f P e t r o l e u m a n d M i n i n g E n g i n e e r i n g , S u e z , EGYPT.
2.TAASI L a b o r a t o r y , 1 4 4 5 Summit S t r e e t , C o l u m b u s , O h i o , 4 3 2 1 4 ,
U.S.A.
ABSTRACT
Several factors have been identified as influencing sulfur

c a p t u r e by s o r b e n t s d u r i n g t h e c o m b u s t i o n of h i g h s u l f u r c o a l s .
Such f a c t o r s include sorbent composition, sorbent to sulfur
r a t i o , a i r t o s o l i d r a t i o and t h e t e m p e r a t u r e o f t h e c o m b u s t i o n
zone.
Thermodynamics of behaviour of s u l f u r d u r i n g combustion of a

h i g h s u l f u r c o a l and s t a b i l i t i e s o f t h e formed s u l f a t e s were
r e v i e w e d . Then c o m b u s t i o n t e s t s were c a r r i e d o u t i n an e l e c t r i c
tube furnace u s i n g small t a b l e t specimens c o n t a i n i n g powdered
c a r b o n a s f u e l , FeS a s s u l f u r s o u r c e and p u r e Ca0,CaC03,Ca(0H)2
o r a m i x t u r e o f Ca(0H)2+Mg0 ( s i m i l a r t o d o l o m i t e ) a s s o r b e n t s .
T e s t s r e s u l t s showed t h a t t h e s o r p t i v e c a p a c i t y i n c r e a s e s w i t h
increasing the air flowrate and/or calcium to sulfur molar
r a t i o up t o l i m i t i n g v a l u e s above w h i c h no d e t e c t a b l e effect
c a n b e o b s e r v e d . I t w a s a l s o o b s e r v e d t h a t Ca(0H)2+Mg0 m i x t u r e
h a s t h e h i g h e r s o r p t i v e c a p a c i t y f o l l o w e d b y Ca(OH)2 , C a 0 a n d
t h e n CaCOj . T e m p e r a t u r e range of 800-1000 C seemed t o be
optimal f o r s u l f u r c a p t u r e by Ca-based s o r b e n t s . At about 1200
C a p a r t i a l s i n t e r i n g o f t h e a s h was n o t i c e d w i t h Ca(0H)2+Mg0
sorbent, which leads t o a r e l a t i v e l y higher s u l f u r r e t e n t i o n .
1. INTRODUCTION
Coal has h i s t o r i c a l l y been one of t h e most important energy

s o u r c e s , a l o n g w i t h p e t r o l e u m and g a s . The c o a l r e s o u r c e b a s e
i s l a r g e , a c c e s s i b l e and c o m p a r a t i v e l y l o w - c o s t . However, its
combustion has been r e c o g n i z e d as t h e main s o u r c e of sulfur
o x i d e s p o l l u t i o n . For t h i s r e a s o n , t o s u s t a i n and i n c r e a s e its
i m p o r t a n c e a s an e n e r g y s u p p l y , t h e h i g h s u l f u r c o a l resources
380
must n o t be viewed as a l o w - q u a l i t y feed s t o c k , but r a t h e r as a

low-cost f e e d s t o c k f o r h i g h - q u a l i t y p r o d u c t s and p r o c e s s e s .
There has been a t r e n d toward t h e removal of s u l f u r o x i d e s from

the flue gases during the combustion process. This involves the
u s e of s u i t a b l e s o r b e n t s t o a d s o r b such o x i d e s from t h e stack
g a s e s stream t o form s o l i d m a t e r i a l s . T y p i c a l s o r b e n t s include
Ca-based sorbents ( e . g . limestone, dolomite or hydrated lime)
or Na-based sorbents ( e . g . sodium bicarbonate or sodium s e s q u i -
c a r b o n a t e ) . However, Na-based s o r b e n t s have been ranked n e x t i n
commercial availability.
S e v e r a l t e c h n i q u e s have been p r o p o s e d and t e s t e d f o r desulfur

ization of the flue gases by a Ca-based sorbent. The dry
sorbent i n j e c t i o n technique [1-4] involves the i n j e c t i o n of a
finely ground dry sorbent inside or outside the burning
chamber. In t h i s c a s e an e l e c t r o s t a t i c p r e c i p i t a t o r o r b a g h o u s e
i s e s s e n t i a l l y t o c o l l e c t t h e f o r m e d s a l t (CaS04 ) i n addition
t o the unreacted sorbent. Another proposed technique for s u l f u r
o x i d e s removal from t h e f l u e g a s e s was done by i n j e c t i n g the
powdered dry s o r b e n t i n t h e f l u i d i z e d - b e d combustor [ 4 - 7 ] . It
was o b s e r v e d t h a t t h e f i n e r t h e p a r t i c l e of t h e s o r b e n t , the
h i g h e r t h e u t i l i z a t i o n r a t e . However, f i n e r p a r t i c l e s are a l s o
more e a s i l y c a r r i e d o u t o f t h e bed by t h e f l u e g a s e s before
completeness of the s u l f a t i o n r e a c t i o n .
An a t t r a c t i v e technique for fixation of sulfur in the ash

d u r i n g c o m b u s t i o n was t e s t e d by Zhuang e t a l [ 8 ] . They o b s e r v e d
that addition of Ca-based sorbents to coal briquets, using
r e a s o n a b l e C a / S m o l a r r a t i o o f 2 - 2 . 5 , c u t s down n e a r l y o n e h a l f
o f SO2 e m i s s i o n f r o m a s t o k e r b o i l e r a t f u r n a c e t e m p e r a t u r e s o f
1 2 0 0 - 1 3 0 0 C. T h i s t e c h n i q u e a p p e a r s t o b e f a v o r a b l e and n e e d s
lower c a p i t a l i n v e s t m e n t compared w i t h t h a t of t h e injection
techniques. In a d d i t i o n , it can be applied to convert the
d i s p o s a l of high s u l f u r c o a l f i n e s i n t o u s e a b l e energy without
contaminating the atmosphere with s u l f u r .
These i n t e r e s t i n g observations warranted further investigations

concerning the important factors a f f e c t i n g the sulfur fixation
in the ash during combustion processes. Such f a c t o r s include
sorbent composition, sorbent to sulfur ratio, air to solid
r a t i o and t e m p e r a t u r e o f t h e c o m b u s t i o n z o n e . T h e r e f o r e , the
present work was undertaken to study the above mentioned
factors, as a contribution t o t h e d e v e l o p m e n t o f an a d e q u a t e
scheme for the nonpollution combustion of the high sulfur
coals.
2. THERMODYNAMICS AND K I N E T I C S CONSIDERATIONS
In c o a l m i n e r a l s , s u l f u r o c c u r s i n t h e form of s u l f i d e sulfur
( m a i n l y FeS2 and F e S ) , s u l f a t e s u l f u r ( m a i n l y FeS04 ) and/or
organic s u l f u r . Let us c o n s i d e r t h e thermodynamic behaviour of
sulfur during combustion of a high sulfur coal. The free
381
energies of the involved reactions are derived from the

c o l l e c t e d thermodynamic data [ 9 , 1 0 ] , in Table 1. Reactions 1
through 9, are described in Table 1.
Table 1 Calculated values of G i b b s f r e e e n e r g y ( AG) f o r

the involved reactions of s u l f u r during combustion
of a high-S c o a l .
AG = - AS
Reaction
AH(J/mole) As(J/ K/mole)
(1) C + 0 2 = CO2 -394968 -0.54

(2) F e S 2 = F e S + 1 / 2 S2 181830 187.5
(3) F e S 0 4 = 1 / 2 2 3 + SO2+ 1 / 4 O2 203273 202.0
(4) F e S 2 + 1 1 / 4 O2 = 1 / 2 F e 2 0 3 + 2 SO2 -793238 -8.7
(5) F e S + 7 / 4 O2 = 1 / 2 F e 2 0 3 + SO2 -613122 -124.0
(6) 1 / 2 S 2 + O2 = SO2 -361319 -72.6
(7) SO2+ 1 / 2 O2 = SO3 -96140 -90.58
(8) F e S + C + 5 / 4 O2 = 1 / 2 2 3 + COS -445421 -54.24
(9) 1 / 2 S 2 + C + 1 / 2 0 2 = COS -202604 9.95
B o t h FeS2 and FeS04 are unstable compounds and dissociate

e a s i l y a t temperatures above about 700 C w i t h a b s o r p t i o n of
heat (reactions 2&3). Oxidation of FeS2 and FeS w i t h air
( r e a c t i o n s 4&5) a r e h i g h l y e x o t h e r m i c r e a c t i o n s a n d s t a r t in
the temperature range of 430-500 C [11] Also free sulfur,
produced from dissociation of sulfide and organic sulfur,
o x i d i z e s w i t h a i r ( r e a c t i o n 6 ) . A s l i g h t f o r m a t i o n o f SO3 a n d
COS ( r e a c t i o n s 7 , 8 & 9 ) c o u l d b e t a k e n i n t o a c c o u n t . H o w e v e r , t h e
significantly large differences in the free energies of
f o r m a t i o n ( T a b l e 1 ) s h o w s t h a t SO2 i s t h e m o r e s t a b l e g a s u n d e r
t h e thermodynamic c o n d i t i o n s of combustion t e s t s .
The mechanism and kinetics of sulfur capture by Ca-based

sorbents (e.g. lime, limestone, hydrated l i m e and dolomite)
during combustion of a h i g h s u l f u r c o a l have been s t u d i e d by
several investigators [1-6]. On t h e b a s i s o f t h e s e studies.
broadly these sorbents undergo the following two-step
reactions:
CaC03 CaO + CO2 , AH +183000 J (10)
Ca(0H)2 CaO + H2O AH +111000 J (11)
Then
CaO + SO2 + 1 / 2 O2 = C a S 0 4 , Ah -461346 J (12)
MgO + SO2 + 1 / 2 O2 = M g S 0 4 , AH -370640 J (13)
During the first step limestone and/or hydrated lime are

calcined (reactions lO&ll). Decomposition o f CaCOs is highly
382
endothermic r e a c t i o n and c o m p l e t e d i s s o c i a t i o n o c c u r s a t a b o u t
900 C ( i . e . a t CO2 p a r t i a l p r e s s u r e o f 1 a t m o s p h e r e ) . However,
dehydration o f Ca(OH)2 consumes l e s s h e a t and t a k e s p l a c e at
a b o u t 5 0 0 C. F o r MgC03 ( i f p r e s e n t ) , a t e m p e r a t u r e o f a b o u t 4 0 0
C i s needed f o r d e c o m p o s i t i o n a n d f o r Mg(0H)2 a temperature
below 200 C i s sufficient for dehydration [12].
I n t h e s e c o n d s t e p SO2 is c a p t u r e d b y CaO a n d MgO i n the

p r e s e n c e of oxygen t o form s u l f a t e s ( r e a c t i o n s 12&13). For a
comparative assessment of the physicochemical nature of the
g i v e n c a r b o n a t e s (CaC03 a n d MgC03) a n d s u l f a t e s ( F e S O a , CaS04
a n d MgS04 ) , t h e e f f e c t o f t e m p e r a t u r e o n t h e i r s t a n d a r d free
energies are i l l u s t r a t e d in F i g . l . I t i s seen that the formed
s u l f a t e s of l i m e and m a g n e s i a appear t o be thermodynamically
stable under conditions similar to that prevailing in the
c o m b u s t i o n z o n e ( i . e . a t h i g h SO2 c o n c e n t r a t i o n a n d e x c e s s O 2 ) .
T h e s t a b i l i t y o f C a S 0 4 a n d MgSOa a t h i g h t e m p e r a t u r e s c a n b e
estimated in terms of the decomposition equilibrium constant.
For the decomposition of CaS04 (reverse reaction 12) the
temperature dependence of the equilibrium constant, determined
by Turkdogan e t a l [ 1 3 ] / i s r e p r e s e n t e d f o r u n i t a c t i v i t i e s of
s o l i d C a S 0 4 a n d CaO a t t e m p e r a t u r e s b e l o w 1 1 9 5 C b y :
24120
log PSO2 .PO2 = - + 12.416 (14)

and from 1196 to 1365 C (melting temperature of CaS04) by:
23680
log PSO2 .P02 = - + 12.111 (15)

A l s o f o r MgS04 ( r e v e r s e r e a c t i o n 1 3 ) , t h e e q u i l i b r i u m constant
f o r u n i t a c t i v i t i e s o f s o l i d MgS04 a n d MgO, a s d e t e r m i n e d b y
Turkdogan and R i c e [ 1 4 ] , i s g i v e n i n t h e t e m p e r a t u r e r a n g e from
900 t o 1 1 3 6 C ( m e l t i n g p o i n t o f MgS04) b y :
19095
log PSO2 .P02 = - + 13.461 (16)

The t e m p e r a t u r e dependence of the decomposition equilibrium

c o n s t a n t s o f p u r e CaS04 a n d MgS04 a r e r e p r e s e n t e d graphically
i n F i g . 2 . The l o w e r t h e e q u i l i b r i u m c o n s t a n t , t h e more stable
w i l l be the s u l f a t e .
Referring to Figs.l&2, i t i s clear that the s t a b i l i t y of pure

C a S 0 4 a t h i g h t e m p e r a t u r e s i s m u c h h i g h e r t h a n t h a t o f MgS04
In a d d i t i o n , Turkdogan and R i c e [14] noticed that traces of
calcium impurity in magnesia lower the d i s s o c i a t i o n temperature
a n d p r e s s u r e o f MgSOa
Fig. 1. Effect of temperature on the Fig. 2. Temperature dependence of the
standard free energy change of formation. equilibrium constant for dissociation
of CaSC>4 and MgS04 .
383
384
Thermochemical calculations conducted by Reid [15] indicate

t h a t CaO i s c a p a b l e o f r e m o v i n g e s s e n t i a l l y a l l SO2 p r e s e n t in
the combustion products of a high s u l f u r coal for temperatures
below 980 C p r o v i d e d enough time i s a v a i l a b l e , w h i l e MgO i s
e q u a l l y e f f e c t i v e i f t h e t e m p e r a t u r e d o e s n o t e x c e e d 6 5 0 C.
3.1. Sample Preparation:
A h i g h s u l f u r (5% S ) c a r b o n a c e o u s f u e l o f - 1 2 0 m e s h g r a i n size
was s y n t h e s i z e d by b l e n d i n g pure carbon powder w i t h powdered
FeS. Several specimens of such fuel were prepared separately.
Then e a c h s p e c i m e n (-'5 gms) w a s m i x e d w i t h a s p e c i f i e d amount
o f a s u l f u r d i o x i d e s o r b e n t . The t e s t e d s o r b e n t s w e r e p o w d e r s
o f p u r e CaC03 , C a O , C a ( 0 H ) 2 a n d a m i x t u r e o f C a ( 0 H ) 2 --MgO w i t h
Ca/Mg w e i g h t r a t i o o f 1 . 6 / 1 ( s i m i l a r t o d o l o m i t e ) . Ca/S molar
r a t i o of t h e prepared f u e l - s o r b e n t m i x t u r e was a d j u s t e d i n t h e
r a n g e from 1 / 1 t o 5 / 1 . The m i x t u r e was t h e n p r e s s e d a t 250
k g / c m ^ i n a c y l i n d r i c a l h a r d s t e e l d i e t o f o r m p e l l e t s ( 1 4 mm
in diameter).
3.2. Combustion Tests:
The f u e l s a m p l e s ( p e l l e t s ) w i t h v a r i o u s C a / S m o l a r r a t i o s w e r e
combusted s e p a r a t e l y i n an e l e c t r i c t u b e f u r n a c e , a s shown i n
Fig.3. Combustion tests were conducted at a constant
t e m p e r a t u r e i n t h e r a n g e of 8 0 0 - 1 2 0 0 C and under a s t r e a m o f
a i r w i t h a s p e c i f i e d f l o w r a t e b e t w e e n 1.0 and 6 . 0 l i t r e / m i n .
The a s h was c o l l e c t e d a f t e r e a c h t e s t f o r s u l f u r a n a l y s i s . The
f u e l samples were c o m p l e t e l y burned, i . e . t h e r e was no r e t a i n e d
c a r b o n i n t h e a s h . The s u l f u r c a p t u r e e f f i c i e n c y , X, w a s t h e n
defined as follows:
A . S
X = . 100 (%) (17)
C . S,
Where A = w e i g h t o f a s h ( g m s ) ; S = s u l f u r c o n t e n t o f a s h ( w t . % ) ;
C = w e i g h t o f f u e l s a m p l e ( g m s ) a n d S^= s u l f u r c o n t e n t o f fuel
sample (wt.%).
4. RESULTS AND D I S C U S S I O N
4.1. Effect of Air Flowrate:
Two s e r i e s o f t e s t s w e r e c a r r i e d o u t a t a t e m p e r a t u r e o f a b o u t
900 C. The f i r s t was d o n e w i t h s a m p l e s o f C a / S m o l a r r a t i o = 1
and t h e o t h e r w i t h Ca/S m o l a r r a t i o = 3 . The r e s u l t s o f these
t e s t s a r e g i v e n i n F i g . 4 . I t i s c l e a r t h a t an i n c r e a s e i n t h e
a i r f l o w r a t e from 1 t o a b o u t 4 l i t r e / m i n l e a d s t o a n o t i c e a b l e
i n c r e a s e i n t h e s u l f u r r e t e n t i o n i n t h e a s h ( f r o m a b o u t 8% t o
385
Air i n l e t
Flow meter
Thermocouple
Electric furnace
combustion boat with sample
Dust c a t c h e r
Gas o u t l e t
Fig.3. Schematic diagram of t h e experimental apparatus.
100
80
60
CL

' L t d L i * C a / S molar ratio 3
C q / S molar ratio 1
( 40
20
_L
2 4
Air flowrate, litre/min.
F i g . 4 . E f f e c t o f a i r f l o w r a t e on S c a p t u r e
during the combustion t e s t s .
[ C a ( O H ) 2 s o r b e n t ; Temp.= 9 0 0 C]
386
24% w i t h C a / S = l a n d f r o m a b o u t 52% t o 73% w i t h C a / S = 3 ) . With

another increase in t h e a i r f l o w r a t e no d e t e c t a b l e e f f e c t on
the degree of sulfur capture could be n o t i c e d .
The n o t i c e d i n c r e a s e i n s o r p t i o n e f f i c i e n c y w i t h i n c r e a s i n g t h e
air flowrate can be attributed to the higher oxygen
concentration prevailing in the combustion zone. This would
tend t o enhance the r a t e of s u l f a t i o n r e a c t i o n ( r e a c t i o n 12),
which is consistent with equilibrium behaviour in CaS04
formation (eqn.14).
4.2. Amount a n d Type o f Ca-Based Sorbent:
Fuel-sorbent samples ( p e l l e t s ) of d i f f e r e n t Ca/S molar r a t i o s ,

in the range of 1/1 - 5/1, were heated at a constant
t e m p e r a t u r e o f a b o u t 900 C. I n t h e s e t e s t s , a constant air
f l o w r a t e of about 4 l i t r e / m i n was c o n d u c t e d . Four s e r i e s of
tests were c a r r i e d out under the same c o n d i t i o n s but with
d i f f e r e n t s o r b e n t t y p e s ( C a C O s , CaO, C a ( 0 H ) 2 a n d C a ( 0 H ) 2 +Mg0
mixture).
F i g . 5 shows t h a t i n t h e four s e r i e s of t e s t s s u l f u r sorption

i n c r e a s e s with i n c r e a s i n g t h e Ca/S r a t i o . This favorable effect
i s due t o t h e i n c r e a s e i n t h e s u r f a c e area of t h e s o r b e n t which
i s e x p o s e d t o SO2 p r o d u c e d i n t h e c o m b u s t i o n z o n e . U s i n g l o w e r
Ca/S r a t i o , t h e s u r f a c e area of t h e sorbent i n t h e combustion
z o n e w o u l d n o t b e e n o u g h f o r s c a v e n g i n g o f a l l SO2 produced.
T h i s l e a d s t o e s c a p i n g o f s o m e o f SO2 p r o d u c e d t o t h e b u l k g a s
stream without reacting with the sorbent.
A c c o r d i n g t o F i g . 5 , i t i s c l e a r t h a t Ca(0H)2 i s more effective

t h a n CaC03 a n d CaO, w h e n u s e d w i t h t h e s a m e C a / S m o l a r r a t i o .
The n o t i c e d d i f f e r e n c e b e t w e e n Ca(0H)2 a n d CaCOs could be
a t t r i b u t e d t o t h a t t h e f o r m a t i o n o f SO 2 s t a r t s a t a b o u t 5 0 0 C
( r e a c t i o n 5 ) , w h i l e d e c o m p o s i t i o n o f CaC03 o c c u r s a t a b o u t 9 0 0
C and d e h y d r a t i o n o f Ca(0H)2 a t a b o u t 500 C. For t h i s reason,
i n c a s e o f u s i n g CaCOs a s S O 2 - s o r b e n t , a h i g h e r a m o u n t o f SO2
would escape i n t o t h e bulk gas stream b e f o r e t h e b e g i n i n g of
sulfation (reaction 12). In addition, Ca(0H)2 consists of
smaller particles and produces calcine with larger pores
[ 1 , 1 6 ] . However, t h e h i g h e r s o r p t i v e c a p a c i t y o f Ca(0H)2 than
CaO c o u l d b e d u e t o t h e p o r o u s s t r u c t u r e o f t h e c a l c i n e d lime
particles (i.e. higher surface area) produced prior to
sulfation. Based on t h e e x p e r i m e n t a l f i n d i n g s o f Hartman and
Coughlin [5], the calcination reaction is essentially
i n s t a n t a n e o u s compared t o t h e s u l f a t i o n r e a c t i o n .
M i x i n g MgO p o w d e r w i t h C a ( 0 H ) 2 , i n p r o p o r t i o n s i m i l a r t o the
natural atmospheric hydrated dolomite, gave higher sorption
e f f i c i e n c y ( F i g . 5 ) . A l t h o u g h MgO, m o s t l y , d o e s n o t participate
in the sulfation reaction at high temperatures (see thermo
dynamic c o n s i d e r a t i o n s ) , i t s p r e s e n c e as f i n e l y d i s p e r s e d phase
in the sample maintains open p o r o s i t y in the calcined lime
d u r i n g s u l f a t i o n [ 1 7 ] . In a d d i t i o n , a s r e p o r t e d by S q u i r e [ 4 ] ,
Fig. 5. Effect of sorbent amount and type Fig. 6. Effect of heating temperature
on S capture during the combustion tests. on S capture during the combustion tests.
[Air flowrate =4 lit./min.; Temp.= 900 C] [Ca/S molar ratio =3 ; Air = 4 lit./min.]
387
388
p r e s e n c e of i r o n o x i d e ( m a i n l y produced from o x i d a t i o n of FeS)

c a t a l y s e s t h e r e a c t i o n o f MgO w i t h SOp a n d O2 t o f o r m MgSOî .
Iron oxide a l s o c a t a l y s e s the corresponding r e a c t i o n of CaO,
w h i c h i s f a s t e r . M o r e o v e r , p r e s e n c e o f MgO c r y s t a l l i t e s i n t h e
s a m p l e a r e c a t a l y t i c f o r s u l f a t i o n o f CaO.
4.3. Effect of Heating Temperature:
The e f f e c t o f h e a t i n g t e m p e r a t u r e , on t h e s o r p t i o n c a p a c i t y o f
t h e t e s t e d Ca-based s o r b e n t s , was s t u d i e d a t Ca/S molar ratio
of 3 and by u s i n g a s t r e a m of a i r w i t h a c o n s t a n t f l o w r a t e of
a b o u t 4 l i t r e / m i n . The h e a t i n g t e m p e r a t u r e s w e r e i n t h e r a n g e
o f 8 0 0 - 1 2 0 0 C. I n g e n e r a l , t h e o b t a i n e d r e s u l t s ( F i g . 6 ) showed
that the d e s u l f u r i z a t i o n a b i l i t y of the t e s t e d sorbents seems
t o be c o n s t a n t i n t h e t e m p e r a t u r e range of 800-1000 C and t h e n
a decrease in sulfur sorption i s noticed at temperatures above
a b o u t 1 0 0 0 C.
Comparing the sorption efficiency of the tested Ca-based

sorbents (Fig.6) showed t h a t a t t e m p e r a t u r e s v a r y i n g between
8 0 0 and 1 1 0 0 C, C a ( 0 H ) 2 gave greater d e s u l f u r i z a t i o n ability
t h a n C a C 0 3 a n d C a O , a n d t h a t o f CaO w a s h i g h e r t h a n C a C 0 3 .
These differences in sorptive capacities tapered off at
t e m p e r a t u r e s above a b o u t 1000 C and r e a c h t h e same v a l u e at
a b o u t 1 2 0 0 C. H o w e v e r , Ca(0H)2+MgO m i x t u r e o f f e r e d relatively
higher sorption efficiency t h a n Ca(0H)2 at all temperatures
t e s t e d (when u s e d w i t h t h e same Ca/S r a t i o ) .
The o b s e r v e d d i f f e r e n c e s in desulfurization abilities of the

d i f f e r e n t types of t e s t e d Ca-based sorbent in the temperature
r a n g e from 800 t o a b o u t 1000 C c o u l d b e a t t r i b u t e d t o t h e same
reasons discussed before (amount and type of Ca-based
sorbents). However, the decrease in sorptive capacity at
temperatures above about 1000 C c o u l d be due t o t h e lower
stability of CaSOa at high temperatures (see thermodynamic
considerations). This conclusion is in agreement with that
o b t a i n e d by Hartman and C o u g h l i n [ 5 ] . They o b s e r v e d t h a t the
s u l f a t i o n r e a c t i o n p r o c e e d s more r a p i d l y a t t e m p e r a t u r e s near
9 0 0 C; a t h i g h e r t e m p e r a t u r e s t h e r a t e o f r e a c t i o n i s l o w e r .
I t i s s e e n from F i g . 6 t h a t a t a h e a t i n g t e m p e r a t u r e of about
1 2 0 0 C t h e s u l f u r r e t e n t i o n i n t h e a s h w i t h Ca{OH)2+MgO m i x t u r e
was r e l a t i v e l y h i g h e r t h a n t h a t w i t h t h e o t h e r s o r b e n t s . This
c o u l d b e a t t r i b u t e d t o t h e n o t i c e d p a r t i a l s i n t e r i n g o f CaO a n d
MgO a t a b o u t 1 2 0 0 C , ( F i g s . 7 & 8 ) , l e a d i n g t o t h a t a c o n s i d e r a b l e
p o r t i o n of s u l f u r does not have enough time t o escape because
of the d i f f u s i o n r e s i s t a n c e and, h e n c e , was r e t a i n e d in the
ash. Squires [4] reported that with injection of dolomite
hydrate, for desulfurizing flue gases, c a l c i u m and magnesium
o x i d e s s i n t e r e d a t t e m p e r a t u r e s a b o v e a b o u t 1 1 5 0 C.
389
(b)
Fig.7. Retained ash after a combustion t e s t a t about 1200 C

of a sample c o n t a i n i n g Ca(0H)2 [Ca/S molar r a t i o = 3]
(a) Scanning e l e c t r o n image.
( b ) X - r a y a n a l y s i s (EDAX).
00 04 1 08
-4-
- t i u
S C F
G A
(b)
F i g . 8 . Retained ash a f t e r a combustion t e s t a t about 1200 C

of a sample c o n t a i n i n g Ca(0H)2+Mg0. [Ca/S molar r a t i o = 3]
(a) Scanning e l e c t r o n image.
( b ) X - r a y a n a l y s i s (EDAX).
390
5. CONCLUSIONS
During the combustion tests of pellets consisting of pure

c a r b o n , F e S a n d a C a - b a s e d s o r b e n t ( p u r e C a C 0 3 , CaO, C a ( 0 H ) 2 o r
a mixture of Ca(0H)2 +MgO), the following conclusions were
drawn:
l.An increase in the air flowrate leads t o a marked increase

i n t h e s u l f u r c a p t u r e by a s h u n t i l a l i m i t i n g v a l u e (about 4
l i t r e / m i n ) above which no d e t e c t i b l e e f f e c t c o u l d be noticed,
2.The e f f i c i e n c y of s u l f u r d i o x i d e adsorption i n c r e a s e s as the

amount of sorbent increases until a limiting value (Ca/S
molar r a t i o of about 4) above which no d e t e c t a b l e difference
could be observed.
3 . W i t h t h e same C a / S m o l a r r a t i o , Ca(0H)2 i s a more effective

sulfur dioxide capture agent than e i t h e r CaC03 and CaO.
H o w e v e r , CaO i s m o r e e f f e c t i v e t h a n C a C 0 3 .
4 . P r e s e n c e o f MgO a s f i n e l y d i s p e r s e d p h a s e in the samples

g i v e s Ca(0H)2 h i g h e r s o r p t i o n efficiency.
5 . The s o r p t i v e capacity of Ca-based sorbents seems to be

optimal in the temperature range of 800-1000 C. H o w e v e r , at
temperatures above about 1100 C adsorption of SO2 is
considerably decreased presumably due to dissociation of
CaS04.
6.Inspection of the retained ash after combustion t e s t s of

samples containing " C a ( 0 H ) 2 +MgO" s o r b e n t s u g g e s t s t h a t the
p a r t i a l s i n t e r i n g a t a b o u t 1 2 0 0 C may e x p l a i n t h e relatively
h i g h SO2 c a p t u r e , c o m p a r e d w i t h t h a t o f t h e o t h e r s o r b e n t s .
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92(1), 1970, pp.11.
16.M.R. Stouffer and H. Yoon, "An Investigation of CaO
S u l f a t i o n M e c h a n i s m s i n B o i l e r S o r b e n t I n j e c t i o n " , AIChE J . ,
V o l . 3 5 , N o . 8 , Aug. 1 9 8 9 , p p . 1 2 5 3 - 1 2 6 2 .
17.E.T. Turkdogan and R.G. Olsson, "Desulfurization of Hot
Reducing Gases with Calcined Dolomite", Ironmaking and
Steelmaking, No.4, 1978, pp.168-176.
M i l d T e m p e r a t u r e , F l u i d i z e d Bed G a s i f i c a t i o n o f Coal/Phosphoric
Acid Mixtures: P a r t i t i o n i n g Coal S u l f u r t o t h e G a s a s H^S
J.M. Stencel, J.K. Neathery, J.L. Schaefer and J . Yang
Center for Applied Energy Research, U n i v e r s i t y of Kentucky, 3572

I r o n W o r k s P i k e , L e x i n g t o n , KY 40511
1. ABSTRACT
The p r o c e s s i n g o f h i g h s u l f u r , I l l i n o i s b a s i n c o a l u s i n g
f l u i d i z e d bed mild temperature g a s i f i c a t i o n of coal/phosphoric
acid mixtures is described. I t i s p a r t o f an o v e r a l l coal
u t i l i z a t i o n p r o c e s s which can minimize the production of wastes
and m a x i m i z e t h e s y n t h e s i s o f v a l u e - a d d e d p r o d u c t s . Comparisons
of p r o d u c t s l a t e s and t h e e x t e n t o f d e s u l f u r i z a t i o n a s a
consequence of u s i n g t h e n o v e l p r o c e s s are compared t o
t r a d i t i o n a l l y practiced mild temperature g a s i f i c a t i o n .
I t i s shown t h a t h i g h s u l f u r c o a l can be d e s u l f u r i z e d a t
t e m p e r a t u r e s a s l o w a s 500C t h a t t h e s u l f u r p a r t i t i o n s t o t h e
g a s p h a s e a s H2S. P r o d u c t y i e l d s and t h e i r characteristics
important for application are discussed.
2. INTRODUCTION
The a n n u a l c o n s u m p t i o n o f c o a l i n t h e U n i t e d S t a t e s is
approximately one b i l l i o n t o n s . Over 1/2 of t h i s c o a l originates
from t h e e a s t o f t h e M i s s i s s i p p i R i v e r , a s i g n i f i c a n t amount of
which contains s u l f u r contents in e x c e s s of a l l o w a b l e l i m i t s for
m e e t i n g F e d e r a l r e g u l a t i o n s f o r SO2 e m i s s i o n s d u r i n g p o w e r
production. These r e g u l a t i o n s are the c o n t r o l l i n g factor
d i r e c t i n g i n d u s t r i a l i n v e s t m e n t i n power g e n e r a t i o n facilities,
t h e p r o d u c t i o n o f c o a l , and t h e d e v e l o p m e n t o f new p o w e r
generation technologies.
M i l d t e m p e r a t u r e ( i . e . < 800C) g a s i f i c a t i o n o f c o a l h a s
b e e n e x a m i n e d f o r o v e r 40 y e a r s i n an e f f o r t t o p r o d u c e v a l u e -
enhanced c h a r , t a r and g a s e o u s p r o d u c t s [ 1 ] . S t u d i e s b e f o r e 1975
c o n c e n t r a t e d on d e f i n i n g t h e d i s t r i b u t i o n and q u a l i t y o f t h e
h y d r o c a r b o n p r o d u c t s and on e n g i n e e r i n g a s p e c t s o f efficient
processing. More r e c e n t l y , m i l d t e m p e r a t u r e g a s i f i c a t i o n o f c o a l
has been examined for i t s a b i l i t y t o e f f e c t s u l f u r removal [2-6].
I t has been determined t h a t a low s u l f u r char cannot be produced
using t r a d i t i o n a l mild temperature f l u i d i z e d bed g a s i f i c a t i o n
(MTFBG) t e c h n o l o g y w i t h o u t c o m p l e x p r o c e s s i n g p r o t o c o l s .
T r a d i t i o n a l MTFBG d i s t r i b u t e s c o a l s u l f u r n o n s e l e c t i v e l y t o
t h e s o l i d , t a r and g a s e o u s p r o d u c t s , e a c h of w h i c h would r e q u i r e
additional treatment for meeting environmental and/or commercial
requirements [7-12]. F o r e x a m p l e . Khan [ 5 , 6 ) s h o w e d t h a t t h e
s u l f u r d i s t r i b u t i o n r e s u l t i n g f r o m g a s i f i c a t i o n o f 2 5 US c o a l s a t
500C c o u l d b e r e p r e s e n t e d b y :
T o t a l s u l f u r i n g a s = 0 . 3 1 S^^^^
T o t a l s u l f u r i n t a r = 0 . 0 6 S^^^^
T o t a l s u l f u r i n s o l i d = 0 . 6 1 S^^^^.
394
T h i s d i s t r i b u t i o n i s a f f e c t e d by f a c t o r s such a s c o a l t y p e ,
s u l f u r c o n t e n t and c h e m i c a l form, p a r t i c l e s i z e , h e a t i n g r a t e s ,
t e m p e r a t u r e , r e s i d e n c e t i m e and p r o c e s s configuration.
Comparisons o f s l o w and r a p i d h e a t i n g r a t e g a s i f i c a t i o n were
r e p o r t e d b y Khan [ 1 1 ] f o r I l l i n o i s , M o n t a n a , a n d O h i o c o a l s .
H e r e , t h e g a s , t a r and c h a r y i e l d s a t 500C v a r i e d b e t w e e n 6 - 1 3 %
( g a s ) , 3-25% ( t a r ) and 91-52% ( c h a r ) . The s u l f u r c o n t e n t o f t h e
t a r was r e l a t e d t o t h e t e m p e r a t u r e of t r e a t m e n t , with
c o n c e n t r a t i o n s n e a r 3.4% a t 650^C.
Various mild temperature g a s i f i c a t i o n processes have been
examined f o r t h e p r o d u c t i o n of l o w - s u l f u r s o l i d f u e l s from c o a l
[12]. A major c o n c l u s i o n was t h a t a c o m b i n a t i o n of s t a g e d
t r e a t m e n t s , i n c l u d i n g H2, s t e a m and p a r t i a l o x i d a t i o n a t
t e m p e r a t u r e s a s h i g h a s 600C w o u l d b e n e c e s s a r y t o d e c r e a s e t h e
s u l f u r c o n t e n t o f I l l i n o i s #6 b y 80%. The p o s s i b i l i t y o f
d e g r a d i n g or o x i d i z i n g t h e char and t h e n o n s p e c i f i c i t y i n s u l f u r
d i s t r i b u t i o n b e t w e e n t h e c h a r , t a r and g a s e s h a s p r e c l u d e d ,
however, commercialization of such p r o c e s s e s .
Another approach t o remove s u l f u r from c o a l i s catalytic
hydropyrolysis [13], Although c a t a l y t i c hydropyrolysis can
r e m o v e u p w a r d s o f 90% o f c o a l s u l f u r , t h e u s e H2 a n d a r e l a t i v e l y
e x p e n s i v e and n o n r e c o v e r a b l e c a t a l y s t i n c u r s h i g h c o s t s .
Similarly, other desulfurization techniques, including oxidative,
hydrothermal, microwave, hot c a u s t i c , flash desulfurization,
ammoniation, m e t a l o x i d e and c h l o r i d e i m p r e g n a t i o n , and h i g h
p r e s s u r e H2 p r o c e s s i n g h a v e n o t b e e n s u c c e s s f u l e c o n o m i c a l l y o r
in s e l e c t i v e l y d i s t r i b u t i n g coal s u l f u r t o a product which can be
easily treated.
One o f t h e p r i m a r y f a c t o r s a f f e c t i n g c o a l desulfurization
d u r i n g m i l d t e m p e r a t u r e g a s i f i c a t i o n i s t h e t y p e and c h e m i c a l
form o f t h e s u l f u r . Only r e c e n t l y has i t become p o s s i b l e t o
d e f i n e chemical forms of t h e o r g a n i c s u l f u r [ 1 4 - 1 8 ] . For t h e
r e l a t i v e l y f e w c o a l s t h a t h a v e b e e n e x a m i n e d , h i g h - s u l f u r , US
bituminous c o a l s have been determined t o contain approximately
30-70% o f t h e i r o r g a n i c s u l f u r i n t h i o p h e n i c f o r m s . Organic
s u l f u r i s n o t removed by p h y s i c a l c l e a n i n g and i s n o t r e a d i l y
d e c o m p o s e d d u r i n g MTFBG [ 1 9 ] .
A s a c o n s e q u e n c e , t h e r e a r e n o c o m m e r c i a l l y v i a b l e MTFBG
processes for the treatment of high sulfur c o a l . However, in t h e
c o u r s e of t r e a t i n g c o a l w i t h phosphoric a c i d m i x t u r e s i t was
discovered that s i g n i f i c a n t d e s u l f u r i z a t i o n could be induced
w h i l e s i m u l t a n e o u s l y p a r t i t i o n i n g t h e s u l f u r t o t h e g a s a s H2S
[20]. T h i s d i s c o v e r y h a s l e d t o p r o p o s i n g a t w o s t a g e MTFBG
process, the f i r s t stage of which uses temperatures in the range
o f 500C t o g a s i f y c o a l / p h o s p h o r i c a c i d m i x t u r e s . The f o l l o w i n g
p r e s e n t s our e x p e r i m e n t a t i o n and d i s c u s s e s i t and p r o d u c t
qualities relative to published information.
3. EXPERIMENTAL
3.1 MTFBG R e a c t o r
The e x p e r i m e n t a l program o r i g i n a l l y u s e d f i x e d b e d
e x p e r i m e n t a t i o n [21] and h a s p r o g r e s s e d t o u s i n g a b e n c h - s c a l e .
395
0 . 2 7 k g / h r c o n t i n u o u s f e e d MTFB g a s i f i e r s h o w n i n F i g u r e 1 . Near
future plans include a s c a l e - u p t o a 1.8 kg/hr u n i t .
Minus 20 mesh s i z e d c o a l was m i x e d w i t h r e a g e n t g r a d e ,
o r t h o p h o s p h o r i c a c i d (HjPO^) i n w e i g h t r a t i o s ( a c i d / c o a l ) between
0.5-1.0. These mixtures were dried at temperatures between 170-
2 1 0 C u n d e r a N2 p u r g e f o r t h r e e h o u r s , a n d u n d e r a v a c u u m f o r
two h o u r s . This d r i e d c o a l / a c i d f e e d mixture was p l a c e d i n t o t h e
p r e c i s i o n s c r e w f e e d e r , a n d e d u c t e d w i t h Ng g a s i n t o t h e b o t t o m
o f t h e 6 . 7 cm d i a m e t e r - b y - 1 0 6 cm h e i g h t f l u i d b e d g a s i f i e r .
F l u i d i z a t i o n g a s was metered i n t o t h e bottom of t h e g a s i f i e r such
t h a t t h e f l u i d i z a t i o n v e l o c i t y was between 0 . 1 5 - 0 . 2 0 m / s . The
residence time of the c o a l / c h a r within the g a s i f i e r using t h i s
v e l o c i t y was as small as f i v e s e c o n d s . The m o i s t u r e c o n t e n t o f
t h e f l u i d i z a t i o n g a s h a s b e e n v a r i e d b e t w e e n 0-87%.
D u r i n g t h e MTFBG e x p e r i m e n t s , t h e c h a r e x i t e d e i t h e r t h e t o p
of t h e r e a c t o r , where i t was c a p t u r e d by a h o t c y c l o n e , or t h e
bottom of the reactor v i a a v e r t i c a l stand-pipe. In the l a t t e r
case, the height of the stand-pipe above the bottom of the
g a s i f i e r was v a r i e d , t h e r e b y v a r y i n g t h e amount o f c h a r u n d e r
f l u i d i z a t i o n in the bed.
A 140 t a r c o l l e c t o r was l o c a t e d s u b s e q u e n t t o t h e c y c l o n e ,
a f t e r w h i c h w e r e p l a c e d 15C a n d i c e - b a t h c o o l e d c o n d e n s a t e
collectors. The n o n c o n d e n s i b l e g a s e s p a s s e d t h r o u g h a w e t - t e s t
meter at the e x i t of the r e a c t o r system.
3.2 Coals
To d a t e , up t o s i x I l l i n o i s b a s i n c o a l s h a v e b e e n t e s t e d ;
t h e p r o d u c t s l a t e s and t h e e x t e n t o f d e s u l f u r i z a t i o n w e r e s i m i l a r
for a l l of t h e s e c o a l s . The p r e s e n t p a p e r w i l l c o n c e n t r a t e on
one o f t h e s e c o a l s f o r which a more e x t e n s i v e d a t a b a s e i s
available. C h a r a c t e r i s t i c s of t h i s coal are presented in Table
1. I t h a s a h i g h s u l f u r c o n c e n t r a t i o n and a o r g a n i c / i n o r g a n i c
sulfur r a t i o of 0.6 before physical cleaning.
Table 1. Analyses of I l l i n o i s basin c o a l s subjected to mild

t e m p e r a t u r e g a s i f i c a t i o n , b e f o r e and a f t e r physical cleaning.
ROM Cleaned
Measurement Indiana #5 I n d i a n a #5
Proximate:
Moisture 6.2 3.5
Ash 7.2 4.9
Voltiles 38.4 41.5
Fixed C 48.3 52.6
Ultimate:
Carbon 69.3 75.4
Hydrogen 5.5 5.4
Nitrogen 1.5 1.6
Sulfur 3.4 2.9
Org S / T o t a l S 0.6 0.7
HHV ( k J / k g ) 28,783 31,012
396
Figure 1. Schematic of the CAER 3-inch Fluidized Bed
Reactor Unit (with water cooled nozzle) .
397
To e x a m i n e t h e e f f e c t s o f p h y s i c a l c l e a n i n g o n
d e s u l f u r i z a t i o n and on t h e q u l i t y o f t h e p r o d u c t s p r o d u c e d d u r i n g
MTFBG o f c o a l / a c i d m i x t u r e s , t h e c o a l w a s s u b j e c t e d t o c o l u m n
f l o t a t i o n cleaning before mixing with phosphoric acid. I t was
w e t g r o u n d t o - 2 00 mesh and p r o c e s s e d w i t h i n t h e K e n f l o t e c o l u m n
technology. I t w a s s u b s e q u e n t l y vacuum d r i e d a t 100C f o r t h r e e
hours; i t s c h a r a c t e r i s t i c s are presented in Table 1.
4. R E S U L T S AND D I S C U S S I O N
As n o t e d i n T a b l e 1, column f l o t a t i o n c l e a n i n g removed
a p p r o x i m a t e l y 15% o f t h e s u l f u r f r o m I n d i a n a # 5 . Primarily,
p y r i t i c s u l f u r was removed, and a s a c o n s e q u e n c e , t h e r a t i o -
(organic s u l f u r ) / ( t o t a l sulfur) - increased to 0.7. The h e a t i n g
v a l u e o f t h e c o a l w a s i n c r e a s e d b y n e a r l y 8% b y t h e p h y s i c a l
cleaning.
T h e r e s u l t s f r o m MTFBG t e s t i n g w i l l b e c o m p a r e d a n d
d i s c u s s e d r e l a t i v e t o d a t a o b t a i n e d from f i x e d bed t e s t i n g o f t h e
same c o a l .
T a b l e 2 d i s p l a y s d a t a from t h r e e c h a r s w h i c h w e r e p r o d u c e d
d u r i n g t h e MTFBG o f m i x t u r e s o f p h o s p h o r i c a c i d w i t h t h e
p h y s i c a l l y cleaned Indiana #5. The v a r i a b l e i n v e s t i g a t e d d u r i n g
t h e s e t e s t s was t h e m o i s t u r e c o n t e n t of t h e f l u i d i z i n g g a s .
The d a t a i n T a b l e 2 show t h a t t h e s u l f u r c o n c e n t r a t i o n o f
the cyclone char increased as the moisture content of the
f l u i d i z a t i o n g a s was i n c r e a s e d . A l t h o u g h t h i s c h a n g e may b e a
function of the type of phosphorus s p e c i e s in the coal during
gasification (see below), i t is also possible that the residence
t i m e of t h e c o a l / c h a r w i t h i n t h e f l u i d i z e d bed was an i m p o r t a n t
factor.
Table 2. Analyses of cyclone catch chars from 500 gasification

of Indiana #5/acid mixtures.
Moisture Content (%)

Measurement 0 13 87
Proximate:
Moisture 2.5 1.5 1.4
Ash 12.2 12.5 13.4
Voltiles 24.4 23.6 25.5
Fixed C 60.9 62.4 59.6
Ultimate:
Carbon 73.8 76.1 73.9
Hydrogen 2.4 2.7 3.2
Nitrogen 1.6 1.5 1.6
Sulfur 0.9 1.0 1.2
Org S / T o t a l S 0.9 0.9 0.9
HHV ( k J / k g ) 27,530 28,412 29,387
The f l u i d i z a t i o n v e l o c i t y was c h o s e n such t h a t i t would be

s l i g h t l y greater than t h e minimum f l u i d i z a t i o n v e l o c i t y f o r t h e
398
coal. H o w e v e r , i n t h e 100% N2 t e s t s , t h e a v e r a g e g a s v e l o c i t y
w a s 0 . 1 5 m / s , w h e r e a s i n t h e 13% N 2 / 8 7 % s t e a m t e s t s t h e a v e r a g e
g a s v e l o c i t y was 0.2 m / s . A l t h o u g h t h i s d i f f e r e n c e may s e e m
i n s i g n i f i c a n t , t h e amount o f c h a r t h a t was c a p t u r e d i n t h e
c y c l o n e - v e r s u s - t h e amount o f c h a r c a p t u r e d u n d e r b e d v a r i e d
s i g n i f i c a n t l y with small changes in the gas fluidization
velocity. For example, t h e w e i g h t r a t i o of t h e c y c l o n e c a t c h - t o -
underbed c a t c h was 1.3 w i t h a 0.15 m/s g a s v e l o c i t y , whereas t h e
same r a t i o was 1 0 . 0 w i t h a 0 . 2 m/s g a s v e l o c i t y . Hence, the
overall residence time of the coal/char in the g a s i f i e r i s a
s e n s i t i v e function of gas v e l o c i t y for the samples under
investigation.
Another i n d i c a t i o n of t h e importance of r e s i d e n c e t i m e was
t h e amount o f d e s u l f u r i z a t i o n . Even though t h e a v e r a g e r e s i d e n c e
t i m e was s m a l l and b e t w e e n 5-7 s e c o n d s , t h e s u l f u r c o n t e n t i n t h e
c h a r c o l l e c t e d u n d e r b e d f o r t h e 100% N2 c a s e w a s 0 . 7 % , i . e . 20%
l e s s than the value l i s t e d in Table 2 for the cyclone catch. The
underbed char would be expected t o have a l o n g e r r e s i d e n c e time
in t h e g a s i f i e r and, as a r e s u l t , have a lower s u l f u r
concentration. F o r t h e 0 . 7 % s u l f u r c h a r , n e a r l y 76% o f t h e
s u l f u r was removed from t h e p h y s i c a l l y c l e a n e d c o a l d u r i n g t h e
5 0 0 C MTFBG p r o c e s s i n g ; n e a r l y 80% o f t h e s u l f u r w a s r e m o v e d
from t h e p a r e n t c o a l c o n s i d e r i n g t h a t i t had a s u l f u r c o n t e n t o f
3.4%. On a b a s i s o f SO2 e m i s s i o n s , t h e u n d e r b e d c h a r w o u l d
p r o d u c e a n SO2 e m i s s i o n e q u i v a l e n t o f 0 . 5 1 g / M J , a v a l u e l e s s
t h a n US r e g u l a t o r y e m i s s i o n r e q u i r e m e n t s o f 0 . 5 2 g / M J .
Y i e l d s o f c h a r , c o n d e n s a t e and g a s e o u s p r o d u c t s , calculated
as a weight r a t i o of product-to-feed, are presented in Table 3.
Increasing the concentration of steam increased the gasification
of t h e coal and, concommitantly, decreased t h e y i e l d of char. In
a l l c a s e s , t h e y i e l d of t h e c o n d e n s a t e ( i . e . o i l or t a r ) was
s m a l l a n d n e a r 1%. Most of t h e s u l f u r r e l e a s e d from t h e c o a l was
Table 3. D i s t r i b u t i o n of products from t h e MTFBG o f Indiana

#5/phosphoric acid mixtures.
%
Fluidization Gas Char Oil/Tar Gas
100% N2 79 ~1 20
8 3% N 2 / 1 7 % Steam 64 -1 35
17% N 2 / 8 3 % Steam 49 --I 50
in the gas phase. In comparison t o p r e v i o u s f i x e d bed

e x p e r i m e n t a t i o n [ 2 1 ] , i t i s a n t i c i p a t e d t h a t t h i s s u l f u r was i n
t h e form o f H2S.
The c h a r y i e l d s f a l l w i t h i n a r a n g e o f p u b l i s h e d v a l u e s
(15). However, t h e y i e l d s o f c o n d e n s a t e and g a s a r e c o m p l e t e l y
d i f f e r e n t t h a n t h a t o b s e r v e d i n t r a d i t i o n a l l y p r a c t i c e d MTFBG o f
coal. Evidently, the phosphoric acid promotes the production of
l i g h t h y d r o c a r b o n s from t h e carbon w h i l e r e t a i n i n g , and p o s s i b l y
causing, c r o s s l i n k i n g of the v o l a t i l e components in the c o a l .
399
The t y p e o f t h e p h o s p h o r u s s p e c i e s c a u s i n g t h e s e s e t o f reactions
i s n o t known.
The s p e c i f i c i t y f o r r e m o v i n g c o a l s u l f u r a t s u c h l o w
temperatures has not been previously observed, although as early
a s 1 9 7 2 [ 2 2 ] i t w a s o b s e r v e d t h a t u p t o 50% o f t h e s u l f u r i n
b i t u m i n o u s c o a l c o u l d be removed by p h o s p h o r i c a c i d t r e a t m e n t .
I t i s w e l l known [ 2 3 ] t h a t h e a t i n g o f o r t h o p h o s p h o r i c a c i d c a u s e s
t h e t r a n s f o r m a t i o n from o r t h o >pyro >meta ( p o l y ) s p e c i e s and
i n v o l v e s t h e l o s s of w a t e r and c o n d e n s a t i o n , a s i n :
,, > ,, > ( , ) .
^ ^ -20(230 4 2 7 -H20(375oC) ^ 3'
H e a t i n g o f coal/H^PO^ m i x t u r e s t o 170C c a n b e a c c o m p l i s h e d
o n l y a f t e r e x c e s s H2O i s e v a p o r a t e d . At 170C, t h e p r e d o m i n a n t
p h o s p h o r u s s p e c i e s w o u l d b e HjPO^; a t temperatures of 230-375C
t h e a c i d w i l l b e c o m e c o n c e n t r a t e d i n ^2^; and, a t temperatures
n e a r a n d a b o v e 3 7 5 , t h e m e t a o r p o l y p h o s p h o r i c a c i d (HPO3)
s p e c i e s w i l l become dominant. Condensed phosphates e x h i b i t
i n s t a b i l i t y t o h y d r o l y s i s , a n d a r e s o l u b l e i n H2O t o v a r i a b l e
degrees. Hence, a s i g n i f i c a n t amount o f t h e p h o s p h o r u s can be
r e c o v e r e d from t h e c h a r . However, t h e form o f t h e p h o s p h o r i c
a c i d d u r i n g t h e 500C g a s i f i c a t i o n i s n o t known s i n c e a c o m p l e x
s e t of r e a c t i o n s i n v o l v i n g t h e a c i d and c o a l m a t r i x a r e e x p e c t e d
to occur. These r e a c t i o n s include dehydration, aromatization,
d e h y d r o g e n a t i o n , and c o n d e n s a t i o n . The i m p o r t a n c e o f t h e a c i d i c
p r o t o n i n t h e a c i d i s a l s o n o t known.
I t i s p o s s i b l e t h a t an a c t i v e o r m i x t u r e o f a c t i v e forms o f
the acid i n i t i a t e s sulfur removal. In our f i x e d bed experiments
i t was o b s e r v e d t h a t d e h y d r o g e n a t i o n and a r o m a t i z a t i o n o f t h e
coal occured during the r e l a t i v e l y extended reaction times of
n e a r l y two h o u r s .
5. CONCLUSIONS
The u s e o f p h o s p h o r i c a c i d / c o a l m i x t u r e s d u r i n g m i l d
t e m p e r a t u r e g a s i f i c a t i o n may e n h a n c e t h e e n v i r o n m e n t a l a n d
economic a s p e c t s of u t i l i z i n g high s u l f u r c o a l . Heretofore
unknown s e l e c t i v i t y f o r c o a l d e s u l f u r i z a t i o n and p r o d u c t i o n o f
H2S a t r e l a t i v e l y l o w t e m p e r a t u r e s n e a r 5 0 0 C h a v e b e e n s h o w n .
The c o a l d e s u l f u r i z a t i o n r a t e was r a p i d , and t h e p r o d u c t i o n o f
o i l s / t a r s was minimized under t h e f l u i d i z e d bed g a s i f i c a t i o n
conditions. F u r t h e r work i s n e c e s s a r y t o u n d e r s t a n d t h e r e a c t i o n
mechanisms t h a t l e a d t o t h e d e s u l f u r i z a t i o n and p r o d u c t
selectivity.
ACKNOWLEDGEMENTS
T h i s work was s u p p o r t e d , i n p a r t , by t h e I l l i n o i s Coal

Development Board through t h e I l l i n o i s Clean Coal I n s t i t u t e .
S p e c i a l t h a n k s t o D r ' s . B.K. P a r e k h and J . Groppo f o r p e r f o r m i n g
the physical cleaning of the coal.
400
BIBLIOGRAPHY
1) Chemistry of Coal U t i l i z a t i o n , a. Supplementary Volume I ,

H.H. Lowry, E d . , 1 9 6 3 , pp. 4 3 6 - 4 3 7 ; and b . Supplementary Volume
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York).
2) H . F . F e l d m a n , J.A. Mima a n d P . M . Yarvorsky, Adv. Chem. Ser.,

131(1974) 108.
3) P . T . F a l l o n , B . L . B h a t t a n d M. Steinberg, Fuel Process.

Technol., 3(1980) 155.
4) R. Cypres and S. Furfari, Fuel, 61(1982) 447.
5) M. R. K h a n , ACS R e p r i n t , Div. Fuel Chem., Vol. 33, No 1,

(1988) 253.
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Fuel Chem., Vol 3 3 , No 1 ( 1 9 8 8 ) 2 6 5 .
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Fuel Chem., Vol 3 3 , No. 1 (1988) 2 7 4 .
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G.L. C l a u s e n , 2nd I n t n ' l Conf. on P r o c e s s i n g and U t i l . o f High
S u l f u r Coal, ( E l s e v i e r S e i . Publ. C o . , 1987) pp. 1 9 2 - 2 0 1 .
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70(1991) 1091.
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2051-2), f i n a l report January 1987.
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Energy & F u e l s , 5(1991) 582.
1 4 ) W.H. C a l k i n s , " D e t e r m i n a t i o n o f o r g a n i c sulfur-containing

s t r u c t u r e s i n c o a l b y f l a s h p y r o l y s i s e x p e r i m e n t s " , ACS r e p r i n t s ,
D i v o f F u e l Chem. V o l 30 ( 1 9 8 5 ) .
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945.
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F. Lu, E n e r g y & F u e l s , 5 ( 1 9 9 1 ) 574.
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401
18) R.B. LaCount, R.R. Anderson, S. Friedman and B.D. B l a u s t e i n ,

P r e p r . P a p . - A m . Chem. S o c . , D i v . F u e l Chem. 3 1 ( 1 9 8 6 ) 70.
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Production of Value-Enhanced Products f r o m C o a l " , US P a t e n t ,
pending.
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J . M . S t e n c e l , D . T a u l b e e a n d M.W. T h w a i t e s , A C S , Fuel Div. Prep.
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T e c h n o l o g y , 3 r d E d i t i o n , V o l . 17 (John W i l e y & S o n s , NY), pp 426-
472.
High sulfur coal burning industrial boilers using Pedco's rotary

cascading bed combustion technology
W.H. Long
Pedco Incorporated
11464 Lippelman Road
Cincinnati. OH 45246
BACKGROUND
Pedco Incorporated is an engineering firm with major experience in the design,

modification, construction and operation of industrial plants including their associated
energy and environmental control systems. This includes the development of
processes as well as the scale up of client processes from the developmental to the
commercial stage.
Pedco was founded in 1967 and, since that time, has gone through a number of
changes. In order to meet the growing environmental concerns in the early 1970's,
Pedco founded and supported Pedco Environmental, a division which grew into a
major environmental engineering firm, providing a broad menu of services to the EPA
and a number of industrial and governmental organizations. Pedco Environmental
continues to provide these services as a part of the IT Corporation. Pedco also started
and spun off successful firms in the architectural and computer services fields.
In addition to its work for well over 200 major corporate clients, many of whom
were repeat customers, Pedco has successfully managed a number of projects for
the State of Ohio, the United States Department of Energy, the United States
Environmental Protection Agency and the Appalachian Regional Commission.
Pedco has developed its own proprietary technology, the Pedco Rotary
Cascading Bed Combustion System, which has been granted United States Patents
4,583,468 and 4,724,777. Patents for this technology have also been issued covering
countries in Europe, the Far East, and the rest of North and South America. Work on
this technology has been underway since 1981 and was solely supported by Pedco
until 1985, when the Ohio Department of Energy became a partner in a project to
speed the development of the technology, particularly in its application to the clean
combustion of high sulfur coals.
This support was furnished by the Ohio Goal Development Office, a Department
of Development successor to the Department of Energy. This support was based on
early experimental data demonstrating the ability of the technology to burn high sulfur
404
and waste coals cleanly, removing the sulfur dioxide by co-feeding the fuels with
limestone.
Since the initial grant by the Ohio Department of Development in 1985, Pedco has
been joined by a growing group of public and private participants, working together
to develop and test, not only the technology, but the systems needed to provide
environmentally sound, cost effective and complementary solutions to complex
problems in industrial energy, coal utilization and waste management that are
confronting industry and government today.
Pedco's objective is the development of worldwide applications in economic and
clean energy production for the Pedco Rotary Cascading Bed Combustion
Technology.
ROTARY CASCADING BED COMBUSTION CONCEPT
The Pedco Rotary Caascading Bed Combustion Technology is a unique and

innovative combination of well known and tested mechanical principles coupled with
chemical process concepts to provide an almost optimum atmosphere for the
combustion process and for the enhancement of acidic gas capture by inexpensive
sorbents.
The basic features of the combustion system are contained in the rotating
cylinder which is, in effect, a chemical reactor designed to provide the almost optimum
conditions for combustion and for beneficial reactions such as the conversion of acidic
gases to inorganic compounds. These conditions are obtained by (1) rotating the
cylinder at a speed sufficient to cause cascading across the entire diameter, which
provides excellent mixing of the fuel, the combustion air, the sorbent and the bed
material and (2) recirculation, internally, of the bed material, following the transfer of
heat to the boiler tubes, to the feed end of the cylinder. Figure 1 shows the effect of
the speed of rotation on cascading. An optimum speed of rotation is that which
produces approximately 50% of the force of gravity. Figure 2 illustrates the interior
flow of solids. Figure 3 is an artist concept of the combustion system.
The warm solids, after surrendering a portion of their heat to the internal tube
bundle are returned, via an internal chute in the form of an Archimedian screw, from
the boiler zone to the feed end of the combustion chamber at a rate of 40 to 100
times the fuel feed rate. This provides for preheating of the incoming fuel and
combustion air. It further serves to control the combustion zone temperature by
surrounding each particle of burning fuel with many times its mass of cooler bed
material. By this technique the combustion zone temperature is controlled to a range
of 1600 to 1650 ""F which limits the formation of the oxides of nitrogen and promotes
the chemical reactions which capture the acidic gases.
405
Intermediate speed Optimum speed

Speed too low Speed too tiigh
Some cascading Maximum cascading
No cascading No cascading
(Kiln Action) No movement of solids
Figure 1. Effect of Rotational Speed on Cascading
S o l i d s fIow Over
Fuel
F
Air and Turndown
Bo i 1 e r Tubes
< 1
Figure 2. Internal Solids Circulation
This recirculation of solids at high rates means that the ratio of fuel to solids in
the combustion chamber at any given time is quite low. It assures that refractory fuels
may make several passes through the combustion zone and that the sorbent is given
multiple opportunities to react with the acidic gases.
406
J

":"
^^^^^^^ il''''I^^^^B
Figure 3. Artists Concept of the Pedco Rotary Cascading Bed Combustion System
The sorbent, used to control sulfur dioxide and other acidic gases, is limestone
in the form of discarded screenings (3/8 " minus). These screenings are co-fed with
the coal. Calcium carbonate in the limestone is calcined to calcium oxide in the
combustion chamber. The calcium oxide combines with the sulfur dioxide to form
calcium sulfate, with hydrogen chloride to form calcium chloride and with other acidic
gases.
In addition to the limestone and the fuel ash, sand is used to assure that a bed
of approximately 10% of the volume of the cylinder is constantly in place. This bed
serves to control the temperature, as described previously, and as a "thermal flywheel"
to conserve and transfer heat. The bed Is heated by the combustion of the fuel in the
combustion zone, carried down the length of the cylinder due to its slope and
surrenders some of its thermal energy to the boiler tubes in the heat transfer zone.
The flow of hot solids from the combustion zone over the internal tube bundle is
controlled by an internal control device, which allows for startup and for a good
turndown ratio.
The combustion gases leaving the rotating cylinder pass over external heat
exchangers which cool them to approximately 300 F before they are exhausted to a
mechanical dust collector and finally a baghouse.
407
DEMONSTRATION AND TEST PROGRAMS
. Pedco Bench Scale Model

In 1981 a 16" diameter 48" long bench scale model was built in the Pedco Model
Shop. This small test unit was cantilevered and could be rotated fast enough to
assure cascading over the entire diameter. A number of different materials were
burned in this device. It was worthy of note that even in this small combustion zone,
it was possible to obtain an 85% reduction of sulfur dioxide from high sulfur coal.
It also demonstrated the capability of the technology to burn such materials as
Eastern oil shale, paint sludges, petroleum sludges as well as coal.
These results were interesting enough to capture the imagination of a waste
disposal firm to the extent that they agreed to finance and operate a prototype
incinerator.
B. Incinerator
The test burn incinerator was built in 1983 and operated through 1984 and 1985.
It was specifically designed for burning low heating value, high moisture-containing
wastes with the intention of making benchmark test burns of a number of industrial
wastes.
This prototype incinerator was 18 feet in length with an inside diameter of 28 inches.
Along its length the first ten feet from the feed end were the combustion zone. The
next four feet included the "heat recovery and solids reheat" zones and the last four
feet constituted an "air preheat" zone.
When burning materials which did not have sufficient heating value to burn
autogeneously, natural gas was used as an auxiliary fuel and cooling water was used
as an adjunct to control the combustion zone temperature.
The materials tested varied widely in physical and chemical characteristics. They
included:
Still bottoms from the distillation of halogenated organics
Biological wastewater treatment sludges
Oil refinery sludges
Acrylic/styrene copolymer reactor washouts
Contaminated soils
High sulfur coals
In these tests, the addition of limestone achieved over 99.5% removal of HCl and
sulfur dioxide removal as high as 99.8%.
The demonstration of this capability of removal of sulfur dioxide impressed the
Ohio Coal Development Office which agreed to co-sponsor the demonstration of a
prototype industrial boiler.
C. Ohio Test Program

Incorporating boiler tubes in the combustion chamber of the Pedco Rotary
Cacading Combustion System had been planned since the earliest conception of the
408
technology and the idea of using the system for steam generation included in the
patent.
In 1985 a Grant Agreement was concluded between Pedco and the Goal
Development Office of the Ohio Department of Development. This Agreement covered
the design, fabrication, installation and operation of a demonstration boiler defined as:
"A commercial scale facility demonstration, within Ohio, of technology which will
reduce sulfur emissions from Ohio-produced coal in an efficient, environmentally
acceptable and timely manner."
Hudepohl Brewing Gompany at their plant in downtown Gincinnati agreed to act
as host and as operator of the demonstration boiler which was sized to produce
steam at the level required when the plant was not brewing or bottling. This was
desireable for Hudepohl since their existing boilers could not comply with EPA
emission limits when operated at the low demand levels required for approximately
three to four days per week.
The Rotary Cascading Bed Boiler was built to provide the 5,000 pounds per hour
of 150 psi steam required for the specified conditions and was installed in space
cleared where an obsolete boiler was removed.
The approximate specifications for the demonstration boiler are given in Table 1.
Table 1
Internal Diameter (feet) 5.5

Overall Length (feet) 25.0
Maximum Design Temperature (F) 1650
Rotary Speed (RPM) 16
Initial Heat Transfer Area (sq. ft.) 376
Final Heat Transfer Area (sq. ft.) 207
Information from the earlier incinerator tests had shown that the Type 309
stainless steel used for the hot parts in that device was not adequate for long term
use in a chloride-sulfur environment. After a study of alternative materials, it was
decided to fabricate all hot parts from a "micro-alloyed", high temperature alloy,
RA253MA. Also, for future design confirmation, it was decided to install a number of
test coupons of stainless steel alloys including: 309, 310, 336 and 330 to check their
behavior when subject to the temperature, the chloride-sulfur environment and the
sliding and falling abrasive bed materials.
The inner liner, lifters and internal solids transfer chutes were fabricated of the
RA253MA. The inner liner was supported from the outer, cool, carbon steel structural
shell by a series of concentric rings where the dynamic and dead loads were
409
transferred to the outer shell through a series of tapered (hot to cool) tangential struts.
The approximate four inch annular space between the outer shell and the inner liner
was packed with ceramic wool insulation.
The combustor assembly was supported on two steel tires mounted fore and aft
on the outer shell normal to the axis of the combustor. Each of the tires was
supported by steel trunnions. Lateral axial forces were absorbed by two horizontal
thrust rollers, mounted on the rear trunnion block.
The combustor was driven through a large chain sprocket attached to the outer shell
midway between the two tires. A saddle drive chain engaged the large sprocket at the
bottom. The chain loop was driven by a hydraulic motor, the speed of which was
regulated by modulating the hydraulic fluid flow through a remote pump and reservoir.
Originally there were thirty-six two inch boiler tubes, with the boiler water supplied
through 3/8 inch bayonet tubes. The tube bundle rotated with the combustion
chamber with the water fed and steam extracted through a Johnson rotary seal.
During the early test series, it became apparent that the original heat transfer area
was substantially above that necessary and, ultimately, the number of boiler tubes was
reduced to eighteen.
Combustion gases leaving the combustor were passed through an economizer
and through an air preheater to lower the temperature to the desired 300 F before
entering the baghouse.
Fuel and limestone flows were controlled by weigh belt feeders from independent
bunkers before mixing in a common hopper and chute for gravity feeding into the
boiler.
A continuous monitoring system capable of reading and recording sulfur dioxide,
oxides of nitrogen, carbon dioxide, carbon monoxide and oxygen was installed and
in service during all operations.
Coal and limestone were provided by a number of Ohio producers. Table 2 gives
the range of demonstration coal characteristics.
Table 2
Ash (% by weight) 7.97 to 27.6

Sulfur (% by weight) 2.10 to 5.60
HHV (Btu/lb) 9,592 to 12,324
In all, during the 13 specific test runs, some 1,400 hours of operation on high
sulfur coal were accumulated.
The most important results were in the area of emission control. After a study of
all runs, it was concluded that after steady state conditions were reached, a Ca/S ratio
410
of 1.2 was sufficient to cause a reduction of 90% in sulfur dioxide emission over the
range of sulfur tested. On the most representative run, the Ca/S ratio was held at 1.3
for 24 hours with a resulting sulfur dioxide emission rate of 0.2 pounds per million Btu.
The relatively low combustion zone temperatures were largely responsible for
limiting the formation of NOx. The observed average value over the series of tests
was approximately 0.2 pounds per million Btu of fuel input.
The baghouse provided excellent control of the overhead particulates, which
constituted approximately 70% of all ash leaving the system. The baghouse was
equipped with Nomex bags which provided for almost 100% capture of all particles
greater than 1 micron in size. Flyash size distribution measurements showed that
99.04% of the particles were above 44 microns in size.
Evaluation of the test coupons clearly indicated the superiority of RA253MA over
the other steels tested. Photomicrographs of sections of the liner and lifter materials
revealed little or no alteration of the crystal structure and physical inspection did not
indicate any substantive effects of erosion or corrosion.
The test series had to be terminated prior to the planned completion since the
Hudepohl firm was merged with another local brewery and all activities were
transferred to the other plant.
D. Tennessee Program
Following the termination of the test work at the Hudepohl Brewery in Cincinnati,
Pedco entered a period of redesign incorporating features identified as desireable
during the program into projected modifications of the demonstration boiler.
In addition, a search was initiated for a new host location for the completion of the
projected test series.
A tentative location was found in the PMC Specialty Group, Inc. chemical plant
in Cincinnati. The requirements in this location called for a boiler to furnish 10,000
pounds per hour at 150 psi steam pressure with 100 degrees of superheat.
The design work incorporated the changes to make the boiler suitable for PMC,
as well as those modifications previously identified. As a result the following
modifications were made in the Hudepohl demonstration boiler:
(1) The capacity was increased from 5,000 pound per hour of steam to 10,000.
(2) The rotating boiler tubes were replaced by a compact, cantilevered fixed
boiler inserted from the rear.
(3) The internal lifters and recycle chutes were modified to incorporate the new
boiler and a solids flow control device to route the hot solids back to the feed
end without passing them over the boiler for startup and maximum turndown
or to allow some or all of them to cascade over the boiler tubes.
(4) External recycle systems for the fly and bottom ash were added.
(5) An external superheater, evaporator and economizer were incorporated into
a single unit which replaced the previous economizer and air preheater.
(6) The boiler was mounted on a permanent steel frame along with as many
components as possible to simplify the installation.
(7) Eventually, a mechanical separator was added ahead of the baghouse.
411
Difficulties in getting permits for any new equipment installation in the PMC facility
ultimately caused the boiler to be located at the North American Rayon Corporation
plant in Elizabethton, Tennessee.
The North American Rayon plant was built in the 1920's. It is the last fine filament
rayon plant in the United States. The plant powerhouse is equipped with ten boilers
burning 400 tons of coal per day. The plant is capable of producing 24 megawatts
of electricity and 400,000 pounds of process steam per hour.
The North American interest in the Rotary Cascading Bed Boiler was due to the
fact that management realized that the current plant could not meet Clean Air Act
requirements without major changes. Further, one of their major manufacturing
expenses is the cost of fuel. They were aware of the Pedco technology and its ability
to burn high sulfur coal as well as other potentially inexpensive fuels cleanly within the
proposed Clean Air Act limits. Therefore, they agreed to act as host and operator of
the modified demonstration boiler for the proposed continuing test series.
Modifications were completed by September 30, 1990 and the boiler shipped by
truck to Elizabethton, Tennessee where the foundations of the test building had been
poured. The boiler was installed and the building completed around it and tests were
initiated on December 17, 1990.
Photographs of the installation are included on the next three pages in Figures
4, 5, 6, and 7.
Figure 4. RCBB Test Facility Adjacent to NAR Powerhouse

412
Figure 5. RCBB Combustion CInamber and Internal Boiler

413
Figure 6. External Superheater, Economizer and Evaporator
In all, during the approximately 2,000 hours of official operations, over thirty three
different fuels and fuel combinations were tested and in all cases gaseous and
particulate emissions were well within the limits imposed by the Tennessee permit
which were as strict, if not more so, than the Clean Air Act requirements.
In the case of high sulfur and waste coals, samples were obtained from Ohio,
Tennessee, Virginia and Kentucky. All of these were burned alone and in some cases
were co-fired with various other materials.
414
Figure 7. Control Panels and Data Recorder
Table 3 summarizes the tests during 1991 and 1992. It includes coal, coal wastes,
biomass, industrial wastes and municipal wastes. In most cases the emission rates are
based on three hour rolling averages.
Emission data on all runs was recorded, at five minute intervals, on a PC and
analyzed by personnel from the Center for Electric Power, Tennessee Technological
University. All analyses of the fuel materials were made by the Western Kentucky
University Coal Laboratory.
The average range of sulfur dioxide emissions for the high sulfur coal tests, after
operating procedures and calibration techniques were fully established, was from 0.31
to 0.43 pounds per million Btu of fuel input. The sorbent used was simple limestone
screenings with a calcium carbonate content ranging from 80 to 85%. The average
calcium to sulfur ratio for the high sulfur coal tests was 1.3.
The average emission rate of NOx over the high sulfur coal tests after the
operating procedures and calibration techniques were fully established average was
0.09 pounds per million Btu of fuel input.
The average particulate emission rate was measured in an official stack test using
EPA method 5. The measured emission rate was 0.04 pounds per million Btu versus
a permitted rate of 0.52 pounds per million Btu.
415
Table 3
Fuel Characteristics Emissions
HHV Ash Sulfur Nitrogen SO2 NO,

Fuel Btu/lb % % % Ibs/MMBtu
HIGH SULFUR COALS

NARC coal 12.582 9.74 1.73 1.39 0.32 0.09
Royal Fuel 9.847 26.20 4.15 1.18 0.93 0.02
Garland Coal 9.639 26.45 3.68 1.05 1.02 0.10
Ohio Valley 7.376 40.82 3.93 0.78 0.43 0.02
Ohio Valley (Washed) 12.572 10.75 4.02 1.19 0.11 0.06
Ohio Waterloo 10,793 16.22 3.68 0.94 0.30 0.15
J&C Coal 11.797 15.19 3.20 1.66 0.60 0.63
Bottom 11.858 15.03 6.77 1.16 0.24 0.08
COAL WASTES
Anthracite Culm 6.978 42.87 0.83 0.78 0.22 0.14
Ponded Fines 8.117 19.18 2.54 0.88 0.38 0.04
BIOMASS
Treated Wood 7.498 0.76 0.02 2.76 0.02 0.20
Treated Wood 7.715 0.49 0.02 1.87 0.03 0.09
INDUSTRIAL WASTES
Rubber & Coal 14.749 6.37 1.61 0.62 0.05 0.14
Rubber 16.252 4.06 0.92 0.01 0.70 0.34
Coal Tar 14.698 2.35 0.68 1.02 0.08 0.08
Movie Film 9,311 0.15 0.12 1.48 0.24 0.05
Carpet(60% coal) 10,459 14.45 0.76 5.48 0.27 0.51
Carpet(80% coal) 11,635 8.46 0.32 8.21 0.16 0.41
Carpet 8.684 14.11 0.46 5.25 0.03 0.58
MUNICIPAL WASTES
RDF # 1 7.256 8.50 0.12 0.22 0.16 0.07
RDF # 2 7.256 8.50 0.12 0.22 0.29 0.07
RDF # 3 8.238 10.41 0.76 0.23 0.27 0.06
RDF & Coal 7.925 8.76 0.77 0.54 0.03 0.07
RDF "Fluff" 6.562 7.09 0.06 0.20 0.02 0.07
Hydrolyzed RDF and coal 6.236 6.57 1.23 0.59 0.63 0.10
416
A test for HCl was made because of the provisions of Title III, Air Toxics, in the
Clean Air Act. This test was made using RDF with a chlorine content of 1,826 parts
per million. The test was conducted using the test protocol in EPA method 26. The
results showed that the HCl, if any, was below the limits of detectability.
Dravo, in its capacity as a prime contractor to the Ohio Coal Development Office
for fluidized bed combustion by-products study, received two drums of fly ash from
the coal runs. The flyash showed a Calcium Carbonate Equivalent (CCE) or Total
Neutralizing Power (PNP) of 58 with a pH of 12.6. The conclusion drawn from this is
that the flyash from the Rotary Cascading Bed Boiler has potential as a liming
substitute and can be of substantial benefit in the reclamation of strip mined areas or
for the treatment of other acidic soils.
The overall conclusion of the test series, as reported to the Ohio Coal
Development Office, is that the Pedco Rotary Cascading Bed Combustion Technology
can burn high sulfur and waste coals either as the sole fuel or in combination with a
wide variety of waste materials, economically, and in full compliance with the Clean Air
Act. This ability to cleanly burn low cost and even negative cost fuels will help
industry compete, both domestically and internationally, while meeting the stricter
standards imposed by the Clean Air Act.
PROJECTED APPLICATIONS
The primary market for the Pedco Rotary Cascading Bed Boiler is for factory built,
over-the-road transportable, industrial units in the general capacity range of 60,000
pounds of steam per hour.
Installations currently in the detailed planning stage cover a wide variation of
steam conditions and total energy output ranging from (1) an eight boiler co-
generation installation at the North American Rayon plant to (2) a single process
steam unit at a carpet mill:
(1) The eight boiler installation at the North American Rayon Corporation plant
in Elizabethton, Tennessee. The basic fuel for this plant will be high sulfur
and waste coals. These will be co-fired with combustible wastes from the
surrounding region. Steam will be produced at 850 psi and 825 degrees F.
It will be used in a topping turbine and several low pressure turbines before
being sent to the plant processes at 14 psi. This installation will be able to
provide up to 400,000 pounds of process steam per hour as well as up to 24
megawatts of electricity.
(2) The single 60,000 pound per hour carpet mill boiler will produce process
steam at 250 psi using high sulfur and waste coal as the basic fuel
supplemented by plant waste and carpet returned by distributors for
disposition. This single plant installation will be replicated at other of the
same companies plants.
A number of similar applications are under study in several states for various
industrial clients.
417
Also, an effort is underway with several major industrial firms to install modules
based on the Pedco technology, at a number of appropriate geographical locations,
to provide inexpensive industrial energy derived from high sulfur and waste coals and
from co-fired spent products such as tires, other rubber products such as hoses and
belts, carpets and film as well as regionally available unmarketable paper, plastic and
wood scrap.
F o r m a t i o n of a n d N2O in t h e f l u i d i z e d - b e d
c o m b u s t i o n of high- and l o w - r a n k coals
Brian G. Young, Michael D. Mann, and Michael E. Gollings
Energy & Environmental Research Genter, University of North Dakota,

Grand Forks, North Dakota 58202
ABSTRACT
Fluidized-bed combustion (FBC) of coal is a technology which affords the

opportunity for significant reduction of sulfur emissions from burning coal due to the
incorporation of lime as a sorbent material. However, during the FBC of coal, nitrogen
is released as oxides of nitrogen, both (nitric oxide and nitrogen dioxide
combined) and N p (nitrous oxide). As well as being a greenhouse gas, N2O, like
, also interferes with the ozone chemistry in the upper atmosphere. Typically, in
FBC systems, as the level is lowered by utilizing lower-temperature regimes, the
N2O level is correspondingly increased.
This paper will describe a pilot plant investigation of the emission behavior of oxides
of nitrogen from the combustion of seven coals, ranging from bituminous to lignite,
including high-sulfur coals. The coals were burned in a 1-MWth circulating FBC over
the temperature range of 730 to 930G, excess air of 0% to 100%, superficial velocity
of 3.6 to 7.0 m/s, and coal particle size of 125 to 500 microns. Continuous in situ
monitoring of O2, GO, GO2, , and N2O was conducted. A chemiluminescence
technique was used for , whereas N2O was detected by a nondispersive infrared
analyzer.
Nitrous oxide emissions are influenced most by the nature of the coal, with
bituminous coals giving the highest emissions and subbituminous coals the lowest.
Temperature is the next most influential parameter on emission levels-the higher the
temperature, the lower the emission. Typical N2O emissions range from 10 to
180 ppm.
Nitric oxide emissions, on the other hand, show the reverse trend with respect to
temperature. The level of typically ranges from 50 to 250 ppm. Goal type and
temperature are also both influential factors in generation.
420
Other factors influencing the formation of and NjO will also be discussed, along
with possible mitigating factors for controlling the emissions. One interesting feature
is the role of sulfur in the N2O-NOX chemistry, with respect to sorbent interaction.
The interrelation between N2O and formation presents some difficulties and
challenges in selecting procedures to minimize the level of nitrogen oxides.
1. INTRODUCTION
Emission standards have been made more stringent with the passage of time.
Control of (NO, NO2), NjO, SO2, and CO is, therefore, an important consideration
when utilizing coal as a fuel source. Fluidized-bed combustion (FBC) offers an
alternative for utilizing coal in an environmentally sound manner. Adopting proper
selection of operating conditions, it is possible to reduce any one of these gases to
very low levels; however, a combined emission strategy is more difficult. Increasing
sorbent feed rate to reduce SO2 will cause an increase in . Changes in
temperature, excess air, and other parameters can likewise be used to reduce the
level of one or more pollutants, while increasing another. It is, therefore, important to
consider the impacts of the entire system when making changes in order to minimize
the total amount of emissions from the FBC.
Information presented in this paper was correlated as part of a study of nitrous

oxide (N2O) emissions from FBC. Data gathered during the initial phase of the project
indicate that coal properties and operating temperatures probably have the greatest
impact on the amount of NjO formed during combustion. Other operating parameters
are considered to have a minimal impact on N2O emissions. is strongly affected
by temperature and primary air split and moderately affected by excess air level and
limestone feed rate. SO2 is most strongly influenced by limestone feed rate and
temperature.
Our work, as well as a number of other studies, has shown an interaction between
sulfur sorbents and nitrogen oxides. This paper will, therefore, focus on emissions of
, N2O, and SO2 and the interactions that occur between limestone and these
gases. A potential combined emission control strategy will be suggested for a high-
sulfur coal.
2. EXPERIMENTATION
Parametric testing has been undertaken at the Energy & Environmental Research
Center (EERC) in a 1-MWth pilot-scale circulating fluidized-bed combustor (CFBC).
The test rig, having an internal diameter of 51 cm and a height of 12.8 m, contains a
series of refractory-lined sections bolted together. Its operating conditions are a
temperature range of TSU"" to 925C, excess air of 0% to 100%, superficial gas velocity
of 3.6 to 7.0 m/s, and a coal size of 125 to 500 microns. The system is
421
comprehensively described elsewhere [1]. Continuous in situ monitoring of O2, CO,

CO2, SO2, , and N2O was performed; in particular, N2O was analyzed by a
nondispersive infrared spectrometer (NDIR). A previously established [2, 3] sampling
protocol for N2O analysis was used to minimize cross interferences from other
gaseous species.
Coals tested at the EERC included two lignites (one from Asia and one from North
Dakota), one subbituminous coal (Black Thunder), and two bituminous coals (Salt
Creek and Blacksville). The properties of the coals are listed in Table 1. In total, 75
separate test conditions are represented by the data presented in this paper.
3. RESULTS
The coals were chosen from a wide range of geographical formations and ranks
(Table 1). The partitioning of the coal nitrogen into the volatile matter and the char is
also presented in Table 1. The char was produced at 950C using the standard
ASTM proximate analysis technique for determining volatile matter. The significance
of the distribution of nitrogen in the volatile matter and char is related to the reaction
pathway in which fuel-bound nitrogen is converted to N2O. The non-matrix-bound
nitrogen released with the volatile matter is free to react through homogeneous or
heterogeneous reaction pathways to form nitrogen or nitrogen oxides (NO, NO2, N2O).
Matrix-bound char nitrogen will produce nitrogen oxides through heterogeneous
oxidation reactions, but is believed to be a minor contributor to N2O formation [4].
The char nitrogen can also devolatilize and react through gas-phase mechanisms.
3.1. SO2 Emissions and Limestone Utilization
A comparison of sulfur emissions and sorbent performance is presented in Table 2.

Sorbent performance is addressed as a function of sulfur capture, ranging from 70%
to 95%. The amount of sulfur capture is mainly determined by the total alkali-to-sulfur
ratio. Total alkali is provided by the inherent alkali (mineral matter and cations
contained within the coal) and by the added alkali supplied by sorbent addition. For
all of the tests, limestone was the sorbent that was used to supply added alkali in the
form of calcium.
Figure 1 shows the added alkali-to-sulfur ratio required for 70%, 90%, and 95%
sulfur capture for the various coals tested. To retain 90% of the sulfur present in the
coal, the required alkali-to-sulfur ratio ranged from 1.4 to 4.9, depending upon the coal
type. However, looking only at the alkali-to-sulfur ratio is misleading. For example,
although an alkali-to-sulfur ratio of 4.9 is required to meet 90% sulfur retention for the
Salt Creek coal versus 1.4 for the Asian lignite, the total amount of sorbent addition
required is much less for the Salt Creek coal. A sorbent add rate of 1805.7 ng/J
~
N
N
Table 1
1
Analysis of coals tested
Coal: Asian Center Black Thunder Salt Creek Blacksville
Rank: Lignite Lignite Subbit. C HVC Bit. HVA Bit.
Location: Asia North Dakota Wyoming Colorado Pennsylvania
Proximate analysis, as-received, wtk

Moisture 17.03 37.26 27.57 7.65 2.37
Volatile matter, VM 37.40 28.76 33.23 31.04 36.40
Fixed carbon, FC 7.60 28.85 34.60 42.74 52.86
Ash 38.03 5.12 4.59 18.58 8.51
FC/VM ratio 0.20 1.00 1.04 1.38 1.45
Ultimate analysis, as-received, wt%
Carbon 24.98 40.95 49.85 58.82 74.47
Hydrogen 4.25 6.98 6.61 4.98 5.21
Nitrogen 0.65 0.53 0.62 1.15 1.36
Sulfur 6.05 0.58 0.31 0.48 2.46
Oxygen 26.10 45.74 37.99 16.02 7.98
Ash 38.03 5.12 4.59 18.58 8.51
Nitrogen distribution,2 wt% of total N
Volatile matter, Nv 88 25 27 43 36
Char, Nc 12 75 73 57 64
Heating value, as-received, MJ/kg
HHV 10.90 16.24 20.08 23.85 30.94
1 All proximate, ultimate, and heating values are a result of averaging several samples for each coal.
2 Nitrogen was measured in coal and in char prepared according to ASTM proximate analysis specifications. Nitrogen in volatile
matter was determined by difference.
423
Table 2
Comparison of sulfur emissions and sorbent performance
Coal: Asian Center Black Thunder Salt Creek Blacksville
Total sulfur, % 5.9 0.58 0.3 0.45 2.4

Inherent alkali/sulfur ratio 0.63 0.9 2.1 0.3 0.1
Inherent sulfur capture, % 70 23 3 2 14
Inherent alkali utilization, % 112 26 1.4 3 64
Optimum temperature for
sulfur capture, "C 852 746 791 827 832
70% Sulfur capture
Test number -J CL5 BT5 SC3 BV15

Added Ca/S ..' 1.1 2.1 2.1 1.6
__1
Added sorbent,^ ng/J 1848.7 1074.8 1289.8 4213.3
Utilization, % 39 31 36 43
90% Sulfur capture
TL1 _j BT2 soil BV2

Test number
Added Ca/S 1.4 2.5 4.9 2.3
Added sorbent, ng/J 26,956.3 1289.8 1805.7 6706.8
Utilization, % 63 31 19 39
95% Sulfur capture
Test number CL8 BT8 SC9 BV13

Added Ca/S 2.3 2.6 5.7 2.9
Added sorbent, ng/J 3353.4 1418.8 3052.5 8297.5
Utilization, % J 35 37 17 32
' No tests were performed at 843* and a corresponding sulfur capture.

' Nanograms sorbent added per Joule coal input.
of Salt Creek coal input is required versus 26,655.3 ng/J of Asian lignite, due to
differences in the levels of sulfur and alkali in the coal. Figure 2 presents the required
limestone addition rates in relation to varying levels of sulfur capture for the five coals
tested.
The coal properties that most affect the required amount of added alkali are total
sulfur and inherent alkali present in the coal (indicated in Table 2 by the inherent alkali-
to-sulfur ratio). Some generalizations on expected sulfur capture behavior as it relates
to coal properties can be made, based upon the testing performed. As the sulfur
content of the coal increases, more limestone will be required, but utilization of the
available calcium in the limestone will be higher due to the higher driving force
supplied by the greater concentration of SO2 in the combustor. The combination of
a low-sulfur coal and a low inherent alkali-to-sulfur ratio will require sorbent addition
at a low feed rate, but because of the diminished driving force within the combustor
due to low SO2 concentrations, the additional alkali-to-sulfur ratio required will be high.
For a given amount of sulfur in the coal, as the inherent alkali-to-sulfur ratio increases,
less added limestone will be required due to the increased capture of sulfur by the
alkali inherent to the coal ash. Overall calcium utilization as a function of added
calcium-to-sulfur ratio is shown in Figure 3.
424
C No. AH07941-041-S
7
70% Sulfur Retention
6H 1 90% Sulfur Retention
O 4
Asian Center Black Thunder Salt Creek Blacksville
Coal Type
Figure 1. Added alkali-to-sulfur ratio required for increasing sulfur capture at ~843'*C
as a function of coal type.
EERC No. MMOBOS?
30,000
26,95
6
6,707
,
3 . 3 53 3 . 0 53
1 0 7 5 1 . 2 9 0 1 .94 1 1 , 2 9 0 ^ ^
A
Asian Center Black Thunder Salt Creek Blacksville
Coal Type
Figure 2. Added limestone required for increasing sulfur capture at -843''C as a

function of coal type.
425
EERC No. AHO 7945-041-S

80
Salt Creek
Center

60 Blacksville
o
c Black Thunder
g *
Asian
40

O 20
- ' \ ' \ '

1 2 3
Added Calcium-to-Sulfur Molar Ratio
Figure 3. Calcium utilizatiori as a function of added calcium-to-sulfur ratio.
3.2 Nitrogen Oxide Emissions
Regulated nitrogen oxide emissions currently include NO and NO2, collectively

termed emissions. emissions from the CFBC are highly coal-dependent.
Table 3 summarizes nitrogen emissions data for all five of the coals tested. Figure 4
compares emissions for the five test coals as a function of temperature. Not only
does the total amount of emitted vary with coal type, the rate at which the
emissions increase when temperature increases also varies with coal type. The rate
of change is the smallest with the lignites and the greatest with the bituminous coals.
Therefore, the lignites are higher emitters of than the bituminous coals at lower
temperatures (790C), but emit less at higher temperatures. emissions also
increase with increasing excess air and sorbent addition rates.
Figure 5 compares emissions as a function of excess air for four different coals
(no excess air tests were performed during the Asian lignite run). In all cases,
emissions increased with increasing amounts of excess air. Figure 6, showing
emissions as a function of primary-to-secondary air split, illustrates a typical trend on
how the staging of combustion air affects emissions. Secondary air is introduced
at about 1.7 m above the distributor plate level. As the percentage of the total
combustion air supplied through the distributor plate increased, increasing the amount
of oxygen in the bottom of the combustor, the emissions correspondingly
increased. The effect of increasing limestone addition on emissions is shown in
Figure 7. With the exception of the Black Thunder subbituminous coal, nitrogen oxide
emissions increased with increasing limestone feed rates for the various ranks of coals
tested.
426
Table 3
Nitrogen emissions
Black
Coal: Asian Center Thunder Salt C r e e k Blacksville
Fuel nitrogen
as-received, % 0.7 0.5 0.6 1.2 1.3
ng/J 593.3 326.7 309.6 481.5 438.5
Baseline case, no limestone
Test number TL4 CLO BT1 SCI BV1
Average combustor temperature, C 851 830 857 875 848
Emissions, p p m
105 141 248 142 121
NÔ 81 48 25 150 168
+ NÔ 186 189 273 292 289
Emissions, n g / J
64.5 86.0 137.6 81.7 64.5
NÔ 47.3 25.8 12.9 81.7 90.3
+ NÔ 111.8 111.8 150.5 163.4 154.8
C o n v e r s i o n of fuel n i t r o g e n , %
3.45 7.23 14.05 4.84 3.87
NÔ 5.29 4.90 2.83 10.20 11.91
+ NÔ 8.74 12.13 16.88 15.04 15.78
Full l o a d , 9 0 % s u l f u r c a p t u r e
Test n u m b e r TL1 CL1 BT2 sen BV2
Average combustor temperature, C 852 846 842 807 840
Emissions, p p m
130 202 189 56 94
NÔ 59 22 44 223 145
+ NÔ 189 224 233 279 239
Emissions, n g / J
77.4 116.1 103.2 124.7 47.3
NÔ 34.4 12.9 25.8 124.7 68.8
+ NÔ 111.8 129.0 129.0 249.4 116.1
C o n v e r s i o n of fuel nitrogen, %
4.24 10.26 10.73 2.10 3.23
N2O 3.84 2.25 4.63 16.40 10.28
+ NÔ 8.08 12.51 15.36 18.50 13.51
427
EERC NO.
300
Salt Crtttk
250 Center
A
Blacksville
o
@ 200 Black Thunder
,
Asian
( 150
100

O 50
700 750 800 850 900 950

Average Combustor Temperature, C
Figure 4. emissions in ppm at 2 0 % - 2 5 % excess air, 4.9-m/s velocity, and

1.5-2.5 alkali-to-sulfur ratio as a function of combustor temperature.
EERC No. MMoaOSO
300
0^250
200
SaH Creek
o.
^ 150 Center
A
Blacksville
o
Black Thunder
50
20 40 60 80 100
Excess Air, %
Figure 5. emissions at '-843C (884C for Salt Creek) as a function of excess

air.
428
EERC No. MhêOCI

140
Test BV4
120
Velocity = 5.6 m/s
O"
100 Test BV2
@
Velocity = 4.8 m/s
80 Test BV7
( Velocity = 4.2 m/s

C
.2 60

40
20
, \ ^ 1 ^ 1 < 1
45 50 55 60 65 70 75
Primary-to-Secondary Air Split
Figure 6. emissions for Blacksville coal at ~843G and 20% excess air as a
function of primary-to-secondary air split.
EERC No. 0902
260
Salt Creek
240
o%ao
@ 200 H

Q. 180
(
I
160
I 140
120 +
100
80 - \ - - 1
10 15 20 25 30 35
Limestone Feed Rate, mg/J coal
Figure 7. emissions at ~843C (877C for Salt Creek), 4.9-m/s velocity, and 25%
excess air as a function of limestone feed rate.
429
New analytical techniques have recently made it possible to measure flue gas
nitrous oxide (N2O) levels. N2O emissions from pulverized coal-fired systems are
typically less than 10 ppm, while those from FBCs range from 25 to 150 ppm for most
fuels on full-scale units. Although N2O emissions are currently not regulated, they may
become important in the future. The trends noted during this study were increasing
emissions of N2O as the rank changed from subbituminous to lignite to bituminous.
Similar trends have been noted on full-scale units. However, the N2O emissions from
full-scale systems are lower than those measured from the pilot scale. Figure 8
compares data from the EERC pilot plant with data from the 100-MWe CFBC at the
former Colorado Ute Nuda Station while burning the same fuel and sorbent. This has
been attributed to increased wall effects inherent to small-scale systems. N2O
emissions are even more dependent on fuel properties than emissions are.
N2O emissions follow a trend opposite that of , decreasing with increasing

temperature (Figure 9), and a trend similar to that of for excess air (Figure 10).
No clear relationship between N2O emissions and primary-to-secondary air split was
evident from the results of testing. A strong interaction exists between N2O emissions
and temperature and excess air. Temperature has a stronger effect on N2O emissions
at lower excess air levels, while excess air has a much stronger effect on NO2
emissions at lower temperatures.
Figure 11 shows N2O emissions as a function of limestone feed rate. N2O

emissions decrease with increasing limestone feed rate for all coals except the Black
Thunder. Most data from other researchers show a similar trend of decreasing NjO
as the sorbent feed rate increases [5-8]. Data from some full-scale units have shown
no trend of N2O with limestone feed rate [9, 10], while a few reveal an increase in N2O
with limestone feed rate [11]. N2O emissions can change with limestone feed rate due
to heterogeneous decomposition with CaO; heterogeneous formation with NO, NH3,
O2, and CaO, and heterogeneous formation through CaSOp and NO. mand and
others (12) have also shown an interaction with SO2, causing high-sulfur coals or low
limestone feed rate cases to have higher N2O emissions. The complex chemistry
affecting the relationship between NjO and limestone feed rate undoubtedly is affected
by the level of nitrogen, sulfur, voltiles, char, and ash in the coal, as well as the
constituents of the ash. An excellent review is given by Hayhurst and Lawrence [13].
The percent conversion of fuel-bound nitrogen to and N2O is illustrated in

Figure 12. For the calculations, it is assumed that only the fuel-bound nitrogen is
converted and that nitrogen introduced with the combustion air is not converted at the
comparatively low operational temperature typical in CFBCs. Total nitrogen oxide
emissions tend to increase as the rank of the coal increases.
N2O emissions tend to decrease with increasing temperature, while increases

with increasing temperature, independent of coal rank. No apparent consistent trend
exists for total nitrogen oxide emissions, plus N2O, as a function of average
430
EERC No. 063

500
EERC High Excess Air
EERC - Low Excess Air

O 400 -|
Nuda High Excess Air
o
@ Nuda - Low Excess Air

300
200
> 100
700 750 800 850 900 950

Figure 8. A comparison of nitrous oxide emissions from the 10-MWe Colorado Ute
CFBC and the EERC pilot plant while utilizing the same coal and limestone.
300 EERC No. 064
Salt Creek
o
250 Blacksville
-
Black Thunder
A
() 200 Asian

. Center
150
o
I 100
O
50
700 750 800 850 900 950

Figure 9. N2O emissions as a function of average combustor temperature, at 4.9-m/s

velocity and 21%-34% excess air.
431
EERC No. Mioses

350
Salt Creek
300 Center
CM
O
803'C Blacksville
^ 250
Black Thunder
i. 200
Q.
g 150
884'C
m 100
O
^ 50
'
20 40 60 80 100
Excess Air, %
Figure 10. N2O emissions at ~843**C (except as noted) as a function of excess air.
EERC No. Mhmooe

200
Salt Creek

Center
O
150 Blacksville
CO .
Black Thunder
Q. Asian
100
O 50
CM

10 15 20 25 30 35
Limestone Feed Rate, mg/J coal
Figure 11. N2O emissions as a function of sorbent add rate at '-843C, 4.9-m/s
velocity, and 21%-34% excess air.
432
EltCNo.AH0nSKH1-S
20
Blacksville Salt Creek S Black Thunder
16.9
Center Asian
15.8
>
15
2 14.1
.tf
11.9 12.1
C
10.2
8
10
m
7.2 ;
LL
C
5
'{2 3.5
\ XI
. NO. + 2
Figure 12. Percent conversion of fuel-bound nitrogen to and N j O at ~ 8 4 3 C ,

4.9-nn/s velocity, and 2 1 % - 3 4 % excess air as a function of coal type.
combustion temperature for the different ranks of coals tested, as shown in Figure 13.
However, it does appear that the total nitrogen oxide emissions do increase with coal
rank.
3.3 Carbon Monoxide Emissions
Carbon monoxide (CO) emissions are the result of incomplete conversion of the
coal carbon to carbon dioxide. CO emissions tend to decrease with increasing
temperature for all ranks of coal (Figure 14). CO emissions also decrease as excess
air increases for all ranks of coal tested. Both of these conditions, higher
temperatures and higher concentrations of oxygen, favor more complete conversion
of the coal carbon to carbon dioxide.
4. CONTROL STRATEGIES
A potential control strategy is proposed for the Blacksville bituminous coal. Since
the operating parameters have been shown to interact with the fuel, this quantitative
analysis cannot directly be extended to include other coals. Table 4 shows the effect
of changing parameters relative to a reference nominal base condition of 2 5 % excess
air, 843C combustor temperature, and 9 0 % sulfur retention by coal ash and sorbent.
Since N2O is the most difficult to control in a postcombustion mode, efforts were made
to minimize N2O by varying operating conditions, while attempting to keep other
emissions at a reasonable level.
433
EERC No. MM0B907

350
Salt Creek
300 Center
t A
CO Blacksville
250 -
Black Thunder
w 200 Asian
.1
O
100
+
o" 50
0
700 750 800 850 900 950
Figure 13. Total nitrogen oxide emissions at 4.9-m/s velocity and 17%-31% excess
air as a function of average combustor temperature.
EERC No.
250
Salt Creek

O Center
o 200
Blacksville
- -
Black Thunder
+
150 Asian
100
I
8 50
700 750 800 850 900 950

Figure 14. CO emissions at 4.9-m/s velocity and 17%-31% excess air as a function
of average combustor temperature.
434
Table 4
Example of control strategy based on data from CFBC test utilizing Blacksville
bituminous coal
Decrease Increase Use
excess Increase sorbent ammonia Change
Base air temperature feed injection from base
Temperature, C 843 843 899 899 899 . ..
E x c e s s air, % 25 10 10 10 10 . ..
C a / S , molar ratio 2.1 2.1 2.1 2.6 2.6 . ..
SO2, ppm 500 550 750 500 500 0%
CO, p p m 95 110 65 65 65 -32%
, p p m 120 55 130 135 60 -50%
N2O, ppm 145 130 60 53 70 -52%
C o m b , efficiency, % 94 93 95 95 95 1%
A decrease in the excess air level from the base case reduces the NjO and
while causing a slight increase in SO2 and CO. An increase in temperature will further
reduce N2O and will serve to keep CO at reasonable levels. Both SO2 and will be
adversely affected by an increase in temperature. To bring SO2 back into compliance,
limestone feed rate is increased. This action causes a slight decrease in N2O and an
increase in . Finally, ammonia (NH3) addition can be used to bring down the
level with only a slight increase in NjO. The final result is a 5 2 % decrease in N2O, 5 0 %
decrease in , 3 2 % decrease in CO, while still maintaining SO2 at 9 0 % retention.
Combustion efficiency increased by 1%. Care must be taken when developing a
control strategy to keep within design limits and economic constraints.
A more detailed discussion of these operating data on N2O emissions has been
presented previously [14-16]. Actual operating data can be obtained from the authors.
5. CONCLUSIONS
The capture of sulfur released during coal combustion is largely controlled by the
total alkali-to-sulfur ratio. Total sulfur and inherent alkali in the coal essentially
determines the amount of added alkali required. For a specific sulfur content, less
limestone addition is required as the inherent alkali-to-sulfur ratio rises.
The rate of emission with temperature is lowest with lignites and highest with
bituminous coals. At lower temperatures, lignites are higher emitters of than
bituminous coals, but lignites emit less at higher temperatures. Increasing the
435
excess air, sorbent additive rates, and primary-to-secondary air split increases
emissions.
Nitrous oxide emissions decrease with increasing temperature but follow a trend
similar to that of for excess air. The impact of temperature on N2O emissions is
stronger at lower excess air levels, but the effect of excess air is greater at lower
temperatures. Except for one coal. Black Thunder subbituminous, N2O emissions
decrease with increasing limestone feed rate for all coals. The interaction between
N2O emissions and limestone feed rate is complex and is influenced by the level of
nitrogen, sulfur, voltiles, char, and ash in the coal, as well as by the ash components.
No consistent trend is noted for total emission of nitrogen oxides with average
combustion temperature for the different ranks of coals. C O emissions decrease with
increasing temperature and increasing excess air with all ranks of coal.
Applying a control strategy to Blacksville bituminous coal for limiting , N2O, SO2,
and C O would involve the following: decreasing the excess air level, increasing the
combustion temperature slightly, and adding limestone and NH3.
REFERENCES
1. Henderson, A.K.; Moe, T.A.; Hajicek, D.R.; Mann, M.D. "Design and Operation of
the EERC Pilot-Scale Circulating Fluidized-Bed Combustor," In Proceedings of the
Sixteenth Biennial Low-Rank Fuels Symposium; 1991, pp 407-420.
2. Montgomery, T.A.; Samuelsen, G.S.; Muzio, L.J. JAPCA 1991, 39, 721.
3. Collings, M.C; Weber, G.F.; Mann, M.D. "N2O Measurement in Coal-Fired Flue
Gas," In Proceedings of the Seventh Annual Coal Presentation, Utilization, and
Environmental Control Contractors Conference; 1991.
4. Kramlich, J . C ; Cole, J.A.; McCarthy, J.M.; Lanier, W.S.; McSorley, J.A.

Combustion and Flame 1989, 77, 375.
5. Yasunaga, K.; Furusawa, T. In Proceedings of the 51st Annual Meeting of the

Chemical Engineers Society; Japan, 1986, 417.
6. Hulgaard, .; Glarborg, P.; Dam-Johansen, K. \n Eleventti International Conference

on Fluidized Bed Combustion; Anthony, E.J., Ed.; American Society of Mechanical
Engineers: New York, 1991; pp 991-998.
7. Kilpinen, P.; Hupa, M. Combust. Flame 1991, 85, 94.

436
8. Duo, W.; Dam-Johansen, K.; 0stergaard, K. In Twenty-Third Symposium

(International) an Combustion; The Combustion Institute: Pittsburgh, 1990;
pp 297-303.
9. Brown, R.A.; Muzio, L. "N2O Emissions from Fluidized-Bed Combustion," In

Proceedings of the Eleventh International Conference on Fluidized Bed
Combustion; 1991; pp 719-724.
10. Cabrita, I.; Costa, M.R.; Esparterio, H.; Gulyurtlu, I. "Determination of Overall Fuel-
N Balance during Fluidized Bed Coal Combustion," In Proceedings of the Eleventh
International Fluidized Bed Combustion Conference; May 1991, pp 985-990.
11. lisa. .; Santala, ; Hupa, . "Formation of Nitrous Oxide from Ammonia on Lime
Surfaces," In Proceedings of the Eleventh International Conference on Fluidized
Bed Combustion; May 1991, pp 1027-1034.
12. mand, L ; Leckner, B.; Dam-Johansen, K. "Influence of SO2 on the NO/N2O

Chemistry in Fluidized Bed Combustion," Fuel 1993, 72 (4), 557.
13. Hayhurst, A.N.; Lawrence, A.D. "Emissions of Nitrous Oxide from Combustion
Sources," Prog. Energy Combust. Sei. 1992, 18, 529-552.
14. Mann, M.D.; Collings, M.C; Young, B.C.; Botros, P.E. "Predicting N2O Emissions
from Circulating Fluidized-Bed Coal Combustion," In Proceedings of the Pittsburgh
Coal Conference; 1992, pp 1006-1011.
15. Mann, M.D.; Collings, M.C; Botros, P.E. "Nitrous Oxide Emissions: Review of
Fundamental Chemistry and Combustion Testing," Prog. Energy Combust. Sei.
1991, 18 (5), 447.
16. Mann, M.D.; Hajicek, D.R.; Henderson, A.K.; Moe, T.A. "EERC Pilot-Scale CFBC
Evaluation Test Facility," EERC publication, Sept. 1992.
NOXSO: A NO-WASTE EMISSION CONTROL T E C H N O L O G Y
R.E. BoUi, M.C. Woods^ D.R.-Madden^ and D.W. Corfman'^
"NOXSO 3, P.O. Box 469, Library, Pennsylvania 15129
''U.S. Department of Energy, Pittsburgh Energy Technology Center, P.O. Box 10940,
Pittsburgh, Pennsylvania 15236
O h i o Edison, 76 South Main Street, Akron, Ohio 44308
1. ABSTRACT
The NOXSO Process is a dry, regenerable flue gas treatment system that simultaneously
removes over 90% of the SO2 and 70-90% of the NO^ from flue gas generated from the
combustion of coal. The 5 MW Proof-of-Concept (POC) Plant was the last in a series of
test programs prior to construction of the first commercial NOXSO installation, a 115 MW
unit to be located at Ohio Edison's Niles Plant. The POC plant logged over 5200 hours of
flue gas operation. Over the period from April to December 1992, the POC plant
availability was 76%. The process operates safely with no lost-time accidents for the
duration of the test program. Both SO2 and NO^ removal efficiency were shown to be a
function of gas residence time, solids residence time and inlet SOj/NO^ concentration. NO^
removal efficiency was also shown to be a strong function of adsorber bed temperature.
Process economics of the 115 MW commercial installation are examined. Including revenue
from sulfur sales and SO2 allowances generated by over compliance with the Clean Air Act,
the process cost is estimated at $328/ton of pollutant removed.
2. INTRODUCTION
The NOXSO Process was successfully tested at small scale (0.017 MW) on high sulfur
coal (2.5%) at the TVA Shawnee Steam Plant. The test results are contained in two U.S.
Department of Energy (DOE) reports.
Tests of a NOXSO Process Development Unit (PDU, 0.75 MW) were conducted at the
Pittsburgh Energy Technology Center (PETC) under a cooperative research agreement
between NOXSO and the DOE. Testing in the adsorber was done by continuously feeding
a batch of sorbent into a fluidized bed adsorber and collecting the spent sorbent from the
adsorber overflow. Regeneration took place in a separate batch reactor. The test results
were reported by Yeh et al. in 1987,^ and by Haslbeck et al. in 1988.^
A Life-Cycle Test Unit (LCTU, 0.06 MW) was built at PETC in 1988 to test the
NOXSO Process in an integrated, continuous-operation mode. The LCTU test program was
438
designed to determine long-term effects of the process on the sorbent reactivity and attrition
properties. The sorbent was successfully tested for over 2000 hours on flue gas. The test
results were published by Ma et al in 1990,^ and by Yeh et al in 1990.^
The Proof-of-Concept (POC) test is the last test prior to full-scale demonstration. The
POC test will collect all of the information needed to design the full-scale NOXSO POC
Plant: e.g., data pertaining to materials of construction, process performance and cost,
process safety, process control, sorbent activity, sorbent attrition, heat recovery, etc. The
NOXSO POC Plant (5 MW) is located at Ohio Edison's Toronto Plant in Toronto, Ohio.
Flue gas was first introduced to the NOXSO POC Plant on November 23, 1991. The
current test results and process performance, along with a summary of process economics,
are presented in this paper.
3. NOXSO PROOF-OF-CONCEPT PLANT: FACILITY DESCRIPTION
The NOXSO POC Plant at Toronto, Ohio is shown schematically in Figure 1. A slip
stream of flue gas (equivalent to 5 MW coal-fired power) is extracted from either Boiler #10
or #11 of Ohio Edison's Toronto Power Plant. The flue gas first flows through a 250 hp,
I.D. fan, then is cooled to 160C (320F) or lower by spraying water into the flue gas
ducts. The cooled flue gas then enters a 3.2m (126") diameter single-stage fluid bed
adsorber. The NOXSO sorbent, 1.23mm diameter -alumina beads impregnated with 5.2
wt% Na, removes the SO2 and NO^ simultaneously from the flue gas as it passes through
the fluid bed adsorber. The cleaned flue gas mixes with the hot offgas from the sorbent
heater, then passes through the baghouse to remove all the attrited sorbent before the gas
vents to the atmosphere through the power plant's chimney. A cyclone is installed after the
adsorber to recycle fines to the bed (50% efficient on 50 micron diameter particles).
The spent sorbent in the adsorber overflows into the dense-phase conveying system
where 128.9 kPa (40 psig) air lifts the sorbent 24.4m (80 ft) high to the top of the sorbent
heater, which is a 2.34m (92") diameter, 3-stage, fluid bed vessel. A natural, gas-fired air
heater supplies the hot air to heat the sorbent in the sorbent heater to 621 C (1150F).
During the sorbent heating process, all the adsorbed NO^^ and a small portion of adsorbed
SO2 desorb from the sorbent. The hot sorbent heater offgas can either be directly vented
to the atmosphere through the power plant's stack or can be mixed with the cleaned flue gas
to enter the baghouse. Mixing with the flue gas is needed to protect the baghouse from
exceeding the high temperature limit of the bags. No cyclone is installed on the top of the
sorbent heater. The hot sorbent in the bottom bed of the sorbent heater underflows into a
J-valve. Either nitrogen or steam can be used to carry the sorbent through the J-valve into
a 1.22m (48") diameter moving-bed regenerator. Natural gas is the first regenerant to treat
the hot sorbent in the regenerator at a temperature of 1130F. The sulfate on the sorbent
is reduced to SO2, HjS, and sulfide. Steam is then used to hydrolyze the sulfide to H2S
which occurs at a temperature of 1080F. The offgas from the natural gas treater mixes
with that from the steam treater before the combined stream enters the incinerator, in which
all the sulfur species are converted to SO2.
The regenerated sorbent flows into a second J-valve from which it enters the 1.73m (68")
diameter, 3-stage fluid bed cooler. A fan supplies ambient air to cool the sorbent. The heat
of the regenerated sorbent is recovered by the cooling air which is then used as the
439
AIR OUTLET
NOXSO
PROCESS
TOWER
TO CLAUS
Figure 1. NOXSO POC Plant at Toronto, Ohio

440
combustion air in the air heater. The cool sorbent in the bottom bed of the cooler overflows
into a 1.83m (72") diameter surge tank. A third J-valve is used to transport the sorbent
from the surge tank to the adsorber.
The first two J-valves isolate the reducing environment (regenerator) of the NOXSO POC
Plant from its oxidizing environment (heater and cooler train). The steam (for normal
operation) or nitrogen (for start-up) enters the two J-val ves to carry the sorbent upward.
Since the steam is introduced at the lowest point of the J-valve, which is also the highest
pressure point between the two vessels, a steam barrier is created to prevent the mixing of
the reducing gas with the oxygen or vice versa. The third J-valve is operated using air to
lift the sorbent from the surge tank to the adsorber.
The NOXSO POC Plant differs from a commercial unit in two respects. First, since the
NOXSO POC Plant uses only a slip stream of flue gas from the power plant, the amount of
NO, evolved from the sorbent heater is too small to affect the NO, thermal equilibrium
inside the boiler furnace. Therefore, NO, is not recycled to the boiler as it would be in a
commercial unit. However, the ability of a coal combustor to reduce excess NO, introduced
into the combustion chamber was proven in simulated NO, recycle tests. The tests were
carried out using the Department of Energy, Pittsburgh Energy Technology Center's tunnel
furnace and 227 kg/hr (500 Ib/hr) pulverized coal combustor. Additional NO, recycle tests
were conducted on a small scale cyclone 227 kg/hr (500 Ib/hr) burner at the Babcock &
Wilcox (B&W) Research Center in Alliance, Ohio to obtain design data for the NOXSO
Demonstration Plant.^ The 115 MW Demonstration Plant will be located at Ohio Edison's
Niles Plant (Unit #1) which utilizes cyclone burners similar to the one at B&W.
The second difference between the POC and a commercial NOXSO installation is the fate
of the regeneration offgases. At the POC, the offgases are simply incinerated so that all
sulfur species are converted to SO2 and then vented to the power plant chimney. In a
commercial unit, the regeneration offgases are sent to a sulfur recovery plant where the
sulfur bearing gases are converted to elemental sulfur. Depending on market conditions and
regional demand, either sulfuric acid or liquid SO2 could be chosen as the end product rather
than elemental sulfur. As the processes for making each of these end products are well
established and commercially available, they were not tested at the POC facility.
4. NOXSO POC PLANT RELIABILITY AND SAFETY
From November 1991 through December 1992, the NOXSO POC Plant processed flue
gas for a total of 5213 hours. An additional 1615 hours was spent in a hot-inert mode of
operation, i.e., sorbent was circulated throughout the system and heated but air, instead of
flue gas, was fed to the adsorber.
The NOXSO POC Plant operated with a high availability factor for an experimental unit.
The plant availability factor is defined as the number of NOXSO POC Plant operating hours
on flue gas expressed as a percentage of the total number of hours in which the power plant
was up and running and flue gas was available for processing. The NOXSO POC Plant
availability factor per month ranged from a low of 0% in January to a high of 94% in June.
The first four months of operation were hampered by the usual start-up/shakedown
problems normally expected in first-of-a-kind installations. For example, the POC Plant was
shutdown the entire month of January (0% availability) to replace all seven grid plates in the
441
fluid beds. The original 1/16" diameter grid holes proved to be too small and became
plugged. However, the monthly average POC Plant availability over the period April -
December 1992 was 76%. This is an excellent result for a POC Plant. The commercial
standard in the utility industry for flue gas treatment is roughtly 80%. Nevertheless, the
NOXSO POC Plant availability factor over the last eight months of the POC test was close
to the industry standard for commercial plant. This demonstrates that the process is reliable
and adjusts easily to changing operating conditions.
The POC Plant was run by two operators. A minimum of two was required for safety
so that, in the event of an injury to one man, the other could assist the injured and call for
help or emergency response. In actuality, our experience is that less than one fuU-thne
operator is needed to operate the POC Plant since process controls and process safety
systems are fully automated through the distributed control system. Auxiliary personnel for
maintenance, instrument calibration and repairs, etc. are required on an as-needed basis.
The NOXSO POC Plant was instrumented for intrinsically safe operation. The process
and installation were thoroughly reviewed to insure safe design and operation. There were
no lost-time accidents during the entire POC project. The process operated safely for over
5213 hours on flue gas and 1615 hours in a hot-inert mode for an 18 month period. This
record is a direct result of proper design and operation of the NOXSO Process. Two system
safety hazard analyses (what ifs) were performed by MK-Ferguson, the engineering and
construction company involved with the POC. One analysis was performed on the process
as designed and a second after the process was constructed. W.R. Grace also performed two
complete haz-op reviews of the process (one as designed, a second as installed). A safety
inspection of the site and operation was performed by MK-Ferguson's director of corporate
safety prior to system start-up.
The process is controlled using a Bailey Network 90 Distributed Control System (DCS)
with two operator interface stations. The DCS system has redundant control modules within
the DCS, and conmiunication modules between the DCS and operator interfaces. If any of
these items fail, the redundant module will automatically replace the failed module. Almost
all of the process measurements and the control elements are tied into the DCS. The
operator interface stations display measured values, control outputs, and alarms through over
20 graphic screens. The system was designed to shutdown safely in the event of a total
power failure, and valve fail modes were designed to shut off all natural gas to the tower
and to begin nitrogen purging of the regenerator.
Alarms on process values occur through the DCS and are displayed on the operator
screens. The control system is designed to automatically take corrective action through
process trips to insure process safety. A total of 34 process criteria interlock into 24 trip
devices. Numerous trips exist to insure separation of the oxidizing environment in the
heater/cooler system from the reducing environment in the regenerator. These are:
1. Sorbent heater bottom bed level: normal operation at 11 inches with trip at 3 inches,
measured by three separate pressure differential measurements and a nuclear level gauge.
2. Sorbent heater to regenerator differential pressure: normal operation at 10" HjO, trip at
0" H2O, measured by three separate pressure differential measurements.
3. Oxygen and methane measurements in the top and middle J-valves to detect gas transfer
through the J-valve.
To insure operator safety against hazardous gas leakage, the process tower is equipped
with 16 remote gas sensors for H2S (8 sensors), SO2 (4 sensors), and CH4 (4 sensors).
442
These sensors are placed on the tower near areas of possible leaks. The sensor displays are
in the control room and the sensor alarms are output to the DCS. An alarm and flashing
light at the base of the tower warns if concentrations of these gases exceed safe levels.
There is some redundancy with respect to trips on the POC unit which will be removed
on conmiercial units. The sorbent heater bottom bed level was measured by three
differential pressure transmitters and a nuclear level gauge. Both these level indicators had
alarm levels and trips. For commercial units, this will be reduced to one differential
pressure measurement and a nuclear gauge or two differential pressure measurements. This
would have two measurements of the heater bottom bed level for independent trips on the
level, while removing some redundancy.
There were three differential pressure transmitters monitoring the pressure difference
between the bottom bed of the heater and the regenerator. These will be reduced to two
transmitters in a commercial unit. Purging the regenerator with high volumes of nitrogen
whenever a trip occurs was found to be unnecessary. The purge nitrogen flows from
pressure transmitters and sorbent sampling stations were sufficient to maintain regenerator
pressure in the event of trips. These process control changes can be made without any
compromise to operating safety.
5. PARAMETRIC TEST RESULTS
A primary goal of the POC test program was to determine the effect of major process
variables on adsorber SO2 and NO, removal efficiencies. The process variables included
flue gas flow rate, sorbent flow rate, adsorber bed depth, gas residence time, solids
residence time, inlet SO2 and NO, concentrations, and adsorber bed temperature. The
effects of selected process variables are discussed below.
Figure 2 is a plot of SO2 removal efficiency versus SO2 inlet to the adsorber at two sets
of operating conditions. One test was conducted at mini-load (typical NO, inlet
concentration of 200 to 300 ppm) and the other was conducted at base load, (typical NO,
inlet concentration of 350 to 450 ppm.) Each data set was obtained at a nearly constant gas
residence time, but sorbent residence times varied by 22% and sorbent inventory varied by
10% in the two tests. The average operating conditions for each data set are shown in Table
1. The lines shown in Figure 2 are the best fits to the data using the method of least
squares.
Table 1
Average Operating Conditions for the Data Sets Shown in Figure 2.
Sorbent Circulation Rate (Ibs/hr)

Test Parameter 9949 6877
Flue Gas Flowrate (SCFM) 7257 6981
Gas Residence Time (sec) 0.88 0.82
Sorbent Residence Time (min) 38 49
Average NO, inlet (ppm) 404 215
Figure 2. S02 Removal as a Function of Inlet S02 Concentration
443
444
The limit as ^ 0 is 100%, but the y intercepts obtained by linear regression are 107
and 117. Nevertheless, the data fit the regression well, leading to the conclusion that SO2
removal efficiency is a linear function of SO2 inlet concentration assuming all the other
adsorber operating variables are constant.
SO2 removal efficiency is higher at lower sorbent residence time (i.e., as residence time
decreases, active adsotion sites circulate through the adsorber at a higher rate) and at
higher NO^ inlet concentration as seen in Figure 2. Each of these effects was found to
independently increase SO2 removal efficiency. In addition, the reduction in SO2 removal
efficiency with SO2 inlet concentration is different by a factor of two for the two lines in
Figure 2, clearly showing the effect of sorbent residence time and NO^ inlet concentration,
since in all other respects the test conditions were nearly identical.
The concentration effect is shown in Figure 3. The data cover a NO^ inlet range
of 400 ppm (base load) to 1000 ppm (flue gas spiking). Flue gas spiking was performed
using compressed gas cylinders of NO to adjust the inlet NO^ concentration to the desired
test value. All data were obtained at constant gas and sorbent residence times and fairly
constant SO2 flue gas inlet concentrations ranging from 2883 to 3132 ppm. A data set was
obtained at each of three adsorber bed temperatures: 345F, 312F, and 297F.
Figure 3 shows that in all tests NO^ removal efficiency was higher at lower adsorber bed
temperatures. This effect is clearly illustrated at 1000 ppm inlet NO^, where NO^ removal
efficiency is 4 1 % at 345F bed temperature, 74% at 312F, and 77% at 297F.
The reduction of NO^ removal efficiency with increasing NO^ inlet concentration is best
approximated by the lines drawn in Figure 3. The effect of temperature on NO^ removal
is illustrated quite dramatically as the decrease in NO^ removal efficiency is three times
faster at an adsorber bed temperature of 345 F compared to the decrease at 297''F and
312F.
6. PROCESS ECONOMICS
The data obtained from the NOXSO POC Plant has been incorporated into the design of
the NOXSO Conmiercial Demonstration at Ohio Edison's Niles Plant Unit # 1 . The
Demonstration Plant is part of the U.S. Department of Energy's Clean Coal Technology
Program. An economic analysis of the Demonstration Plant has been performed based on
projected optimized operating costs. Capital costs were determined through an EPRI
sponsored analysis of the NOXSO Process. The results of the economic analysis are shown
in Table 2.
The site specific values for uncontrolled emissions are from Niles Unit # 1 . Niles Unit
#1 has a gross capacity of 115 MW and burns on average 3% sulfur coal. The annual
operating and maintenance costs of the NOXSO Conmiercial Demonstration Plant are
calculated to be just over $6 million per year. The capital cost is based on an EPRI
sponsored economic evaluation which estimated a value of $252/kW^. Using a fixed charge
rate of 10.6% and accounting for the credit generated by the sale of sulfur, the levelized cost
of the NOXSO Process is $8.6 million per year. This translates to a levelized cost of
$417/ton of pollutant removed (SO2 and NO J .
An additional credit can be taken for the SO2 allowances generated. One allowance is
equivalent to one ton of SO2 removed in excess of the company system requirements. The
S02 INLET = 3132-2883 ppm
Figure 3. NOx Removal as a Function of Inlet NOx Concentration
445
446
Table 2. Economic Analysis of a Future NOXSO Plant (1)
100% CAPACITY 85 % CAPACITY

SITE SPECIFIC
UNCONTROLLED S 0 2 EMISSIONS (TPY) 24,638 20,942

UNCONTROLLED NOx EMISSIONS (TPY) 3,043 2,587
CONSTANT VALUES
CAPACITY FACTOR 85 %
SULFUR VALUE $50.00 /TON
ELECTRICAL ENERGY $0.03 /kWh
NATURAL GAS $2.00 /MSCF
SORBENT COST $3.40 /LB
SORBENT ATTRITION RATE 0.020 % OF FLUID BED INVENTORY/H
S 0 2 ALLOWANCE VALUE $300.00
FIXED CHARGE RATE (2) 10.6 %
GROSS CAPACITY 115 MW
COAL SULFUR 3 %
REMOVAL COST NOx/REMOVAL COST S 0 2 3/1
ENVIRONMENTAL RESULTS
S 0 2 REMOVAL 95 '
NOX REMOVAL 80 '
S 0 2 EMISSIONS (TPY) 1,047
NOX EMISSIONS (TPY) 517
OVERALL EFFICIENCY 93
OPERATING AND MAINTENANCE COSTS
FIXED (3) $2,075,439

VARIABLE (4) $38,235
NATURAL GAS $1,031,822
SORBENT $2,405,058
NET ELEC ENERGY (kWh) 15,487,680
NET ELECTRIC ENERGY $464,630
TOTAL $6,015,184
SULFUR
PRODUCED (TPY) 9,948

VALUE $497,380
CAPITAL COST
115 MW PLANT $29,000,000

($/kW) 252
LEVELIZED COST
($/YEAR) 8,591,805
(mills/kWh) 10.0
($/T0N - S02) W / 0 NOx CREDIT 432
($/TON - S02) 329

($/TON - NOx) 987
447
Table 2. Economic Analysis of a Future NOXSO Plant (1)
S02 ALLOWANCE (PER YEAR) (5) 5,893

$1,797,900
LEVELIZED COST INCLUDING S02 ALLOWANCE CREDIT
($/YEAR) 6,823,939
(mills/kWh) 8.0
($/TON - S02) W / 0 NOx CREDIT 343
($/TON - S02) 261

($/TON - NOx) 784
******** REFERENCE INFORMATION *********************************************
SORBENT
FLUID BED INVENTORY - # 475,000

CIRCULATION RATE - #/HR 300,000
NATURAL GAS (LB/HR)
AIR HEATER 1398

REGENERATION 1304
SULFUR PLANT 386
TOTAL 3088
ELECTRICAL POWER KW % GROSS POWER
FLUE GAS BOOSTER FANS 1884 1.6%

BALANCE OF NOXSO PLANT 2695 2.3%
FD FAN CREDIT (350) (0.3%)
NOx RECYCLE/CLAUS STEAM CREDIT (1906) (1.7%)
COMBUSTION AIR STEAM PREHEAT CREDIT (243) (0.2%)
NET 2080 1.8%
(1) 1993 dollars.

(2) Fixed rate charge includes 2% for insurance and taxes as proposed by EPRI.
(3) Includes operating labor , fringes, and supervision; maintenance labor and equipment;
and general and administrative expenses.
(4) Includes process water and Claus plant catalyst.
(5) One credit = one ton S 0 2 removed in excess of permit requirement.
448
value of a credit will vary over time, but can be estimated based on the value of credits sold
to date. For the puose of this analysis, a value of $300 per allowance has been used. For
the specific case analyzed in Table 2, 4,846 credits per year are generated (assuming the rest
of the company's system is in compliance) for a total value of $1.45 million. This gives an
adjusted levelized cost of $7.2 million which translates to a cost of $380/ton of SO2 removed
or $347/ton of pollutant removed.
Table 2 also summarizes the electrical power requirements of the NOXSO Process. The
Niles installation will require two flue gas booster fans with a combined power requirement
of 1884 kW. The rest of the NOXSO plant utilizes an additional 2695 kW of power. The
fans used to move air through the sorbent heater/sorbent cooler train require 1700 kW of
the 2695 kW additional power. The NOXSO Process could generate electrical power credits
in three areas. First, by supplying 30% of the power plant combustion air (through the NO^
recycle stream), the Niles Plant combustion air fans are expected to use 350 kW less power.
The recycle stream is cooled from 500F to 150F by heating boiler feed water for the
power plant. This can replace extraction steam from the turbine which gives the Niles Plant
additional generating capacity or lowers fuel consumption. In addition, excess steam
generated in the sulfur plant could potentially be used in place of turbine extraction steam.
These two energy credits represent 1906 kW of electric power production of which about
two thirds is from the NO^ recycle credit. An additional 243 kW credit is obtained by a
reduction in the amount of extraction steam required to preheat the combustion air prior to
the forced draft combustion air fans. The heat is now provided by the 150F NO^ recycle
stream.
The gross power consumption of the NOXSO Process is 3.9% of the power plant gross
output. The net power consumption after all credits are accounted for is 1.8%. The
electrical energy cost used in Table 2 is based on the net power consumption.
7. CONCLUSIONS
The NOXSO POC Plant demonstrated the ability of the NOXSO Process to run reliably,
safely and efficiently over a wide range of operating conditions. Over 5200 hours of flue
gas operation and over 1600 hours of hot-inert operation were completed with no lost time
accidents. Over the last eight months of POC testing, the NOXSO plant availability
averaged 76%.
Both adsorber bed temperature and inlet pollutant concentration were shown to have a
significant effect on adsorber removal efficiencies. Lower bed temperatures significantly
enhance NO^ removal efficiencies. At constant operating conditions, higher SO2 and NO^
inlet concentrations cause a decrease in removal efficiency. These and other results have
been incorporated into the design of the NOXSO Demonstration Plant scheduled to be
constructed at Ohio Edison's Niles Plant (Unit #1) beginning in 1994.
8. ACKNOWLEDGMENTS
NOXSO Cooration wishes to thank the following for their conmiitment of personnel
and funds to the successful completion of the NOXSO Proof-Of-Concept Test: The U.S.
449
Department of Energy's Pittsburgh Energy Technology Center, the Ohio Coal Development
Office, Ohio Edison Company, W.R. Grace & Co. and MK-Ferguson.
9. REFERENCES
1. J.L. Haslbeck, C.J. Wang, and L.G. Neal, et al., "Evaluation of the NOXSO Combined
NO./SOo Flue Gas Treatment Process," NOXSO Cooration Contract Report submitted
to U.S. DOE Report No. DOE/FE/60148-T5. November 1984.
2. J.L. Haslbeck, L.G. Neal, and C.J. Wang, et al., "Evaluation of the NOXSO Combined
NO,/SO. Flue Gas Treatment Process," NOXSO Cooration Contract Report submitted
to U.S. DOE Report No. DOE/PC/73225-T2. April 1985.
3. J.T. Yeh, C.J. Drunmiond, and J.L. Haslbeck, et al., "The NOXSO Process:
Simultaneous Removal of SO. and NO, from Flue Gas," Presented at the 1987 Spring
National Meeting of the AIChE, Houston, Texas. March 29 - April 2, 1987.
4. J.L. Haslbeck, W.T. Ma, and L.G. Neal, "A Pilot-Scale Test of the NOXSO Flue Gas
Treatment Process," NOXSO Cooration Contract Report submitted to U.S. DOE
Contract No. DE-FC22-85PC81503. June 1988.
5. W.T. Ma, J.L. Haslbeck, and L.G. Neal, "Life-Cvcle Test of the NOXSO Process,"
NOXSO Cooration Contract Report submitted to U.S. DOE Contract No. DE-FC22-
85PC81503. May 1990.
6. J.T. Yeh, W.T. Ma, and H.W. Pennline, et al., "Integrated Testing of the NOXSO
Process: Simultaneous Removal of SO^ and NO, from Flue Gas," Presented at the
AIChE Spring National Meeting, Orlando, Florida. March 1990.
7. J.E. Cichanowicz, C.E. Dene, and W. DePriest, et al., "Engineering Evaluation of
Combined NO,/SOo Controls for Utility Application." Electric Power Research Institute,
Palo Alto, California. December 1991.
Efficient and Cost Effective NO^ and SO2 Removal from Flue Gases with the
S N O X ^ Process
D.C. Bono and W.H. Kingston
ABB Environmental Systems, 31 Inverness Center Parkway, Birmingham, AL 35243
1. INTRODUCTION
The current global emphasis on environmental protection and pollution abatement has
fostered the development of several new technologies and processes directed at the electric
utility industry. These new technologies represent significant advancements over those
currently employed, offering improvements in the areas of increased pollutant removal
efficiencies, reduced reagent requirements, minimized waste streams, and lower operating
costs. One such process is a catalytic de-SO^/de-NOx process (titled SNOX) being
demonstrated and offered by Asea Brown Boveri/Environmental Systems (ABB/ES).
The SNOX Process was developed in Denmark by Haldor Topsoe A/S and will be offered
under license in North America by ABB/ES. The U.S. Department of Energy (DOE),
through its Clean Coal Technology Program, the Ohio Coal Development Office (OCDO),
Ohio Edison, Snamprogetti USA, as well as ABB/ES are participating in a demonstration of
this advanced new technology. The SNOX Demonstration Project is located at the Niles
Power Plant of Ohio Edison near Niles, Ohio in Trumbull County. In conjunction with the
Ohio Edison demonstration, large scale plants are also being commissioned in Italy and
Denmark as the culmination of pilot scale development and testing.
This flue gas cleaning system is comprised of Selective Catalytic Reduction (SCR) for NO^
control and sulfuric acid production technologies for SO2 removal. Various design features
of the process combine to result in high efficiency NO^ and SO2 removal, minimal particulate
emissions, no liquid or solid waste production, and increased thermal efficiency of the boiler.
The emphasis of this paper is to present SNOX Process information illustrating its impact
on waste generation, gaseous and particulate emissions, the recovery of additional thermal
energy, and capital and operating costs. Demonstration and testing of the SNOX plant in
Ohio is in progress and detailed performance of this unit will be documented in future
technical papers.
2. PROJECT AND PROCESS DESCRIPTION

The Niles Power Plant is situated on 130 acres along the southern bank of the Mahoning
River and is part of the Ohio Edison System, which serves approximately 9,000 square miles
total in central and northeastern Ohio and western Pennsylvania (through its Pennsylvania
Power Company subsidiary). One of eleven power plants in the Ohio Edison system, the
Niles facility was commissioned in 1954.
452
The main power plant structure covers an area of approximately 166 ft by 200 ft, and
houses two cyclone coal-fired steam electricity-generating units with a net demonstrated total
capacity of 216 MW for both units. The boiler units bum high-sulfur coal with a capacity
factor of approximately 67 percent. Flue gases from both boiler units are dispersed into the
atmosphere by a two-flue 393 ft tall stack. The plant utilizes two electrostatic precipitators
to control particulate emissions. The SNOX Demonstration Project at Ohio Edison treats
about one-third of the flue gas stream from Unit No. 2 or approximately 16 percent of the
total flue gas generated at the plant.
The execution of the SNOX Demonstration Project is divided into three phases which span
forty-eight months. These phases are identified as follows:
Phase I: Design and Permitting

Phase IIA: Long Lead Procurement
Phase IIB: Construction and Start-Up
Phase III: Operation, Data Collection, Reporting and
Disposition
Phase I of this project, Design and Permitting, can be further broken down into Basic
Engineering, Detailed Engineering and Permitting. Phase IIA is comprised of the
procurement of long lead time items such as the baghouse, high temperature steel, control
system, gas/gas heat exchanger, and WSA-Condenser (Wet Sulfuric Acid condenser). The
project is currently in Phase III of the program - Testing - which will span approximately
twenty-two months.
The SNOX technology consists of five (5) key process areas which are particulate
collection, NOx reduction, SO2 oxidation, sulfuric acid (H2SO4) condensation and acid
management. Heat addition, transfer, and recovery also represent a significant part of the
SNOX system. The integration of these individual steps is shown in Figure 1, which is the
process flow diagram for a typical full-scale integrated application of the process.
Referring to Figure 1, the flue gas which leaves the boiler air preheater is treated in a
particulate control device and passed through the primary side of a gas/gas heat exchanger
(GGH) which raises the gas temperature to above 700F (370C). An ammonia and air
mixture is then added to the gas prior to the selective catalytic reactor (SCR) where nitrogen
oxides are reduced to free nitrogen and water. The flue gas leaves the SCR, its temperature
is adjusted slightly, and enters the SO2 Converter which oxidizes SO2 to sulfur trioxide (SO3).
The SO3 laden gas is passed through the secondary side of the GGH where it is cooled as the
incoming flue gas is heated. The processed flue gas is then passed through a falling film
condenser (the WSA-Condenser) where it is further cooled with ambient air to below the
sulfuric acid dewpoint. Acid condenses out of the gas phase on the interior of borosilicate
glass tubes and is subsequently collected, cooled, diluted, and stored. Cooling air leaves the
WSA-Condenser at about 400F (200C) and is used for process support and furnace
combustion air after collecting more heat through the air preheater. For the SNOX
demonstration at the Niles facility, the WSA-Condenser cooling air is not returned to the
boiler air preheater because the entire boiler flue gas output is not being treated.
2.1 Particulate Collection

The degree of particulate collection upstream of the SO2 Converter has a direct effect on
CLEAN FLUE GAS ~ WSA- CONDENSER
80 I LER A IR GAS\GAS
HEAT EXCHANGER
SCR
PART I CULATE
COLLECTOR
HEAT
SULFUR I C
ACID
STORAGE
SO 2 CONVERTER
FIGURE 1 SNOX INTEGRATED

PROCESS FLOW
453
~
U'I
W
454
the frequency of cleaning for the SO2 catalyst. This correlation is due to the inherent
characteristic of the catalyst to collect and retain greater than 90% of all particulate matter
which enters the converter. The collection of this particulate matter, over time, increases the
pressure drop across the converter. The original pressure drop can, however, be restored
through catalyst screening. Higher dust loads therefore require more frequent catalyst
screening which provides an incentive to utilize a high efficiency particulate collector
upstream of the SNOX Process area. As a consequence of both the high efficiency dust
collector and the dust retention characteristics of the SO2 Converter, particulate emissions
from the system are predicted to be significantly less than 1 mg/Nm^ (0.0004 gr/SCF) which
is far below any current regulations or standards.
It should be noted that while a very high efficiency particulate collector has benefits related
to catalyst cleaning costs, it is not an essential feature. The SNOX plant in Italy, for
instance, uses an electrostatic precipitator (ESP) and will require SO2 converter catalyst
screening more frequently. For comparison, the Niles Demonstration Project with a baghouse
employing teflon coated filter bags is expected to require screening only once per year.
2.2 Nitrogen Oxide Reduction

After the particulate matter is collected and the temperature of the flue gas is increased to
over TOO^'F (370C) through the GGH, an ammonia (NH3) and air mixture is introduced to
the gas stream through a proprietary nozzle grid located upstream of the SCR. The
proprietary design of the nozzle grid allows for controlled stoichiometric ratios of NH3 to
on a localized scale over the cross-section of the SCR inlet duct. This is controlled in
order to optimize system removal efficiency since any unreacted NH3 which "slips"
across the SCR will be oxidized to , water, and N2 in the SO2 Con\erter downstream.
A slipstream of hot air which leaves the WSA-Condenser is used to evaporate and dilute the
ammonia for injection.
The flue gas/NHs mixture enters the SCR and contacts the Haldor Topsoe DNX monolithic
catalyst which has been demonstrated in pilot and commercial plants in Europe to remove up
to 97% of the entering ^ The reduction of NO follows Equation I.
NO+NH^+025O2^N^ + l.5Hp + 410KJImole (3S9Btulmole) (1)
The small amount of NO2 present in the flue gas is reduced similarly.
The general arrangement of the SNOX Process offers one significant advantage over other
SCR technologies using NH3 in that those processes are limited to NH3/NOX molar ratios of
less than 1.0. This must be done in order to Hmit the NH3 "slip" past the SCR to 5 ppm or
less in order to avoid ammonium salt scaling. The NOx removal efficiency of these processes
is thus limited to less than 90%. Any NH3 slip in the SNOX Process, however, is oxidized
as it contacts the SO2 Converter catalyst downstream. This allows stoichiometric ratios of
1.00 to 1.05 and consequently higher NOx removal efficiencies without the adverse
downstream effects of higher ammonia concentrations. Excess NH3 slippage, however,
should still be minimized in order to maximize overall system NOx removal due to the
oxidation of NH3 in the SO2 Converter downstream.
455
2.3 Sulfur Dioxide Oxidation

The SCR effluent is heated slightly higher with natural gas, oil or steam to reach the
optimum SO2 Converter inlet temperature and passed through Haldor Topsoe VK38 sulfuric
acid catalyst. This catalyst has seen wide use in the U.S. sulfuric acid industry for the past
decade with a high degree of success. Over 95% of the entering SO2 is oxidized via Equation
2K
SO^ + 0.5 ^ SO. + 98 KJ/mole (93 Btu/mole) (2)
The efficiency of the Topsoe catalyst is not affected by the presence of water vapor or
chlorides in concentrations up to 50% and several hundred ppm, respectively. An additional
benefit of the sulfuric acid catalyst is its ability to oxidize most of the carbon monoxide (CO)
and hydrocarbons present in the flue gas stream to carbon dioxide and water. This is of
importance since hydrocarbons and CO emissions are coming under increased scrutiny.
As described in the discussion of particulate collection, the catalyst must be cleaned at
certain intervals depending on the dust loading entering the catalyst vessels. The cleaning
procedure consists of the isolation of an individual catalyst bed, removal and mechanical
screening of the catalyst in that bed, and refilling the bed with the screened catalyst. The
procedure can be automated and is performed while the process is on-line. This procedure
separates and removes virtually all flyash and other contaminants from the surface of the
catalyst pellets. Catalyst loss during screening is estimated at 2-3%.
2.4 Sulfuric Acid Condensation

The SO3 in the gas leaving the SO2 Converter is hydrated and condensed in two steps.
First, the bulk of the SO3 is hydrated to sulfuric acid vapor as the flue gas passes through the
secondary side of the GGH and drops approximately 300F (170C) to 400 - 500 F (200 -
260 C):
5 O 3 -H Hp ^ H^SO^ (vapor) +100 KJImole (95 Btu/mole) (3)
At this point the flue gas is still well above the acid dewpoint thus avoiding acid condensation
and corrosion of the ductwork. The flue gas then enters the WSA-Condenser. The WSA-
Condenser is a unique tube and shell falling film condenser with ambient air used as a cooling
medium on the shell side. Borosilicate glass tubes are used to convey and cool the flue gas.
The design and operating conditions of the WSA-Condenser make possible the virtually
complete condensation and capture of the sulfuric acid at concentrations of 94 to 97 wt. %,
according to the following equation:
456
H^SO^(vapor) H^SO^{liquid) + 69KJImole (65Btu/mole) (4)
The flue gas is cooled to about 210F (99C) at the outlet of the condenser and contains
hydrated and unhydrated SO3 no higher than typical exit flue gas. The condensed sulfuric
acid product is funnelled through an acid brick lined trough at the bottom of the WSA-
Condenser into the acid conditioning and storage system.
2.5 Sulfuric Acid Management

The hot concentrated sulfuric acid product at about 400F (200) is collected and circulated
through a thermoplastic Table 1
lined system consisting of
a holding tank, circulation
pumps, and a water-cooled SNOX Demonstration Project
tube and shell heat at Ohio Edison
exchanger. The purpose Design Data
of this loop is to cool the Inlet Outlet
acid to more conveniently
manageable temperatures Gas Flow (scfm) 78000 82000
(70-100F or 20-40C) Temperature (F) 305 210
and to allow for dilution
of the acid to the Particulate (gr/dscf) 10 <.0004
commercially traded Sulfur Dioxide (ppm) 2500 125
concentration of 93.2
wt. %. Based on prototype Nitrogen Oxides (ppm) 800 80
results, the sulfuric acid Sulfuric Acid (tons/day) 35
produced by the SNOX
Process at the Niles
Station is expected to meet
or exceed U.S. Federal Specification O-S-80E Class 1 and be commercially tradeable without
limitation.
The capacities and emission targets of the SNOX Demonstration at the Niles plant are
shown in Table 1. As described, the system will treat about one third of the flue gas from
the boiler and will produce about 35 tons per day of sulfuric acid.
2.6 Heat Addition, Transfer, and Recovery

Heat addition, transfer and recovery are of significant importance in the SNOX Process as
they influence the operating cost of the technology. The process requires heat only to trim
the flue gas temperature between the SCR and the SO2 Converter. It is anticipated that the
most efficient and cost effective source of this heat in a utility environment will be steam,
however, natural gas or oil can be effectively utilized.
One major piece of equipment in the SNOX Process is the gas/gas heat exchanger (GGH)
which allows the use of the high temperatures in the process area in an economic manner by
transferring sensible heat in the treated flue gas stream to the process inlet stream. Selection
of the type of heat exchanger is of concern since any leakage of flue gas across the GGH
457
would bypass both reactors and result in lower measured system removal efficiencies. This
effect would be proportional to the amount of leakage in these heat exchangers. A stationary-
type or heat pipe GGH has been employed in the SNOX Demonstration Project due to its zero
leakage compared to high leakage rates for a rotary type in this relatively small size. For
larger applications, a rotary type will have lower leakage rates (as a percentage of total gas
flow) and may be the most suitable choice.
The process generates recoverable heat in several ways. All of the reactions which take
place with respect to NO^ and SO^ removal are exothermic and increase the temperature of
the flue gas - NO^/NHs reactions, SO2 oxidation, SO3 + water to form gaseous sulfuric acid
(H2SO4), and condensation of the sulfuric acid. This heat plus any fuel-fired support heat
added after the SCR is recovered in the WSA-Condenser cooling air discharge for use in the
furnace as combustion air. Because the WSA-Condenser lowers the temperature of the flue
gas to about 210F (99C) compared to the 300F range of a typical plant, this additional
thermal energy is recovered along with that from the heats of reaction. A small percentage
of the process air is used for system auxiliaries such as ammonia evaporation and dilution,
burner combustion air, and catalyst screening equipment heatup.
To provide a basis for calculating the amount of heat recovery from a large size utility
generating plant, the following operating conditions for a - 500 MWe plant were assumed
as shown in Table 2. This plant is very similar to the "DOE Reference Plant" (detailed in
the PON for CCII) with small changes in coal sulfur and output.
Table 2
Design Premises For Flue Gas Cleaning Comparisons

Modified DOE Reference Plant
Plant Size (MWe) 510 Coal Flyash (%) 16.4
Firing Rate (tph) 196 Coal Ash to Flyash (%) 71.5
Coal Heating Value (Btu/lb) 12360 Flyash Emission (Ib/MBtu) 9.52
Heat Input (MBtu/hr) 4845 Sulfur in Coal (%) 3.0
Load Factor (%) 75 SO2 Emission (Ib/MBtu) 4.63
Gross Heat Rate (Btu/kWh) 9024 Emission (ppmv) 540
Net Heat Rate (Btu/kWh) 9493 NO, Emission (Ib/MBtu) 0.6
Using the emission rates and gas flows from this plant, along with the target values of 90%
removal and 95% SO2 removal, quantities of heat generated and recovered were
calculated and are shown in Table 3. As can be seen, the total heat recovery is substantial
and is equivalent to about 3.6% of the boilers total heat input without including additional
heat which may be added by fuel between the SCR and SO2 Converter. With this heat
included, the total heat input from the SNOX Process to the boiler is about 5% of plant input.
Looking at these values from another perspective, the amount of heat recovered by SNOX
is equivalent to 19.4 MWe of power without support heat, and 26.6 MWe of power with fuel-
fired support heat (using the plant gross heat rate of 9024 Btu/kWh). By contrast, the amount
of auxiliary power required by the SNOX Process is about 15 MWe for this size plant and
458
conditions. For a retrofit application, the thermal energy recovered by SNOX can be used
to reduce the coal feed rate or to produce more electricity if boiler heat transfer surface is
Table 3
Heat Generated And Recovered By SNOX Process

510 MWe 75% Load Factor
3.0% Sulfur Coal - 95% Removal
540 ppm - 90% Removal
OR SO2 HEAT MWe EQUIV
REMOVED GROSS HEAT
(gmols/hr) (kJ/gmol) (MBtu/hr) RATE
(9024 Btu/kWh)
Reduction 39203 410 15.2

SO2 Oxidation 150778 98 14.0
SO3 Hydration 150778 100 14.3
H2SO4 Condensation 150778 69 9.86
Additional Flue Gas
Cooling 122
( = 304 - 210 = 94 F)
SUB TOTAL 175 19.4
Support Heat 65.0

( = 50 F)
TOTAL 240 26.6
Plant Heat Input 4840

% of Plant Input with 4.95%
Support Heat
% of Plant Input W / 0 3.61%
Support Heat
SNOX Auxiliary 15.0
Power Requirements
adequate or if modifications can easily and economically be made. The above characteristics
make the use of high sulfur, low cost fuels economically attractive with this process.
Given the changes that would be required to generate more electricity in a retrofit
application, the more likely scenario is that coal feed rate would be decreased and plant gross
output would remain constant. However, even in this situation, the SNOX heat recovery is
of value and increases the overall efficiency of the boiler. Using the values from Table 3 the
impact of the SNOX Process on boiler heat rates (gross and net) and overall boiler efficiency
has been determined and is shown in Table 4. The bottom line is that even after subtracting
459
the auxiliary power Table 4

requirements of the
Iherefotebolterefficieiicy Heal Rales And Overa]! Plant Efficiency

is higher than it was BEFORE AFTER
previously. These SNOX SNOX
calculations were done Gross Output (MWe) 536.0 536.0
without including the heat
input to the process from Gross Heat Rate (Btu/kWh) 9024 8697
any fuel-fired support 509.5 494.5
Net Output (MWe)
heater. The fuel-fired
support heater will not Net Heat Rate (Btu/kWh) 9493 9427
increase the efficiency
Plant Efficiency, Gross (%) 37.8 39.3
but only acts to displace
an equivalent amount of Plant Efficiency, Net (%) 36.0 36.2
Btu's fired in the boiler.
In addition to the
economic impact of the heat recovery, an increase in the thermal efficiency of a plant results
in decreased CO2 emissions per MWe generated. Therefore, the SNOX Process can also
contribute to reduced CO2 emissions and enhances its already low gaseous and particulate
emission rates. This aspect of the process will be discussed in the following section.
3. EMISSIONS AND WASTE PRODUCTS

With respect to pollution reduction, the ability of the process to achieve extremely low
emission levels has been demonstrated by extensive prototype testing and verified by initial
performance of the European commercial plants. Sulfur dioxide and nitrogen oxide removal
levels in excess of 95% have been recorded and are well in excess of U.S. Federal
Requirements. Many of the unique design features of the process described in the previous
section of the paper contribute to these low emissions for both gaseous and particulate matter.
Although the target SO2 and NO^ removal efficiencies for the SNOX Demonstration at
Niles Station of Ohio Edison are 95% and 90% respectively, it is expected that removal will
be higher as indicated by both prototype testing and the European plants^ Table 5 was
prepared to compare the projected performance of the SNOX Process to various other flue
gas cleaning technologies and combinations of technologies. For this comparison it is
assumed that the SNOX Process will be capable of 95% NO^ reduction and 97% SO2
reduction. Other technologies and methods listed in the table are: 1) Electrostatic
precipitators (ESP) plus limestone wet flue gas desulfurization (WFGD) to meet New Source
Performance Standards; 2) Low NO^ burners plus WFGD for retrofit applications; 3) ESP
plus WFGD plus Selective Catalytic NO^ Reduction to address non-attainment areas; and 4)
the DOE Low Emission Boiler program intended to reduce emissions through combined
furnace and post-combustion control (low NO^ burners plus ESP plus WFGD).
These cases are compared to a SNOX unit following a baghouse employing teflon coated
filter bags. As described eariier, the SNOX Process will still produce less than 1 mg/Nm^
of particulate at the outlet with less efficient particulate removal devices, but frequency of
catalyst cleaning will need to be increased. By examining Table 5 it can be seen that the
460
projected performance of the SNOX Process is capable of significantly lower emission

quantities than the other methodologies. While some improvement in performance may be
possible with the other cases, they will have difficulty meeting the emissions of SNOX due
to its complementary joining of NO^ catalyst followed by SO2 catalyst. In only one area, HCl
and HP removal, does the SNOX Process not exceed the other cases. Because of the
temperature and concentration of the sulfuric acid, absotion of these two acids is expected
to be minimal. However, as mentioned previously but not included in the table, is the ability
of the SNOX Process to oxidize hydrocarbons such as CO and to decrease CO2 emissions due
to its increase in boiler efficiency.
Table 5
Projected Optimized Emission Rates Of SNOX Process

Versus Other Flue Gas Cleaning Options
510 MWe 75% Load Factor
3.0% Sulfiir 0.6 Ibs/MBtu N O , 16.4% Ash
NSPS A C ID RAIN A C ID RAIN D OE L OW M I N I MM U
N EW R E T R O FTI + N ON A T T ANI E M I S S IN
O E M I S S IN
O
E S P + W FDG B R N + W FDG E SP + W F GD + SCR B R N + EPS + W F GD B H + S NX O
Particulate Emission (Ib/MBtu) 0.030 0.030 0.020 0.015 0.001
Particulate Emission (mg/Nm^) 34 34 23 17 <1
Annual Part. Emission (tons/yr) 476 476 317 238 <16
SO2 Removal (%) 90.0 95.0 95.0 95.9 97.0
SO2 Emission (Ib/MBtu) 0.496 0.248 0.248 0.203 0.149
Annual SO2 Emission (tons/yr) 7350 3675 3675 3013 2205
SO3 Slip (ppmv) <10 <10 <10 <10 <5
HCl and HF Removal (%) >95 >95 >95 >95 0
NO, Reduction (%) 16.7 33.3 83.3 66.7 95.0
NO, Emissions (Ib/MBtu) 0.50 0.40 0.10 0.20 .03
Annual NO, Emissions (tons/yr) 7990 6390 1600 3195 480
Anmionia Slip (ppmv) n/a n/a <10 n/a <1
BRN = Low N O , Burners BH = Baghouse with Reverse Air;

ESP = Electrostatic Precipitators Goretex* and Glass Fiber Bags
WFGD = Limestone Wet Fluegas Desulftirization SCR = Selective Catalytic N O , Reduction
3.1 Waste Products

Since the SNOX Process produces a salable by-product, sulfuric acid, and NO^ is converted
to nitrogen and water, no waste materials are generated from the removal of SO2 and NO^.
Of course ash is still produced as a waste in approximately the same quantities as other
systems, and a small amount of catalyst plus flyash would be sent to a catalyst processor as
a result of the SO2 catalyst cleanings. In addition, both SO2 and NO^ catalysts would be sent
to a catalyst processor at the end of their useful life. It is estimated that the SO2 catalyst will
have a life of about 10 years, and the NO^ catalyst is expected to last for 3 to 6 years^ A
461
large amount of data is Table 6

available on the SO2
catalyst life expectancy
Product and Waste Quantities Generated From Plants
at this time, and the
Employing SNOX Versus WFGD
SNOX Demonstration
Project and European 510 MWe 75% Load Factor
plants will be producing 3.0% Sulfur 95 % Removal 16.4% Ash
more data concerning SNOX WFGD
the catalyst. (tons/yr) (tons/yr)
The products
generated by the SNOX Flyash 151100 150600
Process are listed in Bottom + Econ Ash 57420 57420
Table 6 and are
compared to the CaS04-2H20 187600
quantity of materials Limestone 5455
generated by a forced-
oxidized, limestone WFGD TOTAL 401075
WFGD system. Design
H2SO4 106900
premises for the
calculations are the SO2 Catalyst + Flyash 32
same as for the other 315452
SNOX TOTAL
comparisons (as listed
in Table 2). Although
C a S 0 4 * 2 H 2 0 (gypsum) is also a salable product, the possibility that many locations would
be able to actually sell it is small. It is more likely that force oxidation will be employed as
a way to improve the dewatering and landfilling properties of the sludge. In the case of
sulfuric acid, certainly its use will also be site specific but the market potential is greater and
sulfuric acid is more easily handled and transported than sludge. The size of the sulfuric acid
market in relation to quantities of acid produced by a utility plant will be discussed in the next
section.
3.2 Sulfuric Acid Use

According to a recent estimate, approximately 44.2 million tons of sulfuric acid were used
in the U.S. during 1991. As indicated in Table 3, phosphate fertilizers, ore processing, and
inorganic chemicals account for 80% of the total consumption. The remainder is used by a
wide variety of industries, including refining, paper, rubber and plastics. Total production
of sulfuric acid in the U.S. in 1991 was approximately 46.2 million tons. This represents an
operating load of about 96%. Annual growth in the U.S. sulfuric acid market has historically
been 0.9% but is expected to be only 0.5% over the next few years.
The market is very price competitive and suppliers are utilizing various forms of price
related incentives such as volume discounts in order to encourage sales. Many large volume
suppliers are located near their end-users in order to minimize transportation costs. In fact,
75% of the acid currently being produced is used captively at the production point. Because
of increased by-product acid production in the 1980's, many plant closings have occurred
since that time period. This has helped bring production levels more in line with end-user
demand. In addition, recent increases in fertilizer exports and in the use of sulfuric acid in
462
mineral leaching Table 7

operations, particularly
copper, have helped to
stabilize the market
even further. Sulfuric Acid Use in the U.S.
The majority of (1991 - 44,200 Million Tons Total)
sulfuric acid produced % OF
in the U.S. is from the END USE TOTAL
burning of sulfur in the
"contact" process, Phosphate Fertilizers 69
which accounts for the Petroleum Refining and Other 3
use of approximately Related Products
84% of the elemental
sulfur supply. Sulfuric Industrial Chemicals/Pigments 5
acid generated with this Minerals and Metals 6
process, known as
virgin acid, represents Synthetic Rubber, Plastics, and 2
some 90% of the total Other Synthetics
acid produced. Since Pulp and Paper 2
the 1980's, government
regulations have Organic Chemicals 2
required some Other 11
industries, such as
smelting, to treat their TOTAL 100.0
off gases for recovery
of sulfur compounds. This has resulted in an additional supply of commercial sulfuric acid
which has steadily grown to represent the remaining 10% of the current market.
With the advent of advanced pollution control technologies for utility power plants, such
as the SNOX Process, more of the "made-for-use" or "on-purpose" acid production will be
displaced. A typical 500 MW plant, burning 3% sulfur fuel and employing the SNOX
Process, can recover about 107,000 tons per year of concentrated sulfuric acid. This
quantity, however, represents only 0.24% of the U.S. market. Thus, a substantial number
of utility sulfur recovery plants would be necessary in order to significantly affect the market.
Sulfuric acid quality is quantified by three main properties - concentration, color, and trace
impurities. Concentration requirements are usually specified as one of several industry
standard values with the most common being 93.2 weight % or 66 Baume'. This
concentration is most common as it represents a minimum freezing point allowing
moreconvenient transportation modes without freeze protection. Color and impurity limits
are more strictly tied to the specific end use of the acid. For instance, an end product of a
pigment or synthetic plastic may have color requirements which cannot be satisfied with an
off-color sulfuric raw material. In contrast, an ore leaching operation may have no require
ment as to sulfuric acid color. In general, however, water clarity is standard.
Limitations on trace impurities in sulfuric acid are dictated in much the same way, by the
specifics of the end use. Notably, iron and other metal concentrations are restricted when
the intended use of the acid is as an electrolyte for storage batteries. An industry wide
standard for sulfuric acid concentration, color, impurities, and the test methods to analyze for
463
each is the U.S. Government Specification O-S-801E (current revision). Individual acid
brokers and end users, however, may operate under more or less stringent specifications
tailored to their end user or process. As mentioned, the SNOX acid will meet the required
government specification.
4. ECONOMICS
SNOX system costs are based on the Design Premises shown in Table 2. A typical SNOX
plant includes facilities for the following:
flue gas particulate collection/handling

selective catalytic reduction of
catalytic oxidation of SO2 to SO3
production of H2SO4 in the WSA-Condenser
sulfuric acid storage and loading
ammonia storage
SO2 catalyst screening
balance of plant and auxiliaries
Table 8 has been prepared to compare SNOX with a conventional wet limestone scrubber
on the same basis. One significant fact is that SNOX has no byproduct disposal costs
whereas for limestone scrubbing there will be a significant capital and operating cost if the
gypsum is not sold. As can be seen, SNOX is comparable to wet limestone scrubbing for
capital cost alone when the scrubber is compared on the same basis - with particulate
collection and including SCR. Even without SCR for the wet scrubber, total operating cost
for SNOX will be competitive or better than scrubbing due to the very low operating cost of
the SNOX process.
Fixed and variable operating costs were estimated for the same design plant and are shown
in Table 9. First year operating costs for SNOX are very low - about 1 mill/kWh - with
credits for the heat recovered and the sulfuric acid sold. A wet scrubber under these design
Table 8
Comparative Investment for

New Power Plant
500 MW Capacity
WFGD ($/KW) SNOX ($/KW)

Installed Equipment Cost 115 25 145 15
Other Site Costs (incl waste disp) 75 25 65 25
Subtotal 190 50 210 40
Particulate Removal 40 10 40 10
Selective Catalytic Reduction 30 5
Total 260 65 250 50
464
conditions will typically have operating costs in the 3-4 mills/kWh range. Further details on
SNOX economics and design criteria and assumptions can be located in Reference 2. In
summary, the SNOX process provides a viable method of emission control for industry with
excellent reduction efficiencies, a salable by-product, and no secondary pollution generation.
Table 9
SNOX Operating Cost
510 MW Plant
Annual Levelized
Item $/Unit Units/Yr Cost ($) Mill/kWh
COSTS:
Maintenance 2% X plant cost 2,500,000 .75
Manpower 60K/man-yr 8 man years 480,000 .14
Power .05/kWh 9.86 X 10' kWh 4,930,000 1.47
Ammonia 150/ton 4822 tons/yr 723,300 .22
Support heat 2.47/kscf (CH4) 427,000 kscf 1,054,000 .31
SCR Catalyst 700,000 .21
SO2 Catalyst 550,000 .16
Cooling water .60/K gal 68,300 gal 41,000 .01
Subtotal 10,979,000 3.27
CREDITS:
H2SO4 product $50/ton 106,900 tons/yr (5,345,000) (1.60)
Heat recovered $1.49/MBtu 1.58 X 10* Mbtu (2,345,200) (.70)

Subtotal (7,699,200) (2.30)
Net Total 3,279,800 .97
465
References
1. D J . Collins, R. Ricci, C.H. Speth, and R.E. Bolli, "Initial Operating Experience of the
SNOX Process," presented at EPA/EPRI SO2 Control Symposium, Washington D . C ,
December 1991.
2. W.H. Kingston, R.E. BolH, R.J. Evans, and M.J. Hyland, "Economic Analysis of the
SNOX Process," presented at International Joint Power Generation Conference, Atlanta, GA,
October 1992.
CAPTURE OF GREENHOUSE GASES BY NOVEL AEROGEL SORBENTS

PREPARED BY SOL-GEL TECHNOLOGY
Y o s r y A. A t t i a
The A t t i a A p p l i e d S c i e n c e s I n c . , TAASI L a b o r a t o r y
1445 Summit S t r e e t , Columbus, O h i o 4 3 2 0 1
ABSTRACT
TAASI i s currently investigating the potential commercial

development of advanced s p e c i a l t y aerogel m a t e r i a l s for t h e capture
of w a s t e g a s e s from t h e c o m b u s t i o n o f f o s s i l f u e l . T y p i c a l g a s e o u s
e m i s s i o n s from t h e c o m b u s t i o n o f c o a l , p e t r o l e u m , and n a t u r a l g a s
a r e : c a r b o n d i o x i d e (CO2) , c a r b o n m o n o x i d e (CO) , n i t r o g e n o x i d e s ( N O ^ ) ,
and s u l f u r dioxide(SO2) . T h e s e g a s e s a r e blamed f o r e n v i r o n m e n t a l
p r o b l e m s such a s a c i d r a i n , g l o b a l warming, and i n c r e a s e d t o x i c i t y
o f b r e a t h i n g a i r ( d u e t o CO e m i s s i o n ) .
TAASI's p r o p o s e d a p p l i c a t i o n of t h e a e r o g e l s o r b e n t s i s on t h e
particulate-free gases (i.e., ash, dust, and smoke particulates
will be filtered out first) , and t h u s the dry solid gel-gas
products should not constitute hazardous materials, but
commercially re-usable products as f e r t i l i z e r . For example in a
power p l a n t a p p l i c a t i o n , t h e a e r o g e l s o r b e n t w i l l be p l a c e d after
t h e p a r t i c u l a t e c o n t r o l s y s t e m (ESP o r b a g h o u s e ) .
The o b j e c t i v e o f t h i s i n v e s t i g a t i o n was t o d e m o n s t r a t e the
f e a s i b i l i t y of using aerogel materials t o capture green house gases
s u c h a s CO2, SO2 a n d NO^. T h e p r e l i m i n a r y t e s t r e s u l t s o f this
investigation are reported in t h i s paper.
INTRODUCTION
The u t i l i z a t i o n o f f o s s i l f u e l s ( c o a l , o i l and g a s ) i s faced

w i t h an imminent t h r e a t , u n l e s s f e a s i b l e methods ( s u c h a s t h o s e
p r o p o s e d h e r e ) h a v e b e e n d e v e l o p e d t o r e d u c e t h e e m i s s i o n s o f CO^,
CO, SO2 a n d NO^, w h i c h a r e p r o d u c e d b y t h e c o m b u s t i o n o f fossil
fuel. These g a s e s are blamed for environmental problems such as
a c i d r a i n , g l o b a l warming, and i n c r e a s e d t o x i c i t y o f b r e a t h i n g a i r
( d u e t o CO e m i s s i o n ) . I n t h e a b s e n c e o f a v i a b l e t e c h n o l o g y for
reducing the emission of these gases into the atmosphere,
a l t e r n a t i v e e n e r g y s o u r c e s , such a s s o l a r , n u c l e a r and w i n d , will
e i t h e r d i s p l a c e or s e v e r e l y reduce the use of f o s s i l f u e l s . This
may r e s u l t i n w a s t i n g v a s t e n e r g y r e s o u r c e s d u e t o t h e i n a b i l i t y t o
u t i l i z e them i n an e n v i r o n m e n t a l l y a c c e p t a b l e way. C e r t a i n l y h i g h
s u l f u r c o a l s a r e f a c i n g t h e more i m m e d i a t e t h r e a t .
T h e c u r r e n t l y a v a i l a b l e c o m m e r c i a l t e c h n o l o g y f o r r e d u c i n g SO2
a n d NO^ e m i s s i o n s f r o m p o w e r p l a n t s i s wet scrubbing. However,
since this technology is costly and c r e a t e s hazardous slurry
w a s t e s , i t h a s n o t found w i d e a c c e p t a n c e from t h e power u t i l i t i e s .
Dry s o r b e n t injection technologies seem t o be more promising,
h o w e v e r , t h e y t o o p r o d u c e h a z a r d o u s w a s t e s . The d r y s o r b e n t s a r e
i n j e c t e d e i t h e r i n t h e c o m b u s t i o n f u r n a c e (1204C) , t h e e c o n o m i z e r
zone(538C), or the "cool side" ducts (70C) . T y p i c a l sorbents
468
include finely ground limestone, dolomite, hydrated lime, sodium

bicarbonate and sodium sesquicarbonate. The sorbents react with S O 2
emissions to form solid products such as CaS04 or Na2S04, which are
then removed with the coal ash or with the dust by the particulate
collection system(e.g., electrostatic precipitator or baghouse),
depending on the point of injection. Figure 1 shows the possible
dry sorbent injection points in the power plant.
The potential problems with the above mentioned dry sorbents
are: 1) inefficient sorbent utilization, and 2 ) formation of
hazardous wastes. To increase utilization rate of the sorbent,
finer particle size is used. However, finer particles are more
easily carried out of the reaction bed by the flue gas and as a
consequence, their reaction time is shortened leading to incomplete
reaction and inefficient utilization of the sorbent.
The main objective of this work was to investigate the
feasibility of using aerogel materials to capture waste gases such
as S O 2 , NO^, C O 2 , from the utilization of fossil fuels. Aerogels
have not been used as sorbents for these gases before.
Calcium Calcium Calcium

Sorbent Sorbent Sorbent
P r o p o s e d TAASI
Aerogel s o r b e n t s
Burner Zone
Disposal Recycle
With Calcium Based P r o c e s s e s
Sodium S o r b e n t
Figure 1 Dry s o r b e n t p r o c e s s f o r c a p t u r i n g
w a s t e f l u e g a s e s i n a power p l a n t
469
TECHNICAL BACKGROUND
Perhaps t h e most w i d e l y s t u d i e d g a s c a p t u r e c a s e s by dry

sorbents in recent years, are those involved in the desulfurization
(and t o a l e s s e r e x t e n t d e n i t r i f i c a t i o n ) of flue gases produced
from c o a l c o m b u s t i o n . The s o r b e n t i s u s e d t o a d s o r b a t about
150C f r o m t h e f l u e g a s e s b e f o r e r e m o v a l o f d u s t . A s a r e s u l t o f
evaporation of added moisture or from lime, the temperature
d e c r e a s e s t o a b o u t 5 0 C a t w h i c h a d s o r p t i o n o f SO2 b e g i n s [1].
Typical sorbents include finely ground limestone, dolomite,
h y d r a t e d l i m e , sodium b i c a r b o n a t e and s o d i u m s e s q u i c a r b o n a t e . The
s o r b e n t r e a c t s w i t h SO2 e m i s s i o n s t o f o r m a s o l i d m a t e r i a l , i.e.,
CaSO^ o r Na2S0^, which is then captured by the particulate
c o l l e c t i o n system, e . g . , an e l e c t r o s t a t i c p r e c i p i t a t o r (ESP) o r
baghouse. Some c a l c i u m a n d s o d i u m b a s e d d r y s o r b e n t injection
p r o c e s s e s may u s e a f l u e g a s h u m i d i f i c a t i o n s y s t e m t o i m p r o v e ESP
p a r t i c u l a t e c o l l e c t i o n performance , increase sorbent u t i l i z a t i o n
a n d / o r t o e l i m i n a t e a brown plume s o m e t i m e s formed when i n j e c t i n g
sodium compounds.
S m i t h [ 2 ] p r o v i d e d an e x c e l l e n t o v e r v i e w o f t h e dry s o r b e n t
i n j e c t i o n t e c h n i q u e s which i s l i b e r a l l y and f r e q u e n t l y u s e d i n t h i s
t e c h n i c a l background. According t o Smith, four general approaches
have been e x t e n s i v e l y i n v e s t i g a t e d , and a r e c u r r e n t l y a t v a r y i n g
l e v e l s o f d e v e l o p m e n t and commercial a v a i l a b i l i t y . T h e s e a r e :
(a) i n j e c t i o n o f l i m e s t o n e o r h y d r a t e d l i m e s o r b e n t s i n a 2200F
(1204^0) zone;
(b) economizer injection of calcium hydrate (hydrated lime)
s o r b e n t i n 1000F(538C) zone;
(c) low temperature duct i n j e c t i o n of calcium hydrate a t high
r e l a t i v e h u m i d i t y a t 160F(71C) ;
(d) low temperature duct i n j e c t i o n of sodium based s o r b e n t s at
250-350F(121-177C) .
Of t h e s e a p p r o a c h e s , l i m e s t o n e i n j e c t i o n i s c o n s i d e r e d t o b e
c o m m e r c i a l l y p r o v e n . The s o d i u m - b a s e d p r o c e s s e s a r e r a n k e d n e x t i n
commercial availability. Figure 1 shows how injection is
a c c o m p l i s h e d i n t h e h i g h , mid and low t e m p e r a t u r e r e g i o n s o f a
coal-fired u t i l i t y boiler system.
I n j e c t i o n I n s i d e t h e Combustion F u r n a c e ; The s o r b e n t s w h i c h h a v e
been investigated to date are naturallly occurring limestone/
dolomite or t h e i r hydrated derivatives. Injected as a fine dry
powder i n t o t h e f u r n a c e , t h e s e s o r b e n t s undergo t h e f o l l o w i n g 2 -
step reaction:
heat
Limestone : CaCO^ > CaO + CO2
Calcium Hydroxide: Ca (OH) 2 ^^^^ > CaO + H20(g)
Then : CaO + SO2 + 0 . 5 O2 > CaSO^
The c a l c i t e c o m p o n e n t s o f d o l o m i t e s o r h y d r a t e d d o l o m i t e s u n d e r g o
the same r e a c t i o n s . Thermodynamically, CaSO^ i s not stable at
temperatures 2300F (1260C) i n an e n v i r o n m e n t t y p i c a l of high
470
s u l f u r c o a l - f i r e d c o m b u s t i o n p r o d u c t s , i . e . 2 0 0 0 - 4 0 0 0 ppm SO2 [ 2 ] .
H o w e v e r , t h e l o w e r t e m p e r a t u r e l i m i t f o r t h e f o r m a t i o n o f CaSO^
depends on complex i n t e r a c t i o n s between s u l f a t i o n k i n e t i c s , c r y s t a l
g r o w t h , s i n t e r i n g , and t h e b u i l d up o f a b a r r i e r p r o d u c t l a y e r o f
CaSO^ o n t h e s u r f a c e o f t h e r e a c t i v e C a O .
I n j e c t i o n Outside t h e Combustion Furnace; I n j e c t i o n of t h e s o r b e n t s

o u t s i d e t h e f u r n a c e a t 1000F (538C) , g a v e a s i m i l a r c a p t u r e r a t e
t o i n j e c t i o n i n s i d e t h e furnace w i t h commercial h y d r a t e s , and a
s i g n i f i c a n t l y b e t t e r performance with s p e c i a l l y prepared sorbents
( o n l y h y d r a t e s ) . I n j e c t i o n a t t h e s e m o d e r a t e t e m p e r a t u r e s may n o t
only result in higher sorbent u t i l i z a t i o n , but also facilitates
i n j e c t i o n due t o t h e small c r o s s s e c t i o n ( d e n s e r , h i g h e r velocity
g a s ) , a n d a b i l i t y t o i n s e r t i n j e c t i o n g r i d s . At t h e s e temperatures
SO2 a p p e a r s t o r e a c t v e r y r a p i d l y a n d d i r e c t l y w i t h Ca (OH) 2,
Ca (OH) 2 + SO2 = CaSOj + H 2 0 ( g )
The f o r m a t i o n o f s u l f i t e h o w e v e r , h a s t o c o m p e t e w i t h the reaction

b e t w e e n a b u n d a n t CO2 a n d Ca (OH) 2 t o f o r m CaCOj,*
Ca (OH) 2 + CO2 = CaCOj + H 2 0 ( g )
Therefore: 1 - B e l o w 1000F (538C) , b o t h s u l f i t e and c a r b o n a t e

occur, but s u l f i t e formation dominates.
2 - A b o v e 1 0 0 0 F (538C) , d e h y d r a t i o n o f Ca(OH)^
a c c e l e r a t e s w i t h c a r b o n a t i o n and t h e d e h y d r a t i o n
occurring at the expense of s u l f i t e formation.
Among t h e i m p o r t a n t p a r a m e t e r s i n f l u e n c i n g t h e SO2 r e m o v a l
efficiency by all methods of sorbent injection are sorbent
t y p e , s u r f a c e a r e a , and i n j e c t i o n t e m p e r a t u r e . The amount o f s o r b e n t
r e q u i r e d f o r a g i v e n removal l e v e l depends on t h e c o n c e n t r a t i o n o f
SO2 g a s , a n d t h e s o r b e n t e f f i c i e n c y w h i c h i s s t r o n g l y d e t e r m i n e d b y
t h e s u r f a c e a r e a and p o r o s i t y . T a b l e 1, l i s t s t y p i c a l p h y s i c a l and
chemical properties of the various commercially available sorbents.
From t h i s T a b l e , t h e p a r t i c l e s i z e o f t h e s o r b e n t p o w d e r ranges
from 1-37 m i c r o n s , w h i l e t h e s u r f a c e a r e a r a n g e s b e t w e e n 2 0 t o 1
mVg. I t i s important t o note t h a t t h e proposed a e r o g e l materials
c a n h a v e s u r f a c e a r e a s f r o m 6 0 0 t o 1 6 0 0 mVg, w h i c h i s m u c h h i g h e r
than f o r any commercial s o r b e n t u s e d t h u s f a r f o r SO2 c a p t u r e .
Therefore the aerogels are expected t o be extremely effective
sorbents.
E f f e c t o f S o r b e n t P o r o s i t y o n SO^ R e m o v a l An i m p o r t a n t conclusion
from p r e v i o u s l y c i t e d s t u d i e s i s t h a t f u r t h e r i m p r o v e m e n t s with
c o m m e r c i a l l y a v a i l a b l e s o r b e n t m a t e r i a l s h a s r e a c h e d a l i m i t , and
no l a r g e i n c r e a s e s a r e a n t i c i p a t e d w i t h f u r t h e r work [ 2 ] . However
n e w s o r b e n t s a n d p r o c e s s e s a p p e a r t o h o l d p r o m i s e f o r e n h a n c i n g SO2
r e m o v a l . T h e i m p r o v e d SO2 r e m o v a l i s e x p e c t e d t o d e p e n d o n t h e
p o r o s i t y of t h e sorbent, which in turn i s r e l a t e d t o i t s specific
surface area.
471
Table 1: Typical Calcium-Based Sorbent Properties

( a d a p t e d from r e f . 2 )
Chemical Physical
Analvsis Wt.% Properties SO2
Removal
Particle Surface
Type Formula Ca Mg Size urn area m^/g %
Limestone CaCOj 37-40 0.4-0.5 7.0-13a 1.0-6.Ob 25-40
Dolomite CaCOj-MgCOj 21-25 11-12 12-37a 0.5-1.Ob 40-60
High calcium Ca(OH)2 48-52 0.2-1.4 2.0-4.0 12-21 4 0-60

hydrate
Atmospheric hydrated Ca(0H)2*Mg0 28-30 18-19 14-20 10-21 60-80

dolomite (monohydrated)
Pressure hydrated
dolomite (dihydrate) Ca (OH) 2' 29-30 16-18 1.0-4.0 19-20 60-80
Mg(0H)2
a.Typical grind (size) range t e s t e d t o date.

b . L i m e s t o n e and d o l o m i t e a l s o v a r y i n g r a i n s t r u c t u r e , w h i c h h a s
g r e a t e r i m p a c t on s o r b e n t u t i l i z a t i o n t h a n raw s u r f a c e a r e a s ,
c . I n l e t SO2 = 2 5 0 0 p p m , C a / S = 2 .
A s m e n t i o n e d e a r l i e r , SO2 c a n b e r e m o v e d f r o m t h e f l u e g a s e s
by a d d i n g c a l c i u m - b a s e d s o r b e n t a c c o r d i n g t o t h e f o l l o w i n g c h e m i c a l
reaction;
CaO + SO2 + 0 . 5 O2 = CaSO^
E l e c t r o n m i c r o s c o p e e x a m i n a t i o n [3] showed t h a t t h i s r e a c t i o n t a k e s
p l a c e o n l y w i t h i n a t h i n l a y e r on t h e o u t e r s u r f a c e o f t h e s o r b e n t
p a r t i c l e s . Thus t h e f i n e r t h e p a r t i c l e t h e h i g h e r t h e u t i l i z a t i o n
r a t e of the sorbent. However, finer particles a r e more easily
c a r r i e d o u t o f t h e bed by t h e f l u e g a s ; a s a c o n s e q u e n c e , their
reaction time is shortened leading to incomplete reaction and
i n e f f i c i e n t u t i l i z a t i o n o f t h e s o r b e n t . To s o l v e t h i s p r o b l e m a
method of a g g l o m e r a t i n g f i n e l i m e s t o n e p a r t i c l e s w i t h some a d h e s i v e
s u b s t a n c e s , h a s b e e n d e v e l o p e d and u s e d i n China [ 3 , 2 3 ] . T h i s is
c a l l e d s y n t h e t i c Ca-based sulfur sorbent with high r e a c t i v i t y .
For n a t u r a l l i m e s t o n e , r e a c t a n t g a s e s d i f f u s e i n t o p a r t i c l e s
o n l y t h r o u g h t h e s m a l l p o r e s a m o n g CaO g r a i n s . I n t h e p r o c e s s o f
d i f f u s i o n , SO2 a n d O2 r e a c t w i t h CaO g r a i n s t o p r o d u c e s o l i d CaSO^
w h i c h t h e n c o v e r s t h e s u r f a c e o f CaO g r a i n s . I n a s h o r t t i m e t h e s e
small pores are f i l l e d , which l i m i t s the d i f f u s i o n of reactant
g a s e s i n t o t h e p a r t i c l e s . S o t h e o v e r a l l CaO c o n v e r s i o n r a t e o f
n a t u r a l l i m e s t o n e p a r t i c l e s i s v e r y low. However, w i t h synthetic
s o r b e n t s w h i c h a r e p r e p a r e d by a g g l o m e r a t i n g s m a l l p a r t i c l e s of
limestone with a binder, reactant gases (SO2 a n d O2) n o t only
directly diffuse into grain groups near the surface, but also
directly penetrate to internal groups through the large pores
472
between the grain groups. This i s b e n e f i c i a l for increasing the

o v e r a l l CaO c o n v e r s i o n r a t .
A c t i v a t e d c a r b o n ( c o k e ) h a s b e e n u s e d i n Germany [ 1 , 5 ] , to
a d s o r b SO2 f r o m h o t f l u e g a s e s i n t h e p r e s e n c e o f O2 a n d H2O v a p o r
according to the following reaction:
2 SO2 + O2 + 2 H2O v a p = 2 H2S0^
Sulfuric acid (H2S0^) is later desorbed (released) from the

activated carbon by heating with hot sand according to the
following reaction:
2 H2S0^ + C = 2 H2O + CO2 + 2 SO2
The d e g r e e o f d e s u l f u r i z a t i o n a c h i e v e d by t h i s m e t h o d h a s n o t b e e n
reported. Activated carbon is expected to capture gases by a
physical adsorption mechanism as there are no chemisorption
mechanisms a v a i l a b l e .
Because of the obvious b e n e f i t s of having porous agglomerates

of the calcium based sorbents, or porous activated carbon, in
i n c r e a s i n g t h e e f f i c i e n c y o f SO2 c a p t u r e a n d r e a c t i v i t y [ 1 - 5 ] , w e
b e l i e v e t h a t a e r o g e l s c o n t a i n i n g CaO a n d / o r o t h e r m e t a l l i c o x i d e s
in t h e i r structure, will b e much m o r e e f f i c i e n t sorbents than
calcium based powders, agglomerates, or a c t i v a t e d carbon, due t o
the aerogel's e x t r e m e l y h i g h p o r o s i t y , h i g h s u r f a c e a r e a , and t h e
i n c o r p o r a t e d m e t a l l i c o x i d e s . A l s o , a e r o g e l can be molded t o any
s h a p e and s i z e and t h u s a r e more f l e x i b l e than t h e powder or
agglomerate.
Preparation of Aerogels:
P r o d u c t i o n of s i l i c a a e r o g e l s h a s been d e v e l o p e d and d i s c u s s e d
by several investigators [7-10]. Optimization of the various
parameters i n v o l v e d was a c h i e v e d , a n d improvements of t h e p r o c e s s
were d e v e l o p e d . The method was a l s o e x t e n d e d from p u r e s i l i c a to
v a r i o u s b i n a r y and t e r n a r y s y s t e m s . The v e r y l a r g e s u r f a c e area
that is associated with these materials, currently of several
h u n d r e d m V g ( a p o r e d i a m e t e r d i s t r i b u t i o n e x t e n d i n g f r o m t h e nm t o
t h e um r a n g e ) m a d e t h e m a t t r a c t i v e f o r s e v e r a l a p p l i c a t i o n s , e . g . ,
the f i e l d of c a t a l y s i s [8,13,14,15].
I t i s w e l l known t h a t t h e t e x t u r e and m e c h a n i c a l p r o p e r t i e s o f
the produced aerogels are influenced by several parameters.
C o m p o s i t i o n , pH, t e m p e r a t u r e , a n d t h e a g i n g p e r i o d a r e t h e m o s t
important parameters which a f f e c t g e l a t i o n . However, h y p e r c r i t i c a l
e v a c u a t i o n i n an a u t o c l a v e , t o p r o d u c e h i g h l y p o r o u s monolithic
a e r o g e l s i s m a i n l y a f f e c t e d by p r e s s u r e , t e m p e r a t u r e , and t h e r a t e
of h e a t i n g and c o o l i n g . In t h e e x p e r i m e n t s of Henning [16] and
Zarzycki [17] e x t r a a l c o h o l was added i n t h e a u t o c l a v e t o m a i n t a i n
t h e s a t u r a t i o n p r e s s u r e o f t h e l i q u i d . To o b t a i n m o n o l i t h i c b o d i e s ,
w i t h l o w e r d e n s i t y and h i g h p o r o s i t y , h i g h l y u n i f o r m t e m p e r a t u r e
inside the autoclave vessel i s required. Oversaturation at a cooler
place in the autoclave during heating causes condensation,
r e s u l t i n g in undersaturation, which can g i v e r i s e t o b o i l i n g of t h e
473
l i q u i d e l s e w h e r e . However, i n t h e t e s t s of P o e l z and R i e t h m u l l e r
[18] as well as in those of Van L i e r o p [9] any b o i l i n g was
completely s u p p r e s s e d by i n t r o d u c i n g , at the beginning of the
autoclave treatment, a pressured inert gas ( e . g . N ^ o r Ar) . The
a p p l i c a t i o n of t h i s pressure prevents bubble formation or b o i l i n g
a l l t h e way up t o t h e c r i t i c a l p o i n t . Not o n l y i s t h e g e l not
submerged in e x c e s s a l c o h o l b e f o r e c l o s i n g t h e a u t o c l a v e vessel,
but the autoclave i s kept closed u n t i l the temperature reached
300C ( t h e c r i t i c a l point of ethanol = 243C and 63 b a r ) . The
p r e s s u r e i n c r e a s e s due t o t h e e x p a n s i o n of i n e r t g a s a s w e l l a s t o
t h e e v a p o r a t i o n o f t h e l i q u i d . A t t h e m a x i m u m t e m p e r a t u r e ( 3 00C)
t h e p r e s s u r e o f t h e a u t o c l a v e i s r e l e a s e d . The d e c o m p r e s s i o n r a t e
s t r o n g l y d e p e n d s on t h e s i z e o f t h e g e l , ( e . g . f o r g e l i n t e s t t u b e s
o f 1 5 mm d i a m e t e r t y p i c a l l y 1 5 0 b a r / h r w a s u s e d , f o r g e l s o f 80mm
d i a m e t e r t h e d e c o m p r e s s i o n was r e d u c e d t o 15 b a r / h r ) . O n l y a f t e r
t h e d e c o m p r e s s i o n i s c o m p l e t e d , i s t h e s y s t e m a l l o w e d t o c o o l down
t o room t e m p e r a t u r e .
Currently, TAASI is engaged in programs aimed at the
production of highly porous monolithic aerogels for various
applications, and t h e p r o d u c t i o n o f PZT c e r a m i c m a t e r i a l with
r e l a t i v e l y h i g h d i e l e c t r i c c o n s t a n t and l o w e r d i s s i p a t i o n factor,
from a s o l - g e l p r o c e s s [ 2 1 , 2 2 ] . The r e s u l t s o f o u r r e s e a r c h , w h i c h
are being prepared for publication, showed t h a t t h e mechanical,
e l e c t r i c a l , and s t r u c t u r a l ( i . e . g r a i n growth) p r o p e r t i e s , a s w e l l
as the density and p o r o s i t y of the produced materials, are
influenced by the addition of organic polymers, calcination
t e m p e r a t u r e , and a l k o x i d e t o s o l v e n t r a t i o b e f o r e g e l a t i o n . Jean
and Ring [ 1 9 ] s t u d i e d t h e e f f e c t o f a d d i t i o n o f p o l y m e r s (hydroxy-
propyl c e l l u l o s e ) d u r i n g p r e c i p i t a t i o n o f TO2 p a r t i c l e s b y t h e
sol-gel process. Monodisperse and spherical titanium dioxide
powders were p r e p a r e d by t h e h y d r o l y s i s of t i t a n i u m t e t r a e t h o x i d e
in ethanol with the a d d i t i o n of d i f f e r e n t c o n c e n t r a t i o n s of 2 types
o f HFC p o l y m e r s (MW 3 0 , 0 0 0 a n d MW 6 0 , 0 0 0 ) . Precipitation was
c o n d u c t e d i n a g l o v e b o x u n d e r d r y N2 a t m o s p h e r e a t 2 5 C . When t h e
powders p r e c i p i t a t e d , t h e s o l u t i o n became c l o u d y . The t i m e n e e d e d
for observation of the turbid s o l u t i o n increased with a decrease in
c o n c e n t r a t i o n o f e i t h e r r e a c t a n t and w i t h an i n c r e a s e i n p o l y m e r
c o n c e n t r a t i o n . Powder s i z e was d e t e r m i n e d by t h e d i r e c t measurement
of t r a n s m i s s i o n e l e c t r o n microscopy (TEM) p h o t o g r a p h s u s i n g an
image a n a l y z e r . The c r i t i c a l p o l y m e r c o n c e n t r a t i o n r e q u i r e d for
stabilization of these powder s u s p e n s i o n s was d e t e r m i n e d . The
r e s u l t s showed t h a t t h e p a r t i c l e p a c k i n g becomes more d e n s e and
m o r e u n i f o r m a s t h e p o l y m e r (MW 3 0 , 0 0 0 ) c o n c e n t r a t i o n i s i n c r e a s e d .
I n a d d i t i o n , t h e m e a n p a r t i c l e s i z e d e c r e a s e s a s t h e p o l y m e r (MW
30,000) concentration i s increased. This e f f e c t has been described
by t h e l a t t i c e t h e o r y of p o l y m e r s o l u t i o n s [ 2 0 ] .
DESCRIPTION OF T A A S I ' S CONCEPT
The n o v e l c o n c e p t d e s c r i b e d h e r e i n v o l v e s t h e u s e o f a d v a n c e d
s p e c i a l i z e d aerogel materials for the capture of gaseous
w a s t e s from t h e u t i l i z a t i o n o f f o s s i l f u e l s . As m e n t i o n e d e a r l i e r ,
t h e a e r o g e l m a t e r i a l s c a n h a v e o v e r 90% p o r o s i t y , v e r y l o w d e n s i t y ,
extremely high surface area ( 6 0 0 - 1 6 0 0 mVg) compared w i t h dry
474
s o r b e n t powder ( 1 - 2 0 mVg) / and can be p r e p a r e d i n t h e a p p r o p r i a t e

chemical composition to capture the gaseous species in question.
Because of t h e s e p r o p e r t i e s , t h e s e a e r o g e l s can capture (sorb)
several times t h e i r weight of the gaseous e f f l u e n t s . When the
e f f l u e n t s are captured, t h e g e l s can be r e - g e n e r a t e d for further
re-use and t h e gases may b e further separated and utilized.
Alternatively, gas-gel reaction products w i l l lead to the formation
of materials which should be suitable for utilization as
f e r t i l i z e r s or building m a t e r i a l s .
TAASI's p r o p o s e d a p p l i c a t i o n of t h e a e r o g e l s o r b e n t s i s on t h e
p a r t i c u l a t e - f r e e g a s e s ( i . e . , a s h , d u s t and smoke p a r t i c u l a t e s
w i l l be f i l t e r e d o u t f i r s t ) , and t h u s t h e dry s o l i d a e r o g e l gas
products should not constitute hazardous materials, but
c o m m e r c i a l l y r e - u s a b l e p r o d u c t s . For example, i n a power p l a n t
application, the aerogel sorbent will be placed after the
p a r t i c u l a t e c o n t r o l system(ESP or b a g h o u s e ) , a s shown i n F i g u r e 1.
The h i g h s u r f a c e a r e a ( h i g h p o r o s i t y ) a e r o g e l s w i l l b e a b l e t o
c a p t u r e t h e g r e e n h o u s e g a s e s (CO2, SO2, NO^,CO) t h r o u g h b o t h
physical and chemical sorption mechanisms as these aerogel
m a t e r i a l s w i l l c o n t a i n c o m p o n e n t s s u c h a s CaO a n d MgO i n t h e i r
structure. Reactions between the greenhouse gases and the
c o m p o n e n t s a r e w e l l k n o w n a n d w i l l f o r m p r o d u c t s s u c h a s CaSO^,
CaCO^, MgCOj, and Ca(N03)2. These reactions (as well as
p h y s i s o r p t i o n ) may b e r e v e r s e d a t h i g h e r t e m p e r a t u r e s t o d i s s o c i a t e
t h e s e c o m p o u n d s t h u s r e - g e n e r a t i n g t h e CaO & MgO c o m p o n e n t s o f t h e
aerogel and r e l e a s i n g these gases in a controlled manner for
subsequent u t i l i z a t i o n ( f o r e x a m p l e , SO2 m a y b e u s e d t o produce
s u l f u r a n d h y d r o g e n b y t h e C l a u s p r o c e s s , a n d CO2 m a y b e c o n d e n s e d
and u s e d c o m m e r c i a l l y .
It i s important to note that the chemical composition, surface
a r e a , p o r o s i t y , s h a p e , s i z e , and p h y s i c a l s t r e n g t h o f t h e a e r o g e l s
can be customized for the particular application. The aerogel
filters will have the a b i l i t y for continuous re-use after re
generation cycles either on site or in regeneration plants.
However, a s m e n t i o n e d e a r l i e r , i f i t i s more e c o n o m i c a l l y v i a b l e t o
utilize the reacted aerogels, for example, as fertilizers or
b u i l d i n g m a t e r i a l s t h e n , r e g e n e r a t i o n w i l l not be n e c e s s a r y .
KEY EXPERIMENTAL RESULTS
The primary objective of this research program was to

ascertain whether the aerogel samples prepared in the laboratory
can adsorb t h e greenhouse g a s e s , s p e c i f i c a l l y , CO2 a n d SO2 g a s e s .
Such a d s o r p t i o n has n o t been r e p o r t e d b e f o r e . With t h a t o b j e c t i v e
met, r e s e a r c h w i l l c o n t i n u e t o r e f i n e t h e a e r o g e l p r e p a r a t i o n and
gas adsorption p r o c e s s e s t o maximize the c a p a c i t y of the aerogel t o
capture these gases.
Laboratory t e s t i n g thus far involved the following preliminary
investigations:
( 1 ) P r e p a r a t i o n o f t h e A e r o g e l S p e c i m e n s By v a r y i n g c h e m i c a l a n d
physical compositions through manipulation of the molar r a t i o of
t h e main components, t y p e of p r e c u r s e r s (chemical f e e d s t o c k ) ,
c a t a l y s t t y p e and c o n c e n t r a t i o n , and p o l y m e r t y p e and m o l e c u l a r
475
weight. Both small (200ml) and large (1500ml) monolith and

granulated aerogel specimens were prepared. The a e r o g e l s were
manufactured through f i r s t the preparation of the corresponding
alcogels by the sol-gel processing technology, and then by
subjecting the alcogels to supercritical drying to remove the
alcohol.
(2) C h a r a c t e r i z a t i o n o f t h e A e r o g e l S p e c i m e n s By m e a s u r i n g the
s u r f a c e a r e a u s i n g BET p r o c e d u r e f o r N2 a d s o r p t i o n , p o r o s i t y , and
phase composition using X-ray d i f f r a c t i o n (XRD). A l t h o u g h this
p h a s e o f work i s s t i l l o n - g o i n g , p r e l i m i n a r y s u r f a c e a r e a d a t a on
3-specimens, and XRD spectrograms were obtained. The XRD
s p e c t r o g r a m s f o r two a e r o g e l s a m p l e s 112IC and 112IL b e f o r e
a n d a f t e r a d s o r p t i o n o f CO2 a n d SO2 a r e s h o w n i n F i g u r e s 2 a n d 3 .
( 3 ) T e s t i n g t h e A e r o g e l S o r b e n t s f o r G a s A d s o r p t i o n By p a s s i n g
t h e t e s t g a s (CO2 o r SO2) o v e r t h e a e r o g e l s a m p l e e n c l o s e d i n a
s t a i n l e s s s t e e l p r e s s u r e f i l t e r v e s s e l , and r e c o r d i n g t h e c h a n g e i n
w e i g h t o f t h e a e r o g e l s a m p l e a s an i n d i c a t i o n o f t h e e x t e n t o f g a s
a d s o r p t i o n . I t was found t h a t t h e p r e s e n c e of w a t e r vapor
(steam) e n h a n c e s t h e g a s a d s o r p t i o n o f t h e p r o c e s s a s shown on
T a b l e 2 . Thus h u m i d i f i c a t i o n of t h e a e r o g e l was a t t e m p t e d f o r a few
m i n u t e s by a p p l y i n g vacuum t o t h e p r e s s u r e f i l t e r c o n t a i n i n g t h e
aerogel, which was c o n n e c t e d t o a steam generator. After the
s e l e c t e d t i m e , t h e s t e a m and vacuum were d i s c o n n e c t e d , and t h e
g a s c y l i n d e r was c o n n e c t e d t o t h e p r e s s u r e f i l t e r c o n t a i n i n g t h e
h u m i d i f i e d a e r o g e l . T h e g a s w a s a l l o w e d t o f l o w a t 1 . 0 SCFH u n d e r
a p r e s s u r e o f 1 0 p s i f o r SO2, a n d 2 0 p s i f o r CO2, f o r selected
p e r i o d s o f t i m e . P r i o r t o t h e h u m i d i f i c a t i o n and g a s adsorption
s t e p s , t h e a e r o g e l sample was e v a c u a t e d f o r a p e r i o d o f t i m e and
i t s w e i g h t was r e c o r d e d .
Table-2 E f f e c t of Water Vapor on Gas A d s o r p t i o n [ a W / W o , % ] *

by A e r o g e l s
Aerogel 1121c 1121L 1214
H2O V a p o r No Yes No Yes No Yes
CO2 NA 17.42 0. 714 3.270 NA 3.80

so^ NA 34.60 10 . 9 4 57.23 11.19 104.85
* a W= n e t w e i g h t change due t o g a s a d s o r p t i o n o n l y
Wo = i n i t i a l a e r o g e l s a m p l e w e i g h t a f t e r e v a c u a t i o n
The p r e l i m i n a r y r e s u l t s o f t h e g a s a d s o r p t i o n t e s t s f o r t h r e e
a e r o g e l s p e c i m e n s a n d t w o g a s e s (C02,S02) a r e s h o w n o n F i g u r e s 4 - 8 ,
a n d T a b l e s 3 - 8 . I t c a n b e s e e n t h a t SO2 g a s a d s o r b s r e a d i l y w i t h
a l l t h r e e a e r o g e l s o r b e n t s . The r e a c t i o n i s a l w a y s e x o t h e r m i c and
the temperatures of the adsorption r e a c t o r r i s e s significantly
d u r i n g t h e a d s o r p t i o n p r o c e s s . A e r o g e l 1121L i s s i m i l a r t o 1121C i n
composition, but it did not adsorb CO2 g a s as well. T h e XRD
spectrograms r e v e a l e d t h a t t h i s 112IL a e r o g e l already contained
476
Ca,Mg(C03)2
Caco
b.
MgO
MgO
c. CaO
7 /
20 30 40 50 60 70 80
Figure 2. X - r a y d i f f r a c t i o n s p e c t o g r a m s o f a e r o g e l 1121C
b e f o r e a n d a f t e r a d s o r p t i o n o f CO2 a n d SO2 g a s e s .
a. 1 1 2 1 L a e r o g e l a f t e r SO2 adsorption
b. 1 1 2 1 L a e r o g e l a f t e r CO2 adsorption
c. 1121L o r i g i n a l aerogel
477
Caso
MgSO
CaCO-, CaO MgO

b. /
CaCO-
/
IIr I I I 1 1 I 1I
KlXJijJ^^M^ ,
1 I ^ I I I I I I I "^f
CaC03 cao
c. / / CaCO^
~11 ~ 1 IIIIIII"IIIIIIIIIIIrr
20 30 40 50 60 70 80
Figure 3 . X-ray d i f f r a c t i o n spectograms of a e r o g e l 1121L

b e f o r e a n d a f t e r a d s o r p t i o n o f C02and SO2 g a s e s .
a. 1 1 2 1 L a e r o g e l a f t e r SO2 adsorption
b. 1 1 2 1 L a e r o g e l a f t e r CO2 adsorption
c. 1121L o r i g i n a l aerogel
478
CaC03,and t h u s i t was u n a b l e t o adsorb and r e a c t w i t h m o r e CO^ g a s .
Table-3: Adsorption Results of SO2 b y A e r o g e l 112IC
Time A W / W O Remarks
(min) (gram) %
3 4.05 18.08 i n i t i a l sample w t . : 2 2 . 4 ( g )

6 5.80 25.89 i n i t i a l t e m p . : 25C
10 6.55 29.24 water vapor adsorbed:7.75(g)
15 6.90 30.80 i.e., 34.44%
25 7.55 33.71 temp, i n c r e a s e s t o about
40 7.75 34.60 80C a f t e r w a t e r v a p o r
introduction
* AW = n eyt c h a n g e i n a e r o g e l s a m p l e w e i g h t d u e t o g a s a d s o r p t i o n
onl
Wo = i n i t i a l w e i g h t o f a e r o g e l s a m p l e a f t e r evacuation
Table-4: Adsorption Results of CO2 b y A e r o g e l 1121C
Time AW A W / W O Remarks
(min) (gram) %

6 2.95 13.35 i n i t i a l t e m p . : 2 5 C
15 3.75 16.97 i.e., 49.55%
30 3.85 17.42 temp, a f t e r water vapor
i n t r o d u c t i o n : 7 0 C
Table-5: Adsorption R e s u l t s of SO2 b y A e r o g e l 1214
(min) (gram) %

6 13.45 100.37 i n i t i a l t e m p . : 2 5 C
15 13.85 103.36 60.45%
25 14.05 104.85 temp, a f t e r water vapor
i n t r o d u c t i o n : 7 5 C
Table-6: Adsorption Results of CO2 b y A e r o g e l 1214
(min) (gram) %
3 0.50 3.80 i n i t i a l sample w t . : 16.25(g)

8 0.50 3.80 i n i t i a l t e m p . : 2 5 C
i.e., 66.46%
479
40
Aerogel 1121C
S02 Ad&orption
30 8tm Adsorption: 34.44%
i
< 20 * /
C02 AdftOfpUon
SMAm : 40.55%
ob 10
10 20 30 40 50
Time, minute
Figure 4 A d s o r p t i o n k i n e t i c s o f SO2 a n d CO2 g a s e s b y a e r o g e l

1121c after steam humidification to 34.44% of
a e r o g e l w e i g h t f o r SO2 a n d CO2 a d s o r p t i o n
respectively
80
Aerogel 1121L
70
SO2
Steam AdsorpUon: 39.43% .
60
o
50
1
<
40 -
a 30
I
20

10 C02
SUftm Adftorption: 69.39%
0 k!^^ 1 .
10 20 30 40 50
Time, minute
Figure 5 A d s o r p t i o n k i n e t i c s o f SO2 a n d CO2 g a s e s b y a e r o g e l

1121L a f t e r steam h u m i d i f i c a t i o n to 39.43% and
8 9 . 3 9 % b e f o r e SO2 a n d CO2 a d s o r p t i o n respectively
480
uo
Aerogel 1 2 1 4
120 - -
100
S02 Adsofpiion
> Steam Adsorption: 60.45%
< 80
CO
60
c
40
00
20 C02 Miorpuon
Suam Adtofpon: 66.46%
10 20 30
Time^ minute
Figure 6 A d s o r p t i o n k i n e t i c s o f SO2 a n d CO2 g a s e s on a e r o g e l

1 2 1 4 a f t e r s t e a m h u m i d i f i c a t i o n t o 60.45% and 66.46%
b e f o r e SO2 a n d CO2 a d s o r p t i o n r e s p e c t i v e l y
140
S02 Adsorption
120
AroQel 1214
o 100
5
< 80
CO Aerogel 1121L
% 60
6
'to 40 Aerogel 1121C
10 20 30 40 50
Time, minute
Figure 7 C o m p a r i s o n o f SO2 g a s a d s o r p t i o n kinetics by three
a e r o g e l s 1121C, 1121L and 1214
481
A e r o g e l 112IL was s t o r e d i n an open c o n t a i n e r . Thus i t must have

reacted with atmospheric already over the storage period.
A e r o g e l 1121C on t h e o t h e r hand was s t o r e d i n a c l o s e d c o n t a i n e r ,
t h u s i t d i d n o t r e a c t w i t h a t m o s p h e r i c CO2 t o t h e s a m e d e g r e e a s
1 1 2 I L , a n d a s a r e s u l t i t w a s a b l e t o a d s o r b CO2 g a s . A l l a e r o g e l
s a m p l e s show t h e p r e s e n c e o f c a l c i u m o r magnesium s u l f i t e s as
r e a c t i o n p r o d u c t s o f SO2 g a s a d s o r p t i o n .
Table-7: Adsorption Results of SO2 b y A e r o g e l 112IL
(min) (gram) %

6 7.35 46.23 i n i t i a l t e m p . : 2 5 C
15 8.65 54.40 i . e . , 39.43 %
25 9.10 57.23
40 9.10 57.23
Table-8: Adsorption Results of CO2 b y A e r o g e l 112IL
(min) (gram) %
3 0.35 2.12 i n i t i a l sample w t . : 16.5(g)

6 0.54 3.27 i n i t i a l t e m p . : 2 5 C
25 0.50 3.03 i . e . , 89.39 %
Of s p e c i a l n o t e i s a e r o g e l 1 2 1 4 w h i c h a d s o r b e d a b o u t 105% o f
i t s w e i g h t o f SO2 g a s , i n a d d i t i o n t o a b o u t 6 0 . 5 % o f i t s w e i g h t o f
H2O v a p o r , i.e., 165.50% adsorption capacity. However, CO^
a d s o r p t i o n w a s n o t f a v o r a b l e . T h i s may b e d u e t o t h e a d s o r p t i o n o r
a t m o s p h e r i c CO2 d u r i n g t h e o p e n s t o r a g e o f t h i s g e l a s w a s t h e c a s e
with aerogel 1121L.Investigations are on-going to clarify these
o b s e r v a t i o n s and d e f i n e t h e p a r a m e t e r s f o r m a x i m i z i n g t h e
p o r o s i t y and a d s o r p t i o n c a p a c i t y o f a e r o g e l s .
Preliminary Conclusions
T h e s e p r e l i m i n a r y r e s u l t s show t h a t :
(1) a e r o g e l s c a n a d s o r b CO2 a n d SO2 g a s e s ;
(2) by c o n t r o l l i n g t h e c h e m i c a l c o m p o s i t i o n , p o r o s i t y , and pore
s i z e s of a e r o g e l s , and p a r a m e t e r s of t h e a d s o r p t i o n p r o c e s s ,
capture of t h e s e g a s e s can be improved f u r t h e r ; and,
(3) s i m i l a r l y , t h e c a p t u r e o f o t h e r g a s e s s u c h a s NO^, CO, CH^,
H2S, e t c . , b y a e r o g e l s s h o u l d b e f e a s i b l e .
482
5
<
or
CO
10 20 30 40
Time, minute
Figure 8 Comparison of COp Gas adsorption kinetics by

three aerogels 1121C, 1121L and 1214
ECONOMIC POTENTIAL
It is difficult at this early stage of development, to

calculate the various financial parameters such as operating costs,
capital investment and the payback period with a high degree of
confidence; but, based on current laboratory procedures, a
preliminary cost estimate for a potential manufacturing plant
producing 1 million liters of aerogel per year, indicates that
these aerogel sorbents should be very competitive with current
commercial SO2 and NO^ sorbents for electric utilities for the
following reasons:
(1) Most of the fluids (alcohol,water)and the heat used in
manufacturing the aerogel will be re-cycled in the plant thus
reducing production costs significantly.
(2) On weight basis comparison,the aerogel sorbent will be more
efficient due to: (a) much higher surface area (b) much less
sorbent loss than those in powder form.
(3) Current competing sorbents become hazardous materials as they
are mixed W V I T H ash, smoke and dust, and thus additional
treatment and disposal costs of the hazardous materials must
be considered in their costs.
483
(4) Since a e r o g e l s o r b e n t s w i l l be a p p l i e d a f t e r dust/smoke

f i l t e r s , t h e y a r e n o t e x p e c t e d t o form h a z a r d o u s w a s t e s , b u t
in f a c t produce m a t e r i a l s which can be s o l d as f e r t i l i z e r s or
building materials for extra profit.
If adopted, the aerogel sorbents would have a tremendous p o s i t i v e

impact on t h e e n e r g y u t i l i z a t i o n from f o s s i l f u e l s by r e n d e r i n g
t h e i r u s e more e n v i r o n m e n t a l l y a c c e p t a b l e .
ACKNOWLEDGEMENTS
The a u t h o r g r a t e f u l l y a c k n o w l e d g e s t h e f i n a n c i a l assistance
award from t h e U.S Department of Energy, grant No. DE-FG51-
92R020214, and t h e v a l u a b l e l a b o r a t o r y a s s i s t a n c e of Mr.Mingang
Zhu.
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484
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Molec. C a t a l . , 17, (1982) 171.
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t h e E n e r g y S c e n e , S . K a l i a g u i n e a n d A. Mahay, E d i t o r s ,
E l s e v i e r , Amsterdam,(1984) 471.
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D . R . U h l m a n n a n d N . J . K r e i d l , A c a d e m i c P r e s s , New Y o r k , (1984)
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(1986) 85.
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(1983) Acad. P r e s s , New Y o r k .
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a n d C h a r a c t e r i z a t i o n o f PZT F i l m s a n d P o w d e r s , International
Symposium on A d v a n c e s i n S o l - G e l P r o c e s s i n g and A p p l i c a t i o n ,
August 24-28, 1993, Chicago, Illinois.
2 2 . M . Ahmed a n d Y . A . A t t i a , E f f e c t o f P o l y m e r s o n t h e S t r u c t u r a l
a n d E l e c t r i c a l P r o p e r t i e s o f S o l - G e l P r e p a r e d PZT C e r a m i c s ,
I n t e r n a t i o n a l Symposium on A d v a n c e s i n S o l - G e l P r o c e s s i n g and
A p p l i c a t i o n s , August 24-28, 1993, Chicago, Illinois
(in preparation).
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High S u l f u r C o a l s IV, E d i t o r s , P . R . Dugan,D.R. Q u i g l e y and
Y.A. A t t i a , E l s e v i e r , Amsterdam, (1991) 723-729.
Improvements in wet scrubbing technology developed at the Miami Fort pilot

plant
B. Lani,^ M. Babu^ and H. Johnson^
^Dravo Lime Company, 3600 Neville Road, Pittsburgh, Pennsylvania 15225.
Ôhio Coal Development Office, 77 South High Street, Columbus, Ohio 43266
ABSTRACT
Dravo Lime Company in cooperation with the Ohio Coal Development Office and
The Cincinnati Gas & Electric Company designed and constructed a Wet Flue Gas
Desulfurization Pilot Plant with a comparable scrubber rating of 0.6 - 4.5 MW. Located
at the Miami Fort Station near Cincinnati, the pilot plant has been in operation since
November, 1989. The goals of the pilot plant are two fold. The first is to develop new
scrubber technologies for high sulfur coals utilizing Thiosorbic, or
magnesium-enhanced, lime. The second is to provide technical support and retrofit
capabilities to reduce the operating costs of utilities which utilize Dravo Lime
Company's technologies.
To achieve these goals, three areas of research have been pursued at the Miami
Fort Pilot Plant
1. Improvements in conventional scrubber operation.
2. Production of salable flue gas desulfurization (FGD) by-products.
3. Enhancements to the air pollution reduction capabilities.
This paper reports the developments, chemistry and potential economic impact
in each of these areas.
INTRODUCTION
The pilot plant is located at the Cincinnati Gas & Electric Company's Miami Fort
Station in North Bend, Ohio. Construction of the plant was funded by the Ohio Coal
Development Office, The Cincinnati Gas & Electric Company and Dravo Lime
Company. The facility went into operation at the end of 1989. Continuous testing has
been conducted over the subsequent three years which has included funding from
the Department of Energy (DOE) and the Electric Power Research Institute (EPRI) in
addition to the above sponsors.
486
Figure 1 details the components of the facility which are available for FGD
studies. A slipstream from Miami Fort Unit No. 7 downstream of the precipitator
supplies the flue gas to the pilot plant. The facility includes all components of a typical
wet lime FGD system, including flue gas scrubbing and dewatering equipment,
thickeners and a belt filter, lime reagent preparation equipment and various other
equipment for preparing and metering chemical additives for the scrubbing system.
PILOT PLANT COMPONENTS
1. Lime Silo
2. LimeSlaker
3. Lime Slurry Tank
4. Recycle Sluriy Tank
5. High Velocity Scrubber 3Fr.
6. Low Velocity Scrubber 4FT.
7.12 Thickener
8,8 Thickener
9. Fitter Feed Tank
10. Filter Belt
11. Thickener Overflow Tank
12. Flue Gas Fan
13. Polymer Feed System
17. Oxidizer
Figure 1. Miami Fort pilot plant.
The plant has two 40 foot tall scrubbing towers, one 4 foot and the other 3 foot
in diameter. Aside from enabling the capability to simulate various flue gas velocities
within the scrubbers, the towers allow testing of both countercurrent and cocurrent
modes of gas-liquid contact. Varying degrees of contact between the flue gas and the
scrubbing liquor can be accomplished by operating any number of the three available
recycle pumps, changing the location of the spray nozzles within the tower, or by
installing sieve trays or packing. Liquid to gas (L/G) ratios of 15 to 225/1000 ACFM
can be achieved.
The booster fan utilized for moving the slipstream is located between the access
point downstream of the utility's precipitator and the inlet to the pilot plant scrubber
modules. Flue gas flow rates of 2000 to 15000 ACFM at 300 F, equivalent to 0.6 to
4.5 MW, can be achieved by a controlling damper on the inlet to the fan and by
487
sheave modifications to the drive mechanism of the fan. A venturi flow meter
immediately downstream of the fan is utilized to monitor the gas flow rate for
automatic damper control. Boiler load changes between 260 to 530 MW as well as the
type of coal being fired influence the composition of the flue gas. Typical volumetric
concentration ranges are: 5.5-10.5% for Og, 700 to 2800 ppm for SOg and 500 to 750
ppm for An on-site SOg spiking system, capable of vaporizing up to 150 lb
SOg/hour, enables control of the SOg concentration to the inlet of the scrubber.
Typically, this concentration is maintained at 2500 ppm during testing.
A continuous emissions monitoring system, analyzes the flue gas entering and
leaving the scrubber. Vacuum pumps are utilized to extract the sample gas from the
process stream through heated sample probes which are maintained at 350 "F. Heat
traced sample lines transport the gas from the probe to the precooler which reduces
the gas temperature to 40 F. Upon exiting the precooler, the gas sample passes
through a vacuum pump into a refrigerated dryer system. The dry gas is divided into
three streams for analysis of O^, SOg and NO^ concentrations. A matched set of gas
analyzers are maintained for the inlet and outlet gas analysis. Servomex -
Sybron/Taylor Model 540A Paramagnetic Analyzers, ranged 0-25% monitor the 0^
concentrations. Western Research & Development, Model 721AT2 Ultraviolet
analyzers, ranged 0-1000. 0-3500 ppm on the inlet and 0-500, 0-1000 ppm for the
outlet determine SOg concentrations. Thermo Environmental Instruments, Inc., Model
44 Chemiluminescent Analyzers, ranged 0-1000 ppm analyze for both NO and NO^.
Due to the low concentrations of NOg, typically less than 10 ppm, these analyzers
remained in the NO,^ monitoring mode. During the calibration of the analyzers, the zero
and calibration gases passed through the sample conditioning system before entering
the analyzers. Mid-span gases are utilized to verify the linearity of the analyzers
between the zero and span calibration gases.
The scrubber recycle tank design enables operation with slurry suspended solids
concentrations far lower than present designs. These concentrations are typically in
the 2-4 wt.% range. A variable speed agitator provides a more gentler agitation than
present designs and allows variations in agitation level.
Various auxiliary equipment is available for process modifications. A regeneration
tank oxidizer tower and hydroclone separators are utilized during the production of
gypsum and magnesium hydroxide from the scrubbing process. An 800 gallon mix
tank is utilized for preparing polymer solutions for dewatering studies or for
preparation of chelate solutions for NO^ reduction testing. Accompanying metering
pumps are utilized to control the flow of these additives into the process liquor. A dry
powder feed system incorporating a day bin located above a screw feeder meters dry
chemical additives into the process when required.
The dewatering system includes two thickeners, 8 foot and 12 foot in diameter,
respectively. Total unit area is 51 ft^/TPD of dry sludge when operating at 3 MW of flue
gas from a 2.75% sulfur coal, The thickener underflow is periodically pumped for
storage in the filter feed tank. From this tank, the slurry is filtered on a horizontal belt
filter with an active filter area of lOft^. The filter has provisions for three countercurrent
cake washes. All filtrate collected from the belt is returned to the scrubber system via
the thickener overflow tank.
488
Analysis of the pilot plant performance is accomplished through an on-site

analytical lab and a computerized data acquisition system. Liquid chemistry data is
obtained around the clock by technicians which staff the plant's analytical lab. A data
base of the lab analysis is maintaining on one of the three on-site computers.
Scrubber operating data is displayed continuously on a computer with 30 second
updates. Various menu driven display screens enable operators to monitor
sub-systems of the pilot plant as well as the overall process. The 30 second updates
are stored in a process data base as 5 minute averages. Both the lab and process
data bases are transferred electronically to Dravo Lime Company's Research Center
in Pittsburgh, where additional analysis and evaluation are performed.
IMPROVEMENTS IN CONVENTIONAL THIOSORBIC SCRUBBER OPERATION
The Thiosorbic, or magnesium-enhanced, lime wet flue gas desulfurization (FGD)

process was developed by Dravo Lime Company in the early 1970's. It was
determined that the addition of magnesium oxide (MgO) to high calcium lime
improved the SOg capture of the scrubbing liquor and significantly reduced scaling
within scrubbers. The process is most effective for scrubbing flue gases resulting from
the combustion of high sulfur coals. Currently, twenty electric utility units with a
combined generating capacity of 8500 MW utilize the Dravo technology. An additional
4900 MW of magnesium-enhanced lime scrubbing capacity will be added by utilities
planning to meet the Phase I requirements of the Clean Air Act Amendments of 1990.
The chemistry of the Thiosorbic process takes advantage of the catalytic effect
of magnesium. MgO when added to the scrubber liquor forms a soluble alkaline salt,
magnesium sulfite (MgSOg). This species rapidly neutralizes the absorbed SOg by
forming magnesium bisulfite (Mg(HS03)2) and thereby provides the scrubber liquor
greater capacity in absorbing SOg compared to systems where MgSOa is not present.
The addition of Thiosorbic lime to the process which is composed of -f-90% calcium
oxide (CaO) and 4 to 8% MgO precipitates the absorbed SOg as calcium sulfite
(CaSOa) and regenerates the Mg(HS03)2 to MgSOa. A detailed description of the
chemical reactions which take place in the Thiosorbic process are detailed in Figure
2. When the amount of MgSOg in the scrubber liquor significantly exceeds the
amount of SOg in the flue gas with which the liquor is contacted, SOg removal
depends solely on the degree of contact between the two. Removal is not dependent
upon the dissolution of solids as in limestone systems. Therefore, the Thiosorbic
scrubbing process can achieve SOg removals of 98-99% at practical liquid to gas
(L/G) ratios and scrubber tower gas pressure drops.
Aside from the excellent SOg removal capability, scaling of scrubber internals with
hard calcium compounds is eliminated. The highly soluble magnesium compounds
in the liquor increase the sulfite concentration and depress the concentration of
calcium as a result of the solubility product effect. Therefore, the potential for
precipitating scale-forming calcium compounds like gypsum is minimal. This permits
recycled process liquor to be utilized for mist eliminator wash and allows improved
water management in this FGD process.
489
De- \ C Q S 0 3 ( S )
watering
Mg(OH)^ CaS03(s)
MgS03
SO, + HÔ^ HSO- -f
MgS03 + + HSQ3" ^ MgCHSO^)^
Mg(HS03)2 + Ca(0H)2*ZZZ:^ CaSO^s) + MgS03+2H20
Figure 2. Thiosorbic process principle
For conventional FGD, the objectives of the pilot scale testing are to find the
lowest cost scrubber design and operating conditions which will achieve +90% SOg
removal. Capital costs for wet FGD systems entail the scrubber tower, recirculation
pumps, booster fans to move the flue gas through the scrubber and the dewatering
equipment which is comprised of thickeners and vacuum or centrifugal filtration
equipment. Additional capital costs are incurred for the procurement of land to
dispose of the FGD by-product. Operating costs consist of the electric power required
to operate the recirculation pumps, booster fans, and the dewatering equipment, plus
costs associated with transporting the by-product for disposal. For achieving the cost
reduction, emphasis was placed on reducing the \JG and tower height, and improving
the dewatering characteristics of the FGD by-product. The various design and
operating parameters which were investigated to reduce the l_/G and the tower height
included operating at higher absorber gas velocities, reducing the number of spray
headers and utilizing trays and fine spray nozzles to enhance mass transfer. Testing
to improve the solids dewatering characteristics involved reducing the percent solids
within the recycle liquor, decreasing the residence time of the recycle tank and
inhibiting oxidation of the calcium sulfite crystals.
In this paper, the expressions "percent SO2 removal" and "number of transfer
units (NTU)" are utilized to characterize SOg removal. Although percent SO2 removal
490
is the data of interest, NTU is a more useful form for correlation of data. When SOg
removal is assumed gas-film limited, the following equation expresses the relationship
between NTU, percent SOg removal, and the mass transfer characteristics:
VoSO^removal^
NTU =-In 1- =z (0
100
The advantage of utilizing the NTU expression is that the individual contribution
of the absorber internals such as a spray header, tray, or packing toward SOg
removal can be quantified. Subsequently, contributions as NTU's can be added or
subtracted to evaluate potential SOg removals at conditions which were not specifically
tested.
Higher Gas Velocities

The purpose of this testing is to demonstrate that scrubber velocities greater than
the current design standard of 10 ft/sec are feasible. Higher design gas velocities
would allow reduction in scrubber tower diameter and cost or fewer scrubbers where
several scrubbers are required. By increasing the design flue gas velocity to 15 ft/sec,
an 18% reduction in absorber diameter and material cost will be realized to scrub the
same volume of gas.
The effect of flue gas velocity in the range of 10 to 14 ft/sec on SOg removal in
the 4 foot diameter tower for both spray and tray scrubber modes is shown in Figure
3. At similar L7G and velocity, the difference between the curves for the two scrubber
modes is the NTU contribution by the tray. The removal of SOg increases as the
scrubber velocity is increased. Improved gas liquid contact is provided by the higher
velocity due to the increase in liquid holdup on the tray as well as droplet holdup in
both the spray and tray scrubber modes.
Testing of scrubber velocities between 16 and 24 ft/sec was conducted in the 3
foot diameter spray tower. As shown in Figure 4, the required L/G to obtain a chosen
SOg removal decreases with increasing gas velocity, similar to the trend noted in the
4 foot tower testing. However, the observed increase in gas-liquid contact caused by
higher gas velocity was larger than expected. One explanation is that at the higher
gas velocities caused the mist eliminators to accumulate liquor which enhances the
gas-liquid contact beyond that achieved by the holdup of the droplets alone. This
explanation correlates with the observed carryover from the mist eliminators at the
various velocities detailed in Figure 5. At demister face velocities above 18 ft/sec,
re-entrainment of the accumulation on the mist eliminator occurs resulting in liquor
exiting the tower. Finding means to remove this entrained slurry would allow
scrubbers to take advantage of the high SOg removal and low L/G achieved at the
higher velocities. Current testing at the Miami Fort pilot plant funded by the Ohio Coal
Development Office is evaluating commercially available mist eliminators at absorber
velocities of 20 and 30 ft/sec.
491
Ii a
i^
O 1
(O '
o
10 20 30 40 50
Figure 3. SOg removal in 4 ft tray and spray tower.
6.00 ^
24 fps 22 fps ^ 18fps
D 5.00 ^ ^ 20 fps ^ V^16fps
r 4.00
98% ^ ^ ^ ^ ^
5 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^
90%
I 3.00
y
^ 2.00
g 1.00
0.00 10 15 20 25 30 35 40 45 50 55 60 65 70 75
UG
Figure 4. SOg removal in 3 ft spray tower.
|60
rso
1 40
1 30
20
UJ
2 10
- 0-
12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Mist Eliminator Face Velocity (fps)
Figure 5. Mist eliminator carryover in 3 ft spray tower.

492
Figure 6 shows the gas pressure loss across the 4 foot tower for both the spray
scrubber and the tray scrubber. Gas pressure loss was assumed to be proportional
to gas velocity and to liquid flowrate. The pressure loss within the spray tower
increases proportionally to the square of the velocity as does the additional pressure
drop attributed to the tray when operating in the tray scrubbing mode. Correlation of
the actual data found the spray zone loss increased to the 1.19 power of liquid
flowrate and as the 1.79 power of gas velocity. Tray gas pressure loss increased as
the 0.97 power of liquid flowrate and as the 2.15 power of gas velocity. Pressure loss
attributed to the mist eliminators increased as the 2.32 power of gas velocity.
50 100 150 200 250 300 350
Liquid Flooding Rate (GPM)
Figure 6. Absorber pressure drop in 4 ft tray and spray scrubbers (10 & 14 ft/sec)
In summary, increased gas velocity allows the same removal to be achieved at

lower LVG in both the tray and spray configurations, but the improvement in
performance is better with the tray at the expense of higher but not prohibitive gas
pressure drop.
Reducing Recirculation Flowrates

Investigations into methods to increase the mass transfer effects between the flue
gas and the scrubbing liquor were conducted in order to reduce the recirculation
rates but maintain the same SOg removal efficiency. Cost savings in this area can be
illustrated by the following rule of thumb. For each 20 L/G reduction achieved in the
scrubber, the pressure drop within the scrubber is reduced by 0.5 inches of water and
is equivalent in power consumption costs to fan requirements being reduced by 2.0
inches of water.
As discussed above, one method of increasing mass transfer is accomplished
by installing a tray. Figure 3 illustrated that at similar velocities and between L_/G's of
20 to 45, a tray will contribute from 0.5 to 2 NTU's in addition to that achieved by the
493
spray tower. Figure 7 details the SOg removal contribution of the tray when increasing
liquid loading at a tower velocity of 10 ft/sec when all the nozzles within the scrubber
were removed except for the quench. At a total L/G of 32, of which 24 \JQ was in
contact with the tray and the remaining 8 L/G was directed to the quench nozzle
beneath the tray, the effective SOg removal was 1.1 NTU (0.75 NTU from the tray and
0.35 NTU from the quench nozzle). At higher liquid loadings, the contribution of the
tray increased. This increase in removal is expected as it was during the higher
velocity studies due to the increased holdup time of the liquor on the tray. At lower
L/G when liquid holdup is minimal, the percent open area of the tray can be
decreased to increase the liquid holdup and thereby increase the SOg removal.
7.00

5^6.00
5.00 / TF32FCN
TF40NN
5 4.00
I 3.00
/ 1125M
CN 2 . 0 0
-A
Sprayco
S 1.00
Tray
or
0.00
10 20 30 40 50 60
UG
Figure 7. SOg removal with fine sprays in 4 ft tray scrubber (10 ft/sec).
Investigations into producing smaller droplets to increase the surface area of the
liquor were conducted. Decreasing the droplet size was accomplished by utilizing
various types of nozzles which produce finer spray droplets and by increasing the
flowrate through the standard nozzles. The results of the different nozzle types at a
scrubber velocity of 10 ft/sec and varying L/G are detailed in Figure 7. Little difference
in removal was noted between the nozzles when the scrubber was operated at 20
L/G. With a second spray header in operation which increased the L/G to 35, the
finest nozzles, Bete TF40NN and TF32FCN, provided removals of 0.5 NTU above the
coarser Bete MP1125M and Spraco 11-0308-26. Generally, as the liquid flowrates
increased to individual nozzles to achieve LVG greater than 35 the number of smaller
droplets increases providing additional surface area for improving the SOg removals.
For the TF32FCN nozzles, the increase in removal exceeded what would have been
expected from the increase in surface area alone. This phenomena was probably the
result of the high velocity with which the droplets leave the nozzles. This increases the
contact between the flue gas and the droplets, increasing the absorption rate of SOg.
494
Increasing the contact time for mass transfer between the flue gas and absorber
liquid will enable a reduction in recirculation flowrates. This can be accomplished by
increasing the height of the scrubber which would lengthen the spray zone. Tests
were conducted where the length of the spray zone was increased by 10 feet by
introducing the same liquor flowrate at different spray headers. The additional spray
zone increased the SOg removal by 0.4 NTU regardless of the flowrate. In comparison,
installation of a tray increased the SOg removal from 0.3 to 1.0 NTU when compared
to the spray tower results over the same range of test conditions.
Improving Solids Dewatering

The objective of this testing is to improve the size and shape of the calcium
sulfite crystals formed from the Thiosorbic FGD process to obtain a by-product with
better settling and dewatering characteristics. In the dewatering section of an FGD
system, solids are first allowed to settle in a settling tank, or thickener. Additional water
is then removed by filtering or by centrifuging the thickened solids. Removal of these
solids from the recirculating absorber liquid stream and their subsequent disposal
constitutes a major cost of a wet FGD system. Improvements in the ease with which
solids can be removed from liquid and reduction in the amount of solids produced
would significantly reduce capital and operating costs. In particular, thickener
downsizing or elimination my be possible. Secondary dewater equipment such as
filters or centrifuges can be downsized or replaced by stacking of the material. Life
expectancy of landfills will increase and transportation costs associated with moving
a drier by-product to these landfills would decrease. Two methods to improve
dewatering characteristics have been investigated at the Miami Fort pilot plant. The
first examined modes of conventional scrubber operation and oxidation inhibition.
These changes were readily adaptable to operating facilities. The second method
developed by EPRI required the replacement of the recycle tank and the thickener
with a unique crystallizer tank which performed the functions of the former two
vessels.
In studies to improve the solids dewatering of the conventional Thiosorbic
process, emphasis was placed on determining the effects of operating parameters
which would improve nucleation and reduce shearing and oxidation of the calcium
sulfite crystals. Particle size and shape are influenced by the design and operating
conditions in the recycle tank where the calcium sulfite crystals are formed as the lime
reacts with the absorbed SOg. Reducing the percent solids and the residence time in
the recycle tank would allow fewer but possibly larger nucleation sites and reduce the
shearing of the crystals by limiting the number of passes each would undergo through
the recycle pumps. Limiting oxidation, thereby producing a purer calcium sulfite
by-product was accomplished by adding a sulfite oxidation inhibitor.
Particle size improvement testing was initiated by increasing the bleed to the
thickener to reduce the percent solids in the recycle tank from 3% to 1 %. This change
increased the filter cake solids concentration to 35-37% from the baseline of 28-33%
established prior to the starting of these tests. The next phase of testing entailed the
addition of thiosulfate, a sulfite inhibitor, to the process. The target thiosulfate
concentration was 2000 ppm. The effect of the thiosulfate addition and the resulting
495
oxidation inhibition was to increase the filter cake solids content to 39-42%. The final
phase of testing reduced the volume in the recycle tank from the typical 1800 to 300
gallons by utilizing the lower portion of the scrubber tower as the recycle tank. The
impact was dramatic, increasing to filter cake solids content to 50-54%. This
improvement resulted from minimizing the passes of the slurry through the recycle
pumps by reducing the residence time in the recycle tank to 10 minutes and by
further decreasing the sulfite oxidation. Oxidation inhibition increased due to the fact
that the slurry was in contact with flue gas which has an oxygen content of 5-7% as
opposed to air which is in the head space of the separate recycle tank. Figure 8
shows the resulting lab filtration rate and filter cake solids as a function of the process
changes.
Figure 8. Settling and filtration results.
The EPRI approach to improving the dewatering characteristics of the Thiosorbic

process involved using oxidation inhibition and the development of a crystallizer vessel
known as the classifying crystallizer reaction tank (CCRT). The process flow diagram
is shown in Figure 9. The CCRT produces a clear liquor as opposed to a slurry for
scrubbing which eliminates the shearing of crystals in the recycle pumps. Its flexibility
in controlling the addition of lime to the scrubber effluent minimizes high calcium sulfite
relative saturations which tend to form small fragile crystals. A second vessel known
as the premix slurry tank (PMST) was added to improve the process. The PMST mixes
the Thiosorbic lime which is entering the system with a bleed slurry stream from the
CCRT thickened underflow at a pH greater than 10.5. At this pH, magnesium
hydroxide and calcium sulfite precipitate. The contents of the PMST provide calcium
sulfite seed crystals and pH control to the CCRT. The CCRT operating at a pH of 6.5
to 7.2, neutralizes the liquor from the scrubber permitting the magnesium hydroxide
to redesolve and additional calcium sulfite to precipitate. The crystals formed in this
process settle quickly to the bottom of the CCRT where they are allowed to thicken
and are eventually removed for secondary dewatering. The clear overflow from the
CCRT is returned to the recycle pumps. The chemistry of the process is detailed in
Figure 10.
496
FLUE GAS OUT
CLEAR LIQUOR
/TsT
FLUE G A S IN
.BSORBER
FEED
TANK
SLURRY
RECYCLE
DEWATERING
WASTE SLIDS
Figure 9. CCRT/PMST process flow diagram.
Cg(0H)2
Mg(OH), 30
CaS0ifMgS03 CaS03^:/MgS03
Recycle
~ HSO; +
"\MgS03+ H^+HS03~t=Z:^Mg(HS0j^
Mg(HS03)^+ CQ(QH)f '^CoSQ^ + , ^2H,0
C MgSO, + Ca(0H\*IIZ::^CQS03 + Mg(OH\
Figure 10. CCRT/PMST process principle.

497
Testing of the CCRT/PMST process was conducted at the Miami Fort Pilot plant
for 18 weeks. Goals of the tests were to optimize residence times and agitation rates
for the CCRT and PMST vessels, evaluate control strategies, identify operating and
design parameters which would improve the solids dewatering, and demonstrate the
retrofit capabilities of the PMST to existing Thiosorbic scrubbers. In order to optimize
the CCRT, the functions of mixing the PMST contents with the scrubber effluent and
the thickening of the precipitating crystals were conducted in two separate vessels.
Select results pertaining to the dewatering characteristics of the generated solids from
the CCRT/PMST, PMST-retrofit, and the baseline Thiosorbic mode are displayed in
Figure 11. The testing successfully demonstrated the proof of concept for the
CCRT/PMST and PMST-retrofit processes.
The capital and operating costs of a improved Thiosorbic FGD system based on
the data developed from the pilot plant testing was estimated using the Integrated Air
Pollution Control System (lAPCS) version 4.0 computer model developed by the U.S.
Environmental Protection Agency and the Tennessee Valley Authority. This model
enabled comparisons to be made between the improved Thiosorbic process and
conventional limestone processes. All cases were based on a plant size of 500 MW.
To calibrate the model, cost estimates were performed on the Zimmer Station design
using its actual plant size of 1300 MW. Agreement between the results of the model
and actual published costs of the power plant supported that the model was
reasonably accurate. Table 1 displays the process design values for the FGD systems
and the resulting cost estimates.
Similarly, the data generated from the pilot scale testing of the EPRI CCRT/PMST
process was incorporated into the conceptual design for a single CCRT vessel and
a corresponding economic evaluations conducted. The EPRICOST computer model
developed by EPRI was used for these evaluations. A 300 MW boiler with a capacity
factor of 65% that burns a 2.6% sulfur coal was used as the basis. Various
configurations of the CCRT/PMST, Thiosorbic, and Thiosorbic with PMST retrofit FGD
systems were modeled. Table 2 provides the process design criteria and the
corresponding economic results.
PRODUCTION OF SALABLE PRODUCTS FROM THIOSORBIC LIME PROCESSES
Wet scrubbing is the leading proven commercial post-combustion FGD

technology available today to meet the SOg reductions required by the Clean Air Act
Amendments (C/\AA) of 1990. The CAAA offers incentives for use of high-efficiency
SO2 removal technologies through a provision which allows the accumulation of
excess emissions allowances if control targets are exceeded. These allowances can
be used to meet reductions required at other effected generating units, offset
emissions from new units, or be traded for cash. Thiosorbic FGD systems with their
capability to efficiently scrub flue gases generated from the combustion of high sulfur
coals will have a strong position in the market.
498
Table 1
Design values and system costs
Design Parameters Conventional Conventional Zimmer Improved Improved
Umestone Umestone Thiosorbic Thiosorbic Thiosorbic
500 MWe
Sulfite Oxidation Natural Forced Natural Suppressed Suppressed
S02 Removal (%) 90 90 91 90 98
Absorber Gas Velocity (ft./sec.) 10 10 10 15 15
L/G (gpm/kacfm) 100 110 21 25 45
Suspended Solids in Slurry (wt.%) 15 15 10 4 4
Solids in TUF (wt%) 40 45 25 40 40
Solids in Filter Cake (wL%) 70 85 40 54 54
Thickener Unit Area (sq. ft./tpd) 5 2 45 20 20
Filtration Rate (Ibs./hr-sq. ft.) 150 167 60 150 150
System Costs
Total System Cost ($/KW) 184.9 189.5 152.1 115.4 120.1
operating Costs
First Year Busbar Cost of Power (mills/kwh) 9.4 9.6 8.6 7.3 7.5
First Year Busbar Cost of Power ($/yr.) 26,711.000 27,427,400 24,490.200 20,634,200 21,410,700
First Year Cost of S02 Removed ($/ton coal) 22.51 23.11 20.64 17.39 18.04
First Year Cost of S02 Removed (#/ton S02) 364.95 374.74 330.93 281.93 268.66
Table 2
Design values and system costs
Design Parameters Casel Case 2 Case 3 Case 4 Cases Case 6
Sulfite Oxidation Suppressed Suppressed Suppressed Suppressed Suppressed Suppressed
S02 Removal (%) 90 90 90 90 90 90
Absorber Gas Velocity (ft./sec.) 10 10 10 10 10 10
L/G (gpm/kacfm) 40 40 23.5 40 40 23.5
Suspended Solids in Slurry (wt.%) 6.33 6.33 6.33 6.33 6.33 6.33
Solids in TUF (wt.%) 30 30 37 37 30 37
Solids in Filter Cake 43 50 50 50 43 50
System Costs
Total Capital Required ($/kW) 146.5 148.4 138.8 139.4 111 106.4
30-Yr Levelized Cost ($/ton 802)

Fixed 0 & 110.5 111.5 105.4 106.6 88.3 85.3
Variable Operating 162.4 157 155.4 156.7 162.4 155.4
Fixed Charges 158.4 160.5 150.1 150.8 120 115.1
Total Levelized Cost ($/ton 802) 431.3 429 410.9 414.1 370.7 355.8
Case 1: Thiosorbic lime base case with spray three absorbers.

Case 2: Thiosorbic lime with PMST and three spray absorbers (for PMST retrofit cost, subtract Case 1 cost).
Case 3: Thiosorbic lime CCRT and PMST with three tray absorbers. Absorber dP increase 2" H20.
Case 4: Thiosorbic lime CCRT and PMST with three spray absorbers.
Case 5: Thiosorbic lime base case with single tray absorber.
Case 6: Thiosorbic lime CCRT and PMST with single tray absorber.
499
CCRT/PMST THIOSORBIC P M S T (retrofit)
Figure 11. Dewatering comparison.

500
One drawback of wet FGD systems is the disposal of the calcium-based

by-products. Typically these by-products are landfilled requiring additional capital
costs in land procurement and operating costs for fixation to stabilize the by-product
and transportation to deliver the by-product to the landfill. Recent environmental
restrictions and limitations on the operation of landfills have increase the costs.
Therefore, determining what improvements and advancements can be made to FGD
processes to reduce the costs and generation of landfill materials is important.
To improve the economics of the Thiosorbic FGD process, Dravo Lime Company
developed the Thioclear process. The Thioclear process shown in Figure 12 is a wet
scrubbing system that uses magnesium hydroxide (Mg(0H)2) and magnesium sulfite
(MgSOg) in solution to remove SOg from flue gas. Thioclear continues to utilize the
magnesium based Thiosorbic lime to regenerate its scrubbing liquor. It differs from
the standard Thiosorbic system in that scrubber liquor is clear with very little solids
and the process generates Mg(0H)2 and gypsum (CaSO42H20) instead of calcium
sulfite (CaSOg). In the Thioclear process, the same magnesium reactions occur as with
the Thiosorbic process, achieving similar SOg removal efficiencies. The lime slurry is
not injected into the recycle tank as in conventional Thiosorbic systems. Instead,
recycled Mg(0H)2 is added to control the scrubber pH between 6.0 - 6.5 and maintain
the magnesium balance. The clear scrubber blowdown flows directly to an oxidizer
where liquid phase sulfites and bisulfitos are converted to sulfates at a pH of 5.5. The
oxidized liquid is bled to a regeneration tank where high content magnesium lime
(Thiosorbic lime with 5-6% MgO) is added to achieve a pH of 10. 8 to precipitate
CaSO42H20 and Mg(0H)2. The key to the regeneration step is controlling pH,
residence time, and mixing rate to produce very large CaS042H20 crystals and small
Mg(0H)2 crystals. The regeneration tank slurry is fed to a hydroclones or other
separating devices. In the case of the hydroclone, the larger CaS04*2H20 crystals are
separated to the underflow and eventually dewatered. Mg(0H)2 crystals report to the
overflow and are pumped to a thickener. Some of the thickened Mg(0H)2 is recycled
to the scrubber. The chemistry of the process is detailed in Figure 13.
The gypsum can be utilized as a component for wallboard manufacturing or
landfilled at a lower cost than the existing Thiosorbic by-product as a result of its
improved dewaterability which decreases its weight and eliminates the need for
fixation. The value of the magnesium hydroxide produced will be determined by its
purity. A low grade slurry may be substituted as the caustic to neutralizing waste
water discharges from utility plants. As the purity of the magnesium hydroxide is
improved, the value of this product can increase from $150 per ton to $1000 per ton.
The value of these products not only will off set the operating costs of the FGD
system, but will minimize and possibly eliminate the disposal of the FGD by-product.
The testing of the Thioclear process at the Miami Fort Pilot plant was limited to
a 6 week proof of concept evaluation during the summer of 1990. The results of the
testing showed conclusively that the Thioclear process concept is viable. The SO2
removal during the test program ranged from 90-95% while scrubber gas velocities
of 12-15 ft/sec were maintained. Although the oxidizer was not optimally configured
and resulted in an oxygen stoichiometric ratio of 6:1 to the entering sulfites instead of
the anticipated 2:1 ratio, the exiting sulfites were maintained below the target level of
501
CLEAN GAS
Figure 12. Thioclear process flow diagram.
so, - HÔ^ ÎHSO, +

A ^ M g S O ^ -f- + HSOjt Mg(HS0,)3
~ Mg(OH)j + S t ) , ^ MgS03 + ,
Mg(OH), 4 SOz ^
^^MgSO, + 1/2 O2- MgS04

Mg(0H)2(s)
MgS0 3 ^f^g(HS0j)2 ^- O 2 - MgSO^ + H2SO4
MgS03 Mg(0H)2 .5 , 0
Mg(HS03 D - MgSO 4 Ca(OH);, - C a S O * 2H2O
Mg(OH) <
Recen \.^Co{Oh),
MgSO, ) Mg(OH),
pH = b.5 pH = 10.8
CaS04(s)
Mg(OH),
Gypsunn
Separation
C q S O , ( s )
Mg(0H)2(s)
Product
Figure 13. Thioclear process principle.

502
100 ppm. Scaling tendencies where limited to the regeneration tank, but were
minimized by increasing the residence time of the tank and the percent solids for seed
crystals in the feed stream. Utilization of two hydroclones in series enable a 96%
recovery of the magnesium hydroxide which insures the process will be self sustaining
in regards to magnesium hydroxide consumption. The resulting gypsum product
dewatered to 70-75% solids. Insufficient time in the test plan prohibited optimization
of the recovery process for purity of the products. The gypsum contain between 2-3%
magnesium hydroxide and the product magnesium hydroxide contained 15-20%
gypsum.
As a result of the success of the proof of concept test. The Cincinnati Gas &
Electric Company and Dravo Lime Company have been awarded funding from the
Ohio Coal Development Office for the improvement of the Thioclear process to a level
ready for commercialization. The scope of this program includes refinements to the
process in order to improve process control, process economics, verifying SOg
removals of -i-98%, and increasing the gypsum and magnesium hydroxide purity and
recovery rates. A horizontal flow absorber capable of velocities to 30 ft/sec will be
evaluated while taking advantage of the clear liquor which will allow the use of
advanced spray nozzles, packings and mist eliminators. Testing was initiated in May,
1993 and is expected to require 12 months to complete. A preliminary economic
analysis based on the data generated during the proof of concept testing is detailed
in Table 3 in comparison to the Thiosorbic and limestone forced oxidation with DBA
addition FGD systems.
Table 3
Comparison of FGD economics
Summary of Results Thioclear vs. LSFO

Cost Difference
Thiosorbic LSFO Thioclear Savings Savings
Overall Costs (1990$) System (1) System {^) Sytem (1) Percent
Mills/KW-Hr. First Year 6.8 7.6 6.8 0.8 11

Mills/KW-Hr. Levelized 9.3 10.4 9.4 1 11
Capital costs, $/KW 146 180 150 30 20
$/Ton Coal Burned, First Year 16.3 18.2 16.4 1.9 11

$/Ton Coal Burned, Levelized 22.3 25 22.5 2.5 11
FGD Cost $/Ton S02 Removed. First Year 390 437 392 45 11
FGD Cost $/Ton S02 Removed, Levelized 534 599 540 59 11
(1) Dravo Lime Company Research Center Estimate Based on EPRI Publication GS-7193.
503
EXPANSION OF THE AIR POLLUTION CONTROL CAPABILITIES OF THE

THIOSORBIC PROCESS
The Clean Air Act Amendments (CAAA) of 1990 mandates a substantial reduction
of sulfur dioxide emissions from coal-fired electric generating units. The CAAA also
requires the achievement of both NO and certain air toxics reductions. In the case of
some boilers, the reductions of NO must be achieved by 1995, while other units will
not be effected until the end of the century.
Due to the impact of this legislation on utilities utilizing high sulfur coal, Dravo
Lime Company has developed the ThioNOx process for NO reduction. The process
requires the addition of ferrous chelates to the liquor of the Thiosorbic FGD system.
The ferrous chelates absorb the NO in the flue gas without hindering the absorption
of SOg. Thus, this process for NO^ control has several advantages over other post
combustion processes when a wet FGD system is existing or planned. Scrubbing
equipment utilized for SOg removal also removes the NO, thereby eliminating
additional capital costs for the new function. This compares favorably against selective
catalytic reduction (SCR) which requires a separate reactor and a relatively expensive
catalyst. Since the same equipment is utilized to remove both SOg and NO. the
operating costs will be minimal when compared to those processes which require
additional equipment to achieve the necessary removals.
Testing of the ThioNOx process which was funded by the U.S. Department of
Energy was conducted at the Miami Fort pilot plant from April to December 1991
utilizing the 3-foot diameter, 40-foot tall scrubber. The scrubber was operated at gas
velocities of 4 to 10 ft/sec with recycle flowrates of 25 to 300 gpm corresponding to
L/G's of 15 to 225. Preliminary tests were made using spray nozzles and perforated
plates, but most of the experiments used commercial dump and structured packings.
A flow diagram of the process is shown in Figure 14.
The chemistry of the ThioNOx process detailed in Figure 15 relies on the ability
of the ferrous chelate, ferrous-EDTA (Fe"^ÊDTA), to combine with NO which has
dissolved in the scrubbing liquor. The resulting chemical species then reacts with
sulfites which are found in abundance in Thiosorbic FGD systems to produce
ferric-EDTA (Fe'^ÊDTA) and sulfur/nitrogen compounds. The blowdown from the
recycle tank permits the sulfur/nitrogen compounds to be purged from the process
with the FGD by-products. The returning clarified liquor requires a regeneration step
in which the iron chelate is reduced to its active NO absorbing form, Fe'^^ZEDTA,
before reentering the scrubber.
The testing at the pilot plant was divided into three phases. Phase I investigated
the various scrubber configurations, operating parameters, effects of the inlet NO
concentration, and the concentration of Fe'^ÊDTA in the scrubbing liquor to derive
a mathematical model for NO removal. Phase II examined an alternative regenerating
agent and various scrubber configurations to increase mass transfer and operating
changes which would enhance the NO removal. Phase III entailed two 216 hour
duration tests to simulate expected removals in an existing FGD scrubber retrofitted
for NO removal and in a scrubber designed specifically for NO removal.
504
CLEAN GAS
FeS04
t t
RECYCLE SLURRY ADDITIVE
3 - 8 % SOLIDS MIX
REGEN
PROCESS
JTl TANK
MAKE-UP
F e 2 -h EDTA
SCRUBBER
REGEN
Fe2 + EDTA
FILTRATE
FLUE
GAS 1
THICKENER
MAKE-UP
LIME WATER
RECYCLE
OVERFLOW)
TANK
TANK
FILTER
FILTER
CAKE
Figure 14. ThioNOx process flow diagram.
MqSOi
Mg(hiS0 3 ) 2
Fe EDTA-NO
CqCOHW Recycle
^ A Tank
CaS03(s)
Mg(OH)
MgS03
Fe^^ EDTA + S/N
A NO + (FE^'EDTA)^ (Fe EDTA-NO) ^
(Fe*'EDTA-N0)=+2S03= + 2 O * (Fe EDTA)" + ( H 0 N ( S 0 3 ) 2 ) = -+-0H
C 2(Fe-ÊDTA)- T-2S0; 2(Fe - 2 E D T )A = 4-S,0^
Figure 15. ThioNOx process principle.

505
The primary objective of Phase I testing was to develop a mathematical model

that describes the dependency of NO removal on the absorber flue gas velocity, liquor
rate through the absorber. Fe"^ÊDTA concentration, absorber length, and gas-liquid
interfacial area. Due to load changes of the boiler which varied the NO concentration
from 415 to 720 ppm, testing was able to determine that NO removal in the scrubber
was independent of the inlet concentration as shown in Figure 16. By altering the
quantity of chemical reagent to regenerate the Fe'^ÊDTA, NO removals were
determined to increase at approximately the square root of the Fe"^^ concentration.
0.30
0.25
_
5 in
0.20 a

On
CM
ff
f

ff .

, rf"

-2 0.10
0.05
o 0.00
^ 400 450 500 550 600 650 700 750
Inlet NOx (ppm)
Figure 16. Effect of inlet NO^ concentration on NO^ removal.
These results combined with the assumption that the reaction is liquid film mass
transfer limited aided in deriving the following mathematical model:
%NOremoval aZ
NTU =-\n\ 1- (2)
100 py
The model was used to guide tests and correlate NO removal in Phase II and III.
NO removal data were very well correlated by the model.
Phase II emphasized investigations into enhancements into mass transfer effects
by utilizing commercially available packing at different recycle flowrates and absorber
gas velocities. Commercial packings included 2-inch and 3-inch Norton Plastic Intalox
saddles, Norton Intalox Snowflake packing, and Munters PN-Fill), a structured
packing made of molded polypropylene sheets. Optimal scrubber operating
conditions were determined from these parametric tests and provided the guidelines
for the two 216 hour duration tests in Phase III.
506
In Phase III a 216 hour test was conducted to simulate retrofit of this combined
SO2 and NO removal technology to an existing absorber designed and built solely for
SO2 removal. Twelve feet of Munters PN-Fill() structured packing was installed in the
3-foot diameter tower. The results are summarized in Figure 17. The flue gas velocity
was maintained in the tower at 8 ft/sec and the absorber liquid rate was about 110
gpm, resulting in an L/G of 45 and a tower pressure drop of 4.5 inches of water. The
Fe'^ÊDTA concentration was maintained at 15 mM by the addition of chemical
reducing agents. NO and SO2 removals were 30% and 99.5%, respectively.
Antioxidant (Ib./hr.)
Fe+2 (mM)
Flue Gas (fps)
L/G
5-Nov 6-Nov 7-Nov
Figure 17. NO^ removal achieved in the retrofit mode.
A subsequent 216 hour test was conducted to simulate the application of this
technology to a wet scrubber designed for NO removal. This was accomplished by
maintaining the same absorber internal configuration as in the retrofit mode, but
altering the operating parameters. The results are summarized in Figure 18. The flue
gas velocity was decreased to 4 ft/sec and the absorber recirculation rate increased
to 250 gpm, resulting in an L/G of 200 and a absorber pressure drop of 5.7 inches
of water. NO ::nd SO^ removals were 60% and 99.9% respectively while Fe'^ÊDTA
concentrations were maintained at 15 mM.
A very pleasant finding from the pilot tests was that the resulting calcium sulfite
(CaS03) byproduct dewatered extremely well. The solids content of filter cake was 65
to 77 weight percent. Such solids concentration are unprecedented for Thiosf^r'::!c
systems which typically produce filter cakes with solids contents from 35 to 45 weight
percent.
507
80 220
-,
70 210
60
Antioxidant (Ib./hr.)
200
Fe+2 (mM)
50
190
o Flue Gas (fps)
40
JDI C
180
30 CD r~i
170
20 y L/G
160
10
O 150
18-Nov 19-Nov 20-Nov 22-Nov 23-Nov
Figure 18. NO^ removal achieved in the new plant mode.
As a result of NO removal by ferrous-chelates being independent of the inlet

concentration of NO, this process in combination with low-NO^ combustion strategies
can achieve higher levels of NO^ reduction than either technology alone. An overall
removal of 7 5 % would be realized by combination of 5 0 % removal during the
combustion process and 5 0 % from the ThioNOx process. Comparisons of NO^^
abatement technology costs are shown in Table 4. In determining the costs for the
ThioNOx process, it was assumed that a less expensive method of regenerating the
Fe'^ÊDTA is utilized than the chemical reducing reagents used in the pilot scale
testing. Two such methods are the electrochemical cell and natural reduction by
sulfites at elevated temperatures. The development of these regeneration processes
will be the focus of upcoming Pennsylvania Energy Development Authority (PEDA)
and Ohio Coal Development Office (OCDO) funded work to be conducted by the
Dravo Lime Company. Also included in the scope of this work is the characterization
of air toxics removal resulting from the unique chemistry associated with the ThioNOx
process. This testing is planned to be initiated by the fall of 1993.
508
Table 4
NO^ reduction technologies cost summary
Technology NOx Removal Capital Cost Levelized Operating Cost
(%) ($/kW) ($/ton NOx removed)
Low NOx Burner (1) 35-40 19 225
LNB + A 0 F A ( 1 ) 60 26 170
SCR (2) 80 158 1947
SNCR (NOxOUT) (3) 50-85 10-20 600-1750
ThioNOx w/LNB (4) 75 48-65 646-830
ThioNOx w/o LNB (4) 50 35-52 568-845
(1) Emmel, T.E. et. al. Radian Corp. & U.S. Environmental Protection Agency;
Technology Costs; "Power-Gen 92"; November 18, 1992.
(2) Integrated Air Pollution Control System Costing Model Program, Version 4.0; U.S. EPA
(3) Nalco/Fueltech Brochure on The NOxOUT* Process.
(4) Dravo Lime Company Research Center Estimate.
GLOSSARY
NTU removal as number of transfer units, dimensionless.

length of gas-liquid contact zone, ft.
kg mass transfer coefficient.
a gas-liquid interfacial area per unit volume of contact zone, ft^/ft^.
V flue gas velocity in absorber, ft/sec.
k2 reaction rate constant for second-order reaction between NO (I) and
ferrous-EDTA, 1.4 10^ (m-sec)'^ @ 50C.
[Fe +2i ferrous-EDTA concentration in absorber liquor, mM.
D,NO diffusivity of dissolved NO in absorber liquid, 4.1 10-5 cm2/sec @ 50C.
molar density of flue gas, 0.00235 Ib-moles/ft^ (@ 50 C.
P-P total pressure, 1 ATM.
Henry's law constant for NO in water is 710.7 ATM/M @ 50C.
REFERENCES
1. Dravo Lime Company, Final Report: Advanced Wet Flue Gas Desulfurization and
Denitrification Process; Volumes I and II, OCDO Grant Agreement No:
CDO/D-87-76, November (1991).
509
2. Dravo Lime Company, Final Report: Enhanced NO^ Removal in Wet Scrubbers
Using Metal Chelates; Volumes I and II, DOE Contract No: DE-AC22-90PC90362,
December (1992).
3. Wilhelm, J.. and Stohs, M., Clear Liquor Scrubbing with the Classifying
Crystallizer Reaction Tank - preliminary report prepared for the Electric Power
Research Institute (EPRI), December (1992).
4. Smith, K.J., Tseng, S. and Babu, M., Enhanced NO^ Removal in Wet Scrubbers
Using Metal Chelates - preliminary report prepared for the Air & Waste
Management Association 86th Annual Meeting and Exhibition, June (1993).
Integration of coal gasification and combined cycle facilities on

the Wabash River coal gasification repowering project
Phil Amick^, Dennis Zupan^ and Robert E. Herbster''
^Destec Engineering, Inc., Houston, Texas
^PSI Energy, Inc., Plainfield, Indiana
""Sargent & Lundy Engineers, Chicago, Illinois
ABSTRACT
PSI Energy, Inc. and Destec Energy, Inc., will demonstrate, in a fully
commercial setting, coal gasification repowering of an existing generating unit
affected by the Clean Air Amendments ("CAAA"). The project will demonstrate
integration of the existing station steam turbine generator and auxiliaries, the new
combustion turbine generator/heat recovery steam generator tandem and the coal
gasification facilities to achieve improved efficiency and reduced installation costs.
Upon completion, the project will not only represent the largest CGCC power
plant in operation in the United States but will also emit lower emissions than other
high sulfur coal fired power plant and improve the heat rate of the repowered unit
by approximately twenty percent.
INTRODUCTION
The Wabash River Coal Gasification Repowering Project (WRCGRP), a joint

venture of Destec Energy, Inc., (Destec) of Houston, Texas and PSI Energy, Inc.,
(PSI) of Plainfield, Indiana, will jointly develop, and separately design, construct,
own, and operate a coal gasification combined cycle (CGCC) power plant.
Destec's coal gasification technology will be used to repower one of the six units
at PSI's Wabash River Generating Station in West Terre Haute, Indiana. The
CGCC power plant will produce a nominal 270 net MW of clean, energy efficient,
capacity for PSI's customers. In the repowered configuration, PSI and its
customers may additionally benefit because of the role the WRCGRP plays in PSI's
compliance under the CAAA regulations. The project will use locally mined, high
sulfur coal.
512
BACKGROUND
The Destec Coal Gasification process was originally developed by the Dow
Chemical Company during the 1970's in order to diversify it's fuel base from
natural gas to lignite and other coal. The technology being used at Wabash is an
extension of the experience gained from that time through pilot plants and up to
the Louisiana Gasification Technology, Inc. (LGTI) facility in Plaquemine, Louisiana,
a 160 MW coal gasification facility which has been operating since April 1987.
Sargent & Lundy will provide engineering services to PSI for the design and
procurement of the modifications to the existing station, the new power block
equipment and provide the system integration interface to Destec. PSI will
manage the construction of, own and operate the power generation facilities.
Destec will manage the construction of, own and operate the coal gasification and
air separation facilities. Dow Engineering Company, previously engineer for the
LGTI facility, will provide engineering services to Destec.
The major provisions of the agreements establishing the PSI and Destec
relationship are as follows:
PSI
to own and operate the power generation facility
to build the power generation facility to an agreed common schedule
to furnish Destec with a site, coal, power and services
provide stormwater and wastewater facilities
DESTEC
to own and operate the coal gasification facility
to build gasification facility to an agreed, common schedule
to guarantee performance of the coal gasification facility
to meet environmental conditions
to deliver syngas and steam to the power generation facility
The structure of the Gasification Services Agreement allows the Power
Generation Facility and the Coal Gasification Facility to be integrated for high
efficiency.
FACILITIES INTEGRATION
The site of the project is PSI Energy's Wabash River Generating Station,
located near Terre Haute, Indiana.
Only Unit 1 of the six existing units will be repowered as part of the project.
The existing pulverized coal fired boiler will be decommissioned and the steam
turbine, a Westinghouse reheat unit originally placed in service in 1953, will be
driven by steam from the new facilities.
Early site feasibility studies resulted in locating the new coal gasification
repowering facilities to the north west of PSI's existing facility (Figures 1 & 2). The
location of these facilities minimizes the cost of alloy steam piping connecting the
existing Unit 1 steam turbine and the new heat recovery steam generator. Existing
513
Figure 1. Artist conception drawing
Jl /
WABASH RIVER
Figure 2. Plot plan

514
facilities to be used by the project include the railroad, coal unloading facilities,
condenser and auxiliaries and the ash pond, in addition to the existing steam
turbine generator, steam turbine generator auxiliaries and substation. No new
construction will be required within the existing boiler and turbine buildings except
for the steam piping interconnection.
Repowering the existing unit, and utilizing the existing site facilities mentioned
above, in addition to the existing steam turbine generator, auxiliaries, and electrical
interconnections, represent a installed cost savings of approximately $30 to $40
million as opposed to an entirely new, greenfield installation.
New construction will take place in two areas. A 15 acre plot containing the
gasification island, oxygen plant, water treatment and gas turbine-heat recovery
steam generator block is on a hill overlooking the existing station. The new
wastewater and storm water ponds will be located nearby in an area previously
used as an ash pond. Coal for the WRCGRP, a high sulfur midwestern
bituminous, will be stored separately from the compliance coal that will be burned
in Units 2 through 6 of the existing station. Existing coal unloading facilities will be
shared, with the remainder of the coal handling equipment being part of the new
installation.
Facilities for the project include the following:
DESTEC:
Slurry preparation
Gasification and heat recovery
Slag removal
Gas cleanup
Sulfur recovery
Oxygen plant
Control, administration & maintenance building
PSI:
Combustion turbine
Heat recovery steam generator
Modifications to coal handling
Oil storage tanks
Piping additions
Water treatment facilities
Control room and buildings
Destec and PSI will independently design, procure equipment and construct
their respective portions of the WRCGRP. However, cooperation in design efforts
and integration of systems has allowed the participants to reduce costs by
minimizing redundant systems and maximize efficiency by thermal integration.
THERMAL INTEGRATION
The Destec gasification process features an oxygen-blown, two stage

entrained flow gasifier. The synthetic fuel gas (syngas) is piped to a General
515
Electric MS 7001F high temperature combustion turbine generator. A heat

recovery steam generator (HRSG) recovers gas turbine exhaust heat.
In the gasification process, coal is ground with water to form a slurry (see
Figure 3). It is then pumped into a gasification vessel where oxygen is added to
form a hot raw gas through partial combustion. Most of the non-carbon material
in the coal melts and flows out the bottom of the vessel forming slag - a black,
glassy, non-leaching, sand-like material. Particulates, sulfur and other impurities
are removed from the gas before combustion to make it acceptable fuel for the
gas turbine. Sulfur is removed from the syngas using conventional "cold" gas
clean-up systems. Some of these systems must operate at near ambient gas
temperatures, necessitating that the syngas temperature be reduced by heat
exchange to with streams. Condensate, feedwater and steam streams are
exchanged between the gasification island and the power block HRSG to maximize
efficiency by making the best use of lower levels of heat available in each area.
(See Figure 4).
Condensate from the steam turbine generator hotwell ("cold condensate" at
about 88 F) is pumped to the gasification plant, where it is heated as the syngas
is cooled for the last stages of the cold gas clean up.
This stream, now called "warm condensate", is combined with condensate
from intermediate pressure steam uses at the gasification plant. Intermediate
pressure steam is supplied to the gasification plant from the cold reheat steam to
the combustion turbine heat recovery steam generator (HRSG). The warm
condensate (about 185 F) is returned to the power block, where it is heated in the
last heating section of the HRSG, the feedwater heater. This stream is then heated
further in the power block deaerator.
Boiler feedwater from the new power block deaerator is pumped through the
HRSG economizer section. The water temperature is now elevated to
approximately 560 F. A portion of this boiler feedwater flow continues through the
HRSG in the conventional manner and becomes high pressure saturated (about
640 F) steam in the HRSG evaporator section. The remaining HRSG boiler
feedwater, however, leaves the economizer and is piped across the fence to the
gasification plant, where the flow is again split. The main part of this flow acts as
boiler feedwater for the gasification plant boiler, becoming high pressure saturated
steam (640 F). The remaining boiler feedwater supplied to the gasification plant
is used for heating in the gasification process and is piped to the power block, as
"boiler feedwater return", at about 410F. The boiler feedwater return flow re
enters the HRSG economizer section. High pressure saturated steam from the
gasification plant is piped to the power block where it is combined with the HRSG
high pressure saturated steam. The combined flow passes through the HRSG
superheater, exiting at about 1010F, and becomes the throttle steam for the
repowered steam turbine. The cold reheat extraction flow from the steam turbine
is heated in the HRSG and returned to the steam turbine, less flows for gas turbine
NOx control steam injection and gasification plant intermediate pressure steam
users. This hot reheat flow is expanded through the steam turbine and
condensed.
516
Existing Coal Gasification

Coal Coal Slurry Coal Slurry
Coal Stockpile HRU Particulate
Receiving Unit Removal
& Reclaim
Oxygen
Slag^
Syngas
Steam
Existing Air
Separation Cooling
Steam
; 109 Unit
Turbine
301 MW
Syngas I
MW ^ Sour
Steam
^ i Water
(Gross.
Generation
Water
Syngas |H S R e m o v a l Water
_| GT/HRSG ^ Sulfur
Treatment
192 Recovery
MW
Liquid Water
1 = Existing
Sulfur Purge
Figure 3. Block flow diagram
/ Coal
Syngas \ Main Steam
HP Steam \ ^Cold Reheat
/ Boiler Feedwater NEW Hot Reheat \

GASIFICATION POWER REPOWERED
PUVI^ Boiler FW Retirn BLOCK FACft^lTY
/
Warm Condensate \
/ IP steam
/Make-Up Water
/Cold Condensate
Figure 4. Simplified thermal integration diagram

517
The new power generation facility will include additional water treatment
systems. The combustion turbine has steam injection for NOx control. The
amount of this injection flow is reduced compared to conventional systems
because the syngas burned in the combustion turbine is moisturized at the
gasification facility, making use of low level heat in the process. This flow is
continuously made up at the power block by clarification and treatment of river
water.
The air separation unit (ASU), which provides oxygen and nitrogen for use in
the gasification process, is not an integral part of the plant thermal balance. The
ASU will utilize services such as cooling water and steam from the gasification
facilities, and will be operated from the gasification plant control room. The air
compression at the ASU is not integrated with the combustion turbine compressor.
While some studies show that such integration can improve plant efficiencies,
project participants felt that implementing new compression integration concepts
would detract from the operability and availability of the WRCGRP in most
operating scenarios.
OPERATIONS
Destec and PSI will independently operate their respective gasification and
power generation facilities. Operating interface parameters and other key data will
be interchanged continuously between the gasification and power generation
control rooms. In normal operation, syngas production will follow combustion
turbine fuel demand. Thermal balance between the facilities is flexible to a certain
extent, utilizing the heat recovery steam generator and gasification facility heat
exchangers, and will follow the syngas production.
Operation of the facilities will be closely coordinated during startup and
shutdown. The combustion turbine operates on auxiliary fuel (oil) at low loads
during startup and shutdown. A "flying switch" will be made to syngas and the
combustion turbine will ramp up to full load at its normal rates.
COST AND EFFICIENCY
Integration of the new and existing power generation facilities and the new
gasification facilities have resulted in lower installed cost and better efficiency than
other "environmentally equivalent" coal based power generating projects. Reduced
development effort and shorter schedule can also result from choosing to repower
existing stations, because of the siting problems that even clean coal technologies
may have for greenfield installations.
The net plant heat rate for the entire new and repowered unit is forecast to be
less than 9000 BTU/kWH, representing an approximate 20% improvement over the
existing unit. Certain major component manufacturer margins and guarantees
(combustion turbine, HRSG, HTHRU, etc.) are included in this energy balance
518
calculation; actual operation is expected to be slightly better. This heat rate will be
among the lowest of commercially operated coal-fired facilities in the United States.
The combustion turbine generator will produce approximately 192 MW. Steam
generated by the combustion turbine heat recovery steam generator and in the
gasification island will supply the existing steam turbine generator to produce an
additional 109 MW. Plant auxiliaries in the power generation and coal gasification
areas and the oxygen plant will consume approximately 33-36 MW.
The total estimated installed cost for the Project is $362 million, of which
Destec's and PSI's facilities are $240 million and $122 million, respectively.
These estimated figures include escalation through 1995 (5% annually), startup
costs, and license fees. On this basis, the total estimated developed and installed
cost of the project is approximately $1350 per kW of net generation. These figures
do not include funding from the Department of Energy's Clean Coal program in
which the project is participating.
CONCLUSION
Integration of the physical systems and the thermal cycles of the power
generation and coal gasification facilities at WRCGRP have led to a relatively low
cost coal fired installation, which will operate at an attractive heat rate. Thermal
integration maximizes the utilization of heat available in the coal gasification
process and increases the amount of high pressure steam available for power
generation. Repowering an existing steam turbine generator unit, while minimizing
redundant systems in the power generation and coal gasification plants, reduces
installed cost as well as improving development and construction schedules.
Spent seed regeneration in coal-fired MHD system using weak-base

anion-exchange resins*
A. C. Shetha and S. D. Strevelb
a Associate Professor, Environmental & Process Development Department, Energy

Conversion Research & Development Programs, The University of Tennessee
Space Institute, B. H. Goethert Parkway, Tullahoma, Tennessee 37388-8897
b 1732 Maplecrest Drive, Louisville, Tennessee 37777
1. ABSTRACT
In a coal-fired Magnetohydrodynamics (MHD) system, the combustion gases

are seeded with easily ionized potassium carbonate to provide 1 % by weight of
potassium in the resulting plasma. The potassium carbonate seed serves the dual
purpose of increasing the electrical conductivity of the plasma and of removing the
sulfur-containing gaseous products derived from combustion of high-sulfur coal.
For MHD technology to be economically feasible, a high percentage of the
potassium must be recovered and recycled in the form of sulfur-free potassium salts
such as potassium carbonate. The process of sulfur removal from spent seed, or
K 2 S 0 4 - r i c h material, is termed seed regeneration. A seed regeneration concept
has been developed and tested at the University of Tennessee Space Institute
(UTSI), wherein a commercially available weak-base, anion-exchange resin is
used at ambient conditions to remove sulfur from the alkali metal sulfates.
Currently, under a grant from the University Coal Research (UCR) program
sponsored by the U.S. Department of Energy's Pittsburgh Energy Technology
Center, UTSI is further developing this anion-exchange resin-based desulfurization
concept.
In this paper, results from the following activities performed to date under this
grant are discussed:
Screening of commercially available resins carried out in batch mode

experiments.
Process variables study on three selected resins carried out in fixed-bed
mode experiments.
This work was supported by the U.S. Department of Energy under Grant
No. DE-FG22-90PC90309.
520
Comparison of preliminary economics with the other candidate seed

regeneration option(s), and
Potential applications to conventional power plants and waste
incinerators.
2. BACKGROUND
Magnetohydrodynamics (MHD) involves interactions among electromagnetic

fields and electrically conducting gases and liquids. Faraday's law underlies
MHD's electric power generation capability. In an open-cycle, coal-fired MHD
system, the working fluid or conducting medium is a high-temperature combustion
gas that flows through a magnetic field. A typical coal-fired, combined-cycle system
(see Figure 1) consists of a MHD topping cycle combined with a steam bottoming
Coal
AC
power
Generator Steam h

Inverter Turbinen
\ /
- Combustor
tor KlHD
MHD Channel Dil
Diffuser
Air.
Radiant
Boiler
31 Secondary
Combustor
Super
Heater/
L stack
Particulate
Air Heater Collection
Slag [~SeeT]
Seed
Sulfur and
Particulates
Seed Makeup IL-1505
Figure 1. MHD and steam generation plant
cycle for generating electricity. In the topping cycle, coal Is seeded with a
potassium salt and burned fuel-rich, at high temperature and pressure, in a
combustor to produce the electrically conducting gas, called plasma. This plasma
expands through a nozzle and enters the MHD generator at high velocity.
Temperatures in the MHD combustor approach 3033 (5000F), and pressures are
typically 5 105 pascals (5 atmospheres) or higher. Gas velocities in the generator
may exceed 762 m/s (2500 ft/s), and the generator can be operated with either
521
subsonic or supersonic gas velocities. Combustion gas contains about 1 %

potassium by weight. This amount of potassium is adequate to provide electrical
conductivity of approximately 10 S i e m e n s per meter (S/m) at the entrance of the
MHD generator channel. Following the MHD generator, the gases pass through a
diffuser to recover pressure and reduce velocity, then exit into the steam generation
plant.
The steam generation (or bottoming) plant portion of the MHD system is often
described as a heat recovery/seed recovery system. In the steam plant, the
combustion gases are cooled from more than 2200 (3500F) to less than 422
(300F) to recover the thermal energy. Because the primary combustor is operated
fuel-rich (for control), the secondary combustor uses heated air to burn the
remaining CO and H2. The hot combustion gases generate steam at pressures
usually above 138 105 pascals (2000 psi) and superheat the steam to about 811
(1000F). The steam then is used to drive a turbine/generator-set to produce
additional electrical power. Thus, the combined-cycle MHD system has the
potential of increasing the overall plant efficiency from 35% to about 60%.
The seed (potassium) is collected on tube surfaces in the steam generation

plant and also downstream in a separate particulate collector such as an
electrostatic precipitator or fabric filter. Most of the coal ash is collected as slag in
the high temperature combustor or at the entrance to the steam generation plant
furnace. The remainder of the ash is collected with the spent seed in the
downstream components and separated during the seed recovery/regeneration
operation.
Chemical reactions between SO2, and alkali metal salts, such as NaaCOa,
NaHCOa, KOH, and K2CO3, proceed under relatively moderate conditions. The
products contain mostly sulfates. Similarly, the chemical reactions between CI2-
containing species (e.g. HCl and CI2) and alkali metal salts would be complete
under typical MHD downstream conditions. The resulting chlorides are captured in
the appropriate particulate collection device and can either be processed during
desulfurization of K2S04-containing material or discarded.
From an environmental standpoint, the waste material coming from a MHD

process can not be acceptably and easily disposed of in conventional landfills.
Alkali metal sulfates and other salts are water soluble and would pose the problem
of leaching into the ground water. Surface run-offs from such disposal sites can
also alter the soil pH which is not allowed. Due to the scarcity of land and more
stringent regulations, the disposal costs for such materials have increased
significantly. Because of low demands and the possible presence of other trace
elements, the usefulness of such material as valuable by-products is limited. Also,
the economics of such sulfur-emission control processes are highly sensitive to the
amount of fresh (virgin) sorbent required, since the cost of replacement material to
control the emission of sulfur-containing species is quite significant. Thus, from an
economic as well as environmental point of view, it becomes desirable to
522
regenerate alkali metal spent sorbent recovered from the MHD technology so that it
can be readily reused.
Researchers working in the fields of flue gas desulfurization (FGD), pulp and
paper production, catalytic coal gasification, and MHD power generation have
investigated various options to achieve desulfurization of alkali metal sulfates.
Under the U.S. Department of Energy (DOE) sponsored programs, several
processes capable of separating sulfur from alkali metal sulfates have been
identified and process evaluation studies have been conducted(i-5). All of these
studies have identified significant needs for technology advancement necessary to
design and develop an acceptable, economical regeneration system. An ideal
desulfurization concept should have the following attributes:
easy operation at low operating temperature and pressure

low cost and no significant environmental problems
use of available technology (hence reduced development time and
cost)
high recovery and recycle of alkali metal reagent
The ability to remove simultaneously other anions such as 01-, F-, and NO3- is
considered an added advantage. Since the presently considered options for seed
and spent sorbent regeneration do not meet all or most of the above criteria, a need
exists to develop a simple and readily acceptable option.
3. ANION-EXCHANGE RESIN-BASED DESULFURIZATION CONCEPT
A concept has been developed and tested at the University of Tennessee

Space Institute (UTSI) which employs a commercially available weak-base, anion-
exchange resin to remove sulfur from alkali metal sulfates.
One of the characteristics of anion-exchange resins is their varying affinities

for certain anions. As reported in the literature (6), the affinity of a weak-base, anion-
exchange resin for various anions decreases in the following order.
O H " ^ P O ^ -> SO^- -> N 0 ^ c r HCOi (1)

(strongly attached) > (weakly attached)
A weak-base anion-exchange resin is commercially supplied in a hydroxide

form by the supplier. Based on the above mentioned selective affinity for specific
anions, the active sites in the fresh resin must be converted to the bicarbonate form
before its first time exhaustion or replacement with SO42- ions. This is
accomplished by treating the resin with carbonated water (water saturated with
CO2) to produce active bicarbonate groups according to the following reaction:
+ C02 03 (2)
523
(Here R represents the complex cation groups present in the resin). The resin is
then exhausted by an aqueous solution of alkali metal sulfate as follows:
2R.HC03 + M2SO4 R2*S04 + 2MHCO3 (3)
The bicarbonate containing solution is then converted to a corresponding

carbonate and/or bicarbonate during the evaporation/concentration steps, before it
is recycled to the process, as a dry powder or concentrated solution. Carbon
dioxide released during this conversion can be reused in carbonating the hydroxide
form of the resin in Reaction 2. The exhausted resin is then regenerated to the
hydroxide form using an NH4OH solution.
R2*S04 + 2NH4OH ^ {NH4)2 SO4 + 2 R . 0 H (4)
The ammonium sulfate, (NH4)2S04, produced can then be concentrated (if

necessary) and sold as fertilizer or processed for recovery and recycle of the N H 3
using the following optional step. In this step, an aqueous solution of (NH4)2S04
when heated in a batch reactor to about 473 - 523 (200 - 250C) temperatures,
would decompose into ammonia (boiling point of ~ 240 K) and water vapors
(boiling poing of 373 K). The remaining liquid fraction thus becomes concentrated
in sulfuric acid, H2SO4 (decomposition temperature of 613 K). On controlled
cooling, the ammonia vapors can be separated from the water condensate. The
recovered ammonia can then be recycled to the resin regeneration step.
(NH4)2S04 + 2H2O 473_^523-K> 2NH4OH + H2SO4 (5)
The free base resin thus formed is then treated with carbonated water for
reuse in the next cycle.
3.1 Earlier version

The three steps of resin exhaustion, regeneration, and carbonation are
schematically shown in Figure 2 as an earlier version of UTSI's concept. It involved
two separate steps for regenerating the exhausted resin. Butler(7) demonstrated the
technical feasibility of the UTSI process using this 3-step version of the concept.
3.2 Improved version

Modeste(8) improved upon Butler's concept by combining the carbonation
and exhaustion into one step that was carried out under 50-100 psig (static)
pressure of CO2. Modeste's improved concept is also shown in Figure 2. This
improvement in the process concept achieved the following:
Simplified the concept and reduced the number of processing steps

from three to two.
524
EARLIER VERSION
K2SO4 NH4OH
egenerated
:*: Resin ::"
R234 -R*OH- R-HC03
R-HC03 KHCO3 ' (4)284 ^ Excess CO2
EXHAUSTION REGENERATION CARBONATION
REVISED VERSION
K2S04 NH4OH
R*OH ^ R2 S O 4 R-OH
Excess C O 2 ^ #-KHC03 ^ (4)284
CARBONATION & EXHAUSTION REGENERATION

IL-1506
Figure 2. Schematic of ion-exchange resin-based desulfurization concept
Increased the resin capacity for SO42- by about 50 percent.

Reduced the resin inventory by 33 percent.
4. UCR PROJECT DESCRIPTION
Initial bench scale testing of the resin-based desulfurization concept was

carried out on a limited scope at UTSI with discretionary funding. During these
efforts, a technical feasibility check of the concept and improvement of the process
from a 3-step to a 2-step was accomplished. Subsequently, in August 1990, the
University received a DOE grant under the University Coal Research (UCR)
program to carry out a systematic bench scale evaluation and further develop the
UTSI concept. A detailed description of this 3-year long, UCR project is available in
Reference 9, however, a brief summary follows.
525
The specific objectives to be accomplished during UTSI's UCR grant project

are:
Further improve the UTSI concept by identifying the best available resin
and optimizing the resin exhaustion, regeneration and carbonation
conditions, and
Develop Best-Process Schematic and related economics.
To accomplish the above objectives, the following approach has been

planned:
- Perform screening of the commercially available candidate resins

- Perform process variables study and improve resin performance
- Optimize the resin regeneration step
- Evaluate the effect of potential performance enhancers
- Develop the Best-Process Schematic and related economics, and
- Develop plans for Proof-of-Concept (POC) scale testing.
To date, the project is at the stage where the resin regeneration step is being
optimized and the effect of potential performance enhancers is being evaluated.
Once this is completed, the cycle efficiency of the selected resin will be evaluated,
and the Best-Process Schematic as well as related process economics will be
developed.
5. RESULTS & DISCUSSIONS
5.1 Major results f r o m p r e v i o u s UTSI s t u d i e s

Using the 3-step process and reagent grade chemicals, Butler(7)
demonstrated the technical feasibility of UTSI's concept by performing fixed-bed
experiments at the bench scale level. In doing so, he showed that a particular resin
(Amberlite IRA-68) maintained the capacity for SO42- for at least four consecutive
cycles of exhaustion and regeneration, and that the solution concentration and bed
height did not affect the ion-change kinetics significantly. However, from Butler's
work, the product inhibition effect caused by the presence of KHCO3 in the initial
sulfate containing solution was noted (above certain molar ratios of KHCO3 /
K2SO4) as an apparent reduction in the resin's capacity for the SO42- ions.
Using the 2-step process (where exhaustion and carbonation steps were
combined), Modeste(8) demonstrated that by increasing the static CO2 pressure
from 0 psig to 40 psig, the equilibrium capacity of the Amberlite IRA-68 resin could
be increased by about 50%. His work also showed that the fixed-bed kinetics data
can be better satisfied by a math model that incorporates a non-linear equilibrium at
the solid/liquid interface and a solid-phase diffusion as the overall mass transfer
controlling step. Such a model was found to resolve the problem Butler had faced
526
in satisfying his bench scale data with a math model which incorporated the liquid-
film mass transfer as the overall rate controlling step.
5.2 Major results f r o m batch mode s c r e e n i n g e x p e r i m e n t s

In the proposed program to DOE, there was no plan to carry out screening
experiments in the batch mode. All of the candidate resins were to be evaluated in
fixed-bed mode experiments. However, from contacts with the resin suppliers,
eleven candidate resins were identified. Evaluations of so many resins in the fixed
bed mode would take an exceptionally long time, so a decision was made to
evaluate them first in batch mode experiments. In this mode, parameters such as
K2SO4 solution concentration (1000 - 50000 ppm), cyclic operations (4 consecutive
cycles), dissolved impurities (reagent grade K2SO4 solution versus MHD spent
seed extract), and cation effect (i.e., sodium versus potassium chemistry) were
evaluated. Results of these batch mode experiments are documented in Reference
10. These results were then further evaluated by the analysis of a variance, two-
way fixed-effects model to identify parameters which have a significant effect on
resin performance. The results from this statistical analysis are given in Table 1.
Table 1
Parameter effects on exhaustion and regeneration efficiencies
(from batch mode experiments)
Parameter Effect on
Exhaustion Efficiency Regeneration Efficiency
Resin Type Significant Significant
Solution Concentration Varies inversely No effect
Cyclic Operation No effect Significant
Cation (Na vs. K) No effect No effect
Dissolved Impurities (spent seed) No effect No effect
These batch mode screening experimental results were also used in the
multiattribute analysis to determine ranking of the candidate resins. This analysis is
described in detail in Reference 1 1 . The result of this particular analysis is
expressed in terms of the calculated utility for the given resin. For a resin to achieve
a utility of 1.0, all of the percent removal and percent retained values must be ideal
and equal to 100 and 0%, respectively. The calculated resin utilities are given in
Table 2, which shows that based on the statistical analysis and arbitrarily assigned
weighting factors, the best resins are IRA-68, IRA-35, and IRA-93. These three
527
resins, therefore, were used in the process variables study carried out in a small
fixed-bed set-up.
Table 2
The calculated resin utilities
Resin Utility ( U r )
IRA-68 0.46
IRA-35 0.43
IRA-93 0.29
A-305 0.18
UNKNOWN 0.16
IRA-94 0.12
MWA-1 0.11
WGR-2 0.11
A-7 0.10
AFP-329 0.10
A-365 0.07
5.3 Major results from process variables study

To carry out the process variables study, a fixed-bed rig was designed and
constructed that included two different diameter glass columns, a semi-automatic
sampling device, and appropriate tanks, valves and instrumentation to provide
long-time unsupervised operation. This rig and the related experimental procedure
are described in Refr'nce 12. Using this rig and three candidate resins (IRA-68,
-35, and -93), the fouwing process variables were evaluated.
C02-pressure
solution concentration
product inhibition
bed height
dissolved impurities
superficial velocity
solution pH
Results from this process variables study are discussed in detail in References 11
and 12. However, some of the major findings are as follows:
5.3.1 Effect of static COa-pressure

The effect of static C02-pressure during the combined exhaustion/
carbonation step on the equilibrium capacity of the three candidate resins is shown
in Table 3. As seen from this table, the equilibrium loading increases with the CO2-
pressure and appears to level off at around 80-120 psig. Based on these results, it
528
is believed that the higher static C02-pressures would create more bicarbonate ions
on the resin sites, which are then substituted by sulfate ions in the solution resulting
in an increased capacity. This possibility can be represented by the following
reaction:
2R*HC03 ^ R2^C03 + CO2 + H2O (6)
where R is the complex cation group on the resin.
Table 3
Effect of C02-pressure on equilibrium loading
Basis: 0.028 gm S04=/ml solution
COg-pressure lRA-35 IRA-68 IRA-93

(psig) (g S04=/mlR) (g S04=/mlR) (g S04=/mlR)
0 0.068a _
10 0.073 0.065 0.074

20 - 0.087b -
40 0.098 0.124b 0.096
80 0.130 0.164
120 0.126 0.136 0.168
a Butler(7)
b Modeste(8) with 0.039 gm S04=/ml solution
mlp - represents volume of resin in c m 3 .
The effect of C02-pressure on ion-exchange kinetics was evaluated in terms of the

diffusion parameter, (D/R2), that was derived by matching the experimental and
theoretically generated model breakthrough curves. In the range of C02-pressures
that were employed, the D/R2 values for candidate resins changed very little with
the C02-pressure indicating that the kinetics did not change significantly.
5.3.2 Effect of solution concentration

Experimental results on equilibrium capacities of each resin at different
solution concentrations and C02-pressure were fitted to the Langmuir isotherm
given by
a, C, (7)
^^"1+a2Co
where Co = sulfate concentration in bulk solution

q = sulfate concentration at equilibrium on resin, and
ai and a2 are Langmuir constants.
529
The typical fitted isotherms for the three candidate resins at a COa-pressure of 10
psig are shown in Figure 3. As shown in this figure, at a given solution
concentration the IRA-93 resin seems to provide a slightly greater loading than the
other two resins.
g. 0 0.005 0.01 0.015 0.02 0.025 0.03

^ Initial S o l u t i o n C o n c e n t r a t i o n
(gmS04=/mlsoiution)
CG-2679
Figure 3. Langmuir isotherms for IRA-35,
IRA-68, and IRA-93 at 10 psig
C02-pressure
The effect of solution concentration on the ion-exchange kinetics was

measured in terms of the D / R 2 parameter and is shown in Figure 4. Based on this
figure, the diffusion parameters for IRA-68 resin seem to be affected significantly by
the concentration, whereas the IRA-35 and -93 resins seem to show no or very little
effect. This effect on the IRA-68 resin may be attributed to its gel-type structure as
such resins have usually larger pores, and therefore, possibly better (or faster)
intraparticle diffusion.
5.3.3 Effect of product inhibition

Product inhibition (PI) is defined as the interference caused by the product,
KHCO3, to the operation of the ion-exchange resin. By retarding the transfer of
HCO3 - ions from the resin, the KHCO3 present in the bulk solution can affect the
transfer of SO42- ions from the bulk solution to the resin sites, and thereby, can
reduce the resin's capacity for sulfates. The magnitude of the PI effect in the
experiments was determined by using bulk solutions containing initially known
molar ratios of KHCO3 / K2SO4. Resulting equilibrium capacities of the candidate
resins for SO42- are compared with the results reported by Butler(7) in Table 4.
Within experimental scatter, there seems to be no effect of PI on the loading of IRA-
35. However, for IRA-68 and -93, the loadings increase for molar ratios up to 0.1
and then show a significant decrease at a molar ratio of 1.0 and higher. The
530
possible reasons for such behavior are still being explored. Presence of varied
levels of KHCO3 in the bulk solution did not change the ion-exchange kinetics
which was observed as similar shapes of breakthrough curves at different molar
ratios of KHCO3 / K 2 S O 4 .
oc
Q
1 0.01 0.02 0.03 0.04 0.05 0.06
Initial S o l u t i o n C o n c e n t r a t i o n
(gm S O / m i solution)
CG-2684A
Figure 4. Effect of solution concentration on
diffusion parameter
Table 4
Effect of product inhibition (PI) on equilibrium loading
Basis: 0.028 gm S0427ml solution and 10 psig CO2 - pressure
Molar Ratio IRA-35 IRA-68 IRA-93

(PI) (g S04=/mlR) (g S04=/mlR) (g S04=/mlR)
0.0 0.073 0.065 0.063b 0.074

0.1 0.068 0.095 0.087b 0.098
1.0 0.072 0.061 0.047b 0.088
is for Butler's(7) runs at atmospheric pressure

mlp - represents volume of resin in c m 3
5.3.4 Effect of superficial v e l o c i t y

In general, unless a very high superficial velocity is employed, the
equilibrium loading of the given resin should not vary with the velocity. At very high
velocities there exists a potential of bulk solution by-passing the resin bed material
completely or partially, and thereby, resulting in low values for the observed
equilibrium capacity. Experiments were carried out for the IRA-35 resin using
531
similar volumetric flow rate and a nominal 5 wt % K2SO4 solution in two columns of
different diameter (which provided different superficial velocities). The resulting
curves, Co/ . when plotted against the grams of sulfate introduced per unit volume
of resin (i.e., gm SO42- / mlresin), showed a finite displacement (see Figure 5). If
there was no difference in the rate controlling mass transfer step at these two
velocities, the two curves should overlap or be close to each other within
experimental scatter. The fact that the curve for lower velocity (e.g., 0.009 cm/s)
broke through earlier, indicates that most likely the mass transfer across the liquid
film surrounding the resin particle controlled the rate. As a result, less SO42- was
being removed by the resin particles, and therefore, more SO42- showed up in the
effluent as unexchanged.
uJ 0.0'
1 0.04 0.08 0.12 0.16
G r a m s of S u l f a t e / m l of R e s i n
CG-2688A
Figure 5. Effect of superficial velocity on
IRA-35
Later, it will be shown that most of the experiments carried out under the
present program at higher velocities, were well satisfied by the Antonson's(i3) fixed-
bed model that considers solid-phase (intraparticle) diffusion as the rate controlling
step. Hence, it is believed that for experiments carried out at lower velocities (e.g.,
at 0.009 cm/s and lower), one should use the Seike and Bliss m o d e l ( i 4 ) that
considers liquid-film transfer as the rate controlling mass transfer step. Butler(7),
using the SeIke and Bliss model also saw a significant effect of superficial velocity
on the ion-exchange kinetics of IRA-68 resin. He measured this effect in terms of
the parameter K l S , (that is the product of liquid-film mass transfer coefficient ( K l )
and the resin's effective surface area (S)). From his observations, Butler provided
the following empirical relationships between the superficial velocity, u and K l S O S ) .
Reynolds number. Re, in these relationships is calculated based on the particle
diameter.
for u < 0.02 cm/s (or Re < 0.09)

K l S = 0.00367 ( ^ ^ ^ ^ ^ ) 9 9 (in cm^ /g resinas)
(8)
532
for u > 0.02 cm/s (or Re > 0.09)

K l S = 0.011 (in cm^ /g resinas) (9)
Thus, the superficial velocity can significantly affect the mass transfer
coefficient as well as the overall rate-controlling step; and care needs to be taken in
selecting the fixed-bed model for data analysis.
5.3.5 Effects of other variables

Under the UCR grant, experiments were also carried out to evaluate the
effects of variables such as bed height, dissolved impurities and solution pH. Within
the range of values tried, the bed height (from 20.3 cm to 40.6 cm high) did not
affect the ion-exchange kinetics suggesting the absence of possible channeling in
the bed.
The effect of dissolved impurities tested using the MHD spent seed extract
proved to be inconclusive. A slight decrease in the equilibrium capacity of IRA-35
was noted; however, there were no similar reductions in the capacities of the IRA-68
and IRA-93 resins. In earlier work(7) with a different batch of spent seed, a slight
decrease in the capacity of IRA-68 was observed. Hence, it is believed that the
concentrations of the dissolved impurities (CI- and F-) could change from test to test,
especially during MHD testing at UTSI where different process parameters such as
K2/S ratio and coal type, etc., are attempted. A more systematic study with known
initial concentrations of dissolved impurities is therefore necessary. In any case, the
shapes of breakthrough curves for all the resins (in our earlier study and this study)
were similar, implying that the small levels of dissolved impurities such as CI- and F-
ions did not change the ion-exchange kinetics significantly.
The effect of initial solution pH on the resin performance was evaluated by

carrying out fixed-bed experiments using 50,000 ppm K2SO4 solution (pH = 7.5),
and a mixture of 50,000 ppm K2SO4 solution with a small amount of acetic acid
solution (pH = 4.25). For all three resins, the effect was similar in the sense that the
breakthrough curves for pH = 4.25 moved slightly to the right of the curves for pH =
7.5 (Figure 6). However, the shape of the curves remained the same. These results
can be interpreted as slightly acidic solutions at the bed inlet either helping in
maintaining the acidic to neutral conditions (as recommended by the
manufacturers) in the entire bed, and thereby, improving the resin capacity or
helping in improving the ionic mobility of the sulfate ions. From the similar shapes
of the breakthrough curves it can be stated that the solution pH did not change the
ion-exchange kinetics significantly, and therefore, the diffusion parameter D/R2.
5.4 Fixed-bed mathematical model and data interpretation

Based on Butler(7) and Modeste's(8) work, Antonson's model was used to
analyze the fixed-bed data(i3). This model assumes a non-linear equilibrium at the
solid/liquid interface and solid-phase (intraparticle) diffusion as the mass transfer
controlling step. This model requires two inputs: a2Co (non-linear equilibrium
parameter) and X (dimensionless column length). With these inputs, the model will
533
20 30 40 50 60 70 80
T i m e (min.)
CG-2689A
Figure 6. Effect of solution pH on
breakthrough curve for
IRA-68
generate a theoretical breakthrough curve which when plotted on a semi-log plot

can be visually fitted to an experimental curve. From the best fit, the diffusion
parameter, D/R2, can be determined using the equation for the dimensionless
column length, X. (D is the effective diffusion coefficient and R is the particle
radius). An example of the typical best fit for a run is presented in Figure 7, and
shows that the Antonson's model well satisfied the experimental fixed-bed data.
3 1.0
^ 0 . 8
2 0.6
0 Run 59
Model Curve
0.4
0.2
0.0
100 1000 10,000 100.000
R u n T i m e (min)
CG-2682
Figure 7. Typical best fit: run 59 (IRA-68, 10
psig, 0.004 g S04=/ml, 20.3 cm bed
height, 4.96 cm2 column area, and
11.0 cc/min)
6. PRELIMINARY ECONOMICS
At present, under DOE sponsorship, the TRW Company is developing a seed

regeneration option called the "Econoseed Process" which is based on the old
534
"Formate Process". The major chemical reactions involved and the related
operating conditions are as follows:
Ca-formate production:
(0H)2.2CO , , o o - ? 3 ? O p s i g > ( 1 0 )
K-formate production:
Ca (HC00)2 + K2SO4 j ^ ^ > CaS04 + 2 K C 0 0 H ^^
The preliminary cost of seed regeneration based on the 3-step version of the
anion-exchange resin-based concept was estimated by the Resources
Conservation Company(16). This estimate was modified using the 6/10th rule to be
consistent with the assumptions made by TRW for the Econoseed Process. In Table
5, the two costs are compared for a 300 MWt plant burning Illinois #6 coal for
Table 5
Comparison of seed regeneration costs
(mils/kwhr)
Basis 300 MWt MHD plant burning Illinois no. 6 coal
Availability of seed regeneration & main MHD plant same
-Total Cost,* mils/kwhr-
Overall
Efficiency 33.8% 33.8% 40% 40% 50% 50%
Availability 95.9% 65% 95.9% 65% 95.9% 65%
Econoseed
Process - 21.3 - 18.1 - 14.4
Ion-Exchange
Resin-Based
Process 7.6 8.9 6.4 7.5 5.1 6.0
* Includes capital and operating costs
different plant availability factors and overall efficiencies. The improvements made
and still being made in the resin-based concept are not incorporated in this
estimate. Even without these potential improvements the preliminary indications
are that UTSI's process will be up to 2.4 times less expensive (in mils/kwh) than
TRW's Econoseed Process. In addition, chloride buildup in the MHD seed has now
535
been identified as undesirable and it appears that appropriate controls will be

required to remove the chlorides from the spent seed. The resin-based UTSI
concept can remove simultaneously the sulfate and chlorides without additional
cost. The Econoseed Process also will need some additional measures, such as
discarding a slip-stream (thereby throwing away some potassium) or using
fractional crystallization. These measures will increase its cost, lower its efficiency,
and, therefore, make the Econoseed Process less attractive.
7. APPLICATIONS TO CONVENTIONAL POWER PLANTS & WASTE

INCINERATORS
Besides MHD seed regeneration, the resin-based UTSI concept can be

applied to desulfurize and simultaneously dechlorinate the spent sorbents (alkali
metal compounds) used in conventional power plants and waste incinerators.
NaHCOa, N a 2 C 0 3 , and Trona type sorbents when injected either as a

solution, slurry or dry powder at relatively lower temperatures after the air heater in
the duct work of conventional power plants, can remove S O 2 more efficiently with
higher sorbent utilization than lime/limestone scrubbers. The spent sorbent
materials in such a case contain mostly Na2S04 and N a 2 S 0 3 . UTSI's resin-based
scheme can be applied to desulfurize this spent sorbent material for recycle and
reuse rather than disposal in a lined landfill. The process schematic for such an in
duct sorbent injection type FGD option coupled with UTSI's sorbent regeneration
concept is shown in Figure 8. The capital cost for this scheme is compared with the
commercially available Wellman Lord (a high temperature sodium-based) process
and MgO scrubbing process in Table 6. This comparison shows that the FGD
system, based on in-duct sorbent injection coupled with resin-based regeneration,
is cheaper and probably easier to operate than these commercially available
options.
Similarly, closed water loops in lime/limestone-based flue gas

desulfurization (FGD) systems, combined with the combustion of high chlorine coals
and the use of cooling tower blowdown as makeup water, produce detrimentally
high concentrations of chloride in the absorbing scrubber liquor. Chloride buildup
in the scrubber liquor can affect material selection, S O 2 removal efficiency and
limestone utilization. The capability of simultaneously removing chloride and
sulfate from such scrubber liquor was tested using a simulated mixture and UTSI's
resin-based conceptea). The preliminary results from this study are given in Table 7
and show that more than 90% of the S O 4 2 - and CI- can be simultaneously removed
from the scrubber liquor.
In waste incinerators, the emissions of S O 2 and HCI/CI2 can be controlled

using the same type of technology as MHD, by introducing alkali metal sorbent at
high temperature (along with the waste and auxiliary fuel) or at low temperature
using a spray dryer or scrubber type unit. The resulting spent sorbent material will
contain CI- and SO42-. Instead of disposing this material in a landfill as users of
536
^ Sulfuric A c i d
for Sell
Flue Gases
From Boiler
Water
DISSOLVER
7
[
Insolubles to
Waste Disposal IL-1507
Figure 8. Process schematic for anion-exchange resin-based desulfurization of
sodium-based spent FGD sorbent
Table 6
Preliminary cost estimate for regenerable sodium-based FGD system
Basis: 1000 MWt power plant
Capital Cost-
OPTION Low-Sulfur High-Sulfur

Coal ($/kw) Coal ($/kw)
Ion-Exchange Resin-Based Concept

- Cost of Sorbent Regeneration 33 108
- Cost of Desulfurization* 25 50
- Total 58 158
Wellman Lord & MgO Scrubbing

Process ** 275
Stearns-Roger Engineering Corporation's Estimate, EPRI

Journal, p. 20, March 1984 Issue
EPRI CS-3324 Report
small incinerators would do, one can employ the UTSI process to reactivate the
spent sorbent either on-site or at a centralized location and then recycle the
reactivated sorbent. Ability of simultaneous removal of CI- and SO42- from the MHD
spent seed material is being evaluated at UTSI under a separate DOE project.
However, preliminary results from an earlier test are shown in Table 8.
537
Table 7
Simultaneous removal of chloride and sulfate from simulated scrubber liquor(a)
Basis: Mixing at room temperature for one hour
Sol'n Concentration, ppm % Anion-Removed

Resin ml Solution
Pescription per ml Resin Chloride Sylfat? Chlgride Sulfate
A305 2 12,300 12,700 49.6 32.9

IRA-68 62.8 62.1
A305 2 6,300 6,800 58.0 50.9

IRA-68 69.5 77.9
A305 2 2,600 2,790 79.5 88.3

IRA-68 82.7 96.2
A305 2 1,200 1,290 77.9 90.0

IRA-68 89.7 98.9
A305 2 600 680 85.7 96.2

IRA-68 93.1 99.5
A305 1 12,200 13,400 66.4 47.1

IRA-68 82.2 88.4
A305 20 1,200 1,330 19.1 50.4

IRA-68(b) 17.2 70.9
A305 20 1,230 1,320 24.6 48.8

IRA-68(b) 27.6 73.5
A305 2 12,900 0 52.6 _
IRA-68 64.4 -
A305 2 0 14,600 _
52.0
IRA-68 - 75.6
(a) Simulated scrubber liquor contained aqueous solution of MgCl2, MgS04 and
CaCl2 with pH adjusted to 4.0 using glacial acetic acid.
(b) Duplicate Tests
538
Table 8
Simultaneous removal of SO42- CI- and F- ions from MHD spent seed
by anion exchange resin
-Concentration in PPM-
8 0 4 2 " Ion CI" Ion p- Ion

Solution Concentration Concentration Concentration
Initial/untreated 18000 50 31
Treated 0 3 19
% Removal 100 94 39
Thus, besides MHD seed regeneration, the resin-based concept can be

useful in conventional power plants and waste incinerators.
8. CONCLUSIONS
The work under the UCR grant is ongoing. The major activities such as
optimizing the resin regeneration step, evaluating the effect of potential
performance enhancers and development of the "Best-Process Schematic" and
related economics are to be completed soon. However, based on the work done to
date, one can reinforce the results and claims made in the past from the Butler and
Modeste's work and can show that the UTSI's resin-based
desulfurization/dechlorination concept offers a better alternative than the presently
considered options. In particular, based on the work done to date, the following
conclusions/ observations can be drawn:
Efficiencies of resin exhaustion step and regeneration step differ from

resin to resin. This implies that physical and chemical structures of
candidate resins must play a role as to the accessibility of the active
sites in the resin interior and the affinity with which the various ions are
held or can be exchanged from these sites.
The efficiency of exhaustion step decreases with an increase in the
solution concentration. This implies that for commercial applications a
trade-off will be required to optimize the resin cost versus the cost of
evaporation and concentration load for the ensuing effluents.
Based on the statistical analysis of the batch mode screening results,
the IRA-68, -35 and -93 performed better than the rest of the candidate
resins.
539
Under the static CO2 atmosphere, the equilibrium capacity of IRA-68, -35
and -93 resins increases as the C02-pressure increases and then levels
off around 80-120 psig range. However, the C02-pressure does not
affect the ion-exchange kinetics.
The solution concentration affects the resin performance in two ways.
First, the equilibrium capacity of resin increases with the solution
concentration and then levels off (hence satisfied by the Langmuir
isotherm type relationship). Second, the diffusion parameter, D/R2
either increases (for IRA-68) or remains constant (for IRA-35 and -93)
with the increase in the solution concentration.
Product inhibition effect caused by different amounts of KHCO3 in the
initial solutions indicates that up to a molar ratio of KHCO3/K2SO4 equal
to 0.1 there is a positive effect on the resin's capacity. However, beyond
0.1, the capacity decreases significantly with the further increase in the
molar ratio. This ratio, however, does not affect the ion-exchange
kinetics.
Superficial velocity seems to affect the rate controlling step. At low
velocity, most likely the liquid-film diffusion seems to control the overall
mass transfer rate and which can be satisfied by the Seike and Bliss
type model. At higher velocity, the solid-phase diffusion seems to
control the overall rate and can be satisfied by the Antonson's model.
Within the range of values tried, the bed height and dissolved impurities
did not significantly affect the performance of the candidate three resins.
On the other hand, a slightly acidic pH of the initial solution seems to
improve the equilibrium capacity of the resin.
UTSI's resin-based desulfurization concept can simultaneously remove
chlorides also, and therefore, can be applied to conventional power
plants as well as waste incineration for reactivating spent sorbents.
Based on preliminary economics, the UTSI concept is also more
attractive than the Econoseed Process being developed by TRW, and
the commercially available Wellman Lord and MgO scrubbing
processes.
In summary, from the work done to date under the UCR grant, a conclusive
winner has yet to be identified out of the three candidate resins evaluated.
However, after optimizing the resin regeneration step and carrying out a limited
number of cyclic operations, the "best" resin should be evident. In any case, UTSI's
resin-based concept could provide an attractive option that can be applied to MHD
seed regeneration and spent sorbent reactivation in conventional power plants and
waste incineration facilities.
540
9. REFERENCES
1. Sheth, A. C. and T. R. Johnson, "Evaluation of Available MHD Seed-

Regeneration Processes on the Basis of Energy Consideration," ANL/MHD-
78-4, a report prepared by Argonne National Laboratory for DOE under
contract no. W-31-109-Eng-38, September 1978.
2. Sheth, A. C , et al., "Seed Recovery and Regeneration in Coal-Fired, Open-

Cycle Magnetohydrodynamic Systems," Proceedings of the 9th Annual
Energy-Sources Technology Conference and Exhibition, New Orleans,
February 23-27, 1986. Published in Technical Economics, SynFuels and
Coal Energy-1986, PD-Vol. 5, edited by J. B. Dicks, sponsored by ASME,
February 1986.
3. Matty, R. E., "Evaluation of Alternative Seed Regeneration Processes

Applicable to Coal-Fired MHD Power Plant," FE-1760-33, a report prepared
by The University of Tennessee Space Institute for DOE under contract no.
EX-76-C-01-1760, January 1979.
4. Krumreich, B. M., "Seed Regeneration Processes for Coal-Fired MHD Power

Plants," DOE/CH-10018-14, a report prepared by The Babcock and Wilcox
Company for DOE under contract no. DE-AC02-79CH10018, May 1985.
5. Jackson, D. M., "Evaluation of Seed Regeneration Processes for Coal-Fired

MHD Power Plants," FE-1760-36, a report prepared by The University of
Tennessee Space Institute for DOE under contract no. DE-AC02-
79ET10815, July 1985.
6. "Application of Ion-Exchange Technique in Seed Regeneration Experiments

for MHD Power Generation," an internal document, Chong Sho Chemical
Fraternity, Su Chow Area Chemical Institute, China, 1980.
7. Butler, W. ., "Bench Scale Evaluation of Anion-Exchange Resin-Based

Seed Regeneration Concept for Coal-Fired Magnetohydrodynamics Power
System," a thesis presented for M.S. degree. The University of Tennessee
Space Institute, Tullahoma, Tennessee, December 1986.
8. Modeste, D. C , "Evaluation of Improved Anion-Exchange Resin-Based Seed

Regeneration Concept for Coal-Fired MHD Power System," a thesis
presented for M.S. degree. The University of Tennessee Space Institute,
Tullahoma, Tennessee, December 1988.
9. Sheth, A. C. and Strevel, S., "Anion-Exchange Resin-Based Desulfurization

Process," Quarterly Technical Progress Report for period August 9, 1990 -
December 3 1 , 1990, DOE/PC/90309-1, The University of Tennessee Space
Institute, Tullahoma, Tennessee, January 1991.
541
10. Sheth, . C. and Strevel, S., "Anion-Exchange Resin-Based Desulfurization

Process," Annual Technical Progress Report for period August 9, 1990 -
September 30, 1991, DOE/PC/90309-4, The University of Tennessee Space
Institute, Tullahoma, Tennessee, October 1991.
11. Sheth, A. C , et. al., "Anion-Exchange Resin-Based Desulfurization Process,"

Annual Technical Progress Report for period October 1, 1991 - September
30, 1992, DOE/PC/90309-8, The University of Tennessee Space Institute,
Tullahoma, Tennessee, October 1992.
12. Strevel, S., "The Anion-Exchange Resin-Based Desulfurization Concept," a

thesis presented for M.S. degree. The University of Tennessee Space
Institute, Tullahoma, Tennessee, December 1992.
13. Antonson, C. R., "Adsorption of Ethane in Molecular Sieve Particles," a Ph.D.

dissertation, Northwestern University, Evanston, Illinois, 1968.
14. SeIke, W. A. and Bliss, H., "Application of Ion-Exchange, Copper-Amberlite

IR-120 in Fixed Beds," Chemical Engineering Progress, vol. 46, p. 509, 1950.
15. Sheth, A. C. et. al., "Desulfurization of Alkali Metal Sulfates Using Anion-
Exchange Resins," AIChE Journal, vol. 35, no. 3, pp. 519-522, March 1989.
16. Sheth, A. C , et. al., "Anion-Exchange Resin-Based Desulfurization Process

for Alkali Metal Sulfates," presented and published in the Proceedings of the
26th Symposium on Engineering Aspects of Magnetohydrodynamics,
Nashville, Tennessee, June 1988.
17. Sheth, A. C , et. al., "Anion-Exchange Resin-Based Dechlorination Concept,"

presented and published in the Proceedings of the 1990 SO2 Control
Symposium sponsored by EPRI/EPA, New Orleans, Louisiana, May 1990.
Elemental sulfur production from SOg-rich gases
S i d n e y G. N e l s o n *
1. ihtroductioh
M a n y industrial e x h a u s t g a s e s c o n t a i n h i g h l e v e l s of sulfur d i o x i d e ( S O 2 ) , a
m a j o r p o l l u t a n t requiring control u n d e r t h e 1 9 9 0 C l e a n Air A c t . E x a m p l e s
i n c l u d e t h o s e e m a n a t i n g from fossil-fuel p o w e r plsmts, sulfuric a c i d plcmts.
sulfur i n c i n e r a t i n g p l a n t s , or sulflde-ore r o a s t i n g p l a n t s . In t h e U . S . i n r e c e n t
y e a r s , coal-fired p o w e r p l a n t s h a v e r e c e i v e d particular a t t e n t i o n . S u l f u r d i o x i d e
e m i s s i o n s from t h e s e p l a n t s are currently b e i n g c o n t r o l l e d b y w e t or dry flue-gas
desulfurization (FGD) p r o c e s s e s . Most FGD p r o c e s s e s e m p l o y l i m e or l i m e s t o n e
slurries t h a t are i n t r o d u c e d into a n d m i x e d w i t h t h e SOa-containing flue g a s e s .
T h e s e p r o c e s s e s p r o d u c e m i l l i o n s of t o n s of w a s t e s a n n u a l l y i n s c r u b b i n g S O 2
from t h e g a s e s .
T h e h u g e q u a n t i t i e s of w a s t e s t h a t are a c c u m u l a t i n g a t m a n y s i t e s i n t h e
U . S . h a v e g e n e r a t e d i n t e r e s t in r e g e n e r a b l e FGD t e c h n o l o g i e s . R e g e n e r a b l e FGD
t e c h n o l o g i e s p r o d u c e little or n o w a s t e s b e c a u s e g e n e r a l l y t h e s o r b e n t s t h a t are
e m p l o y e d are r e g e n e r a t e d c m d u s e d o v e r agciin. S o m e r e g e n e r a b l e t e c h n o l o g i e s ,
s u c h a s W e l l m a n - L o r d , W e t M a g n e s i a , Citrate, a n d C o p p e r Oxide, h a v e b e e n
cUOund for s o m e t i m e . S e v e r a l n e w e r r e g e n e r a b l e t e c h n o l o g i e s , s u c h a s S o r b e n t
T e c h n o l o g i e s Corporation's M a g S o r b e n t P r o c e s s , t h e N O X S O P r o c e s s , a n d t h e
A c t i v a t e d C o k e P r o c e s s , s h o w p r o m i s e a s b e i n g m o r e e c o n o m i c a l t h a n t h e older
regenerable technologies.
W h e n sulfur i s t h e d e s i r e d by-product, m o s t r e g e n e r a b l e F G D p r o c e s s e s t o d a y
incorporate a G l a u s p l a n t i n their d e s i g n to c o n v e r t S O 2 , d e r i v e d d u r i n g
r e g e n e r a t i o n , to e l e m e n t a l sulfur. C l a u s p l a n t s , h o w e v e r , are e x p e n s i v e a n d
m o s t p r o d u c e a tail g a s t h a t requires further p r o c e s s i n g . T h e r e q u i r e m e n t of a
C l a u s plcmt generadly i n c r e a s e s t h e c o s t of r e g e n e r a b l e F G D p r o c e s s e s
significsmtly. If cm i n e x p e n s i v e direct m e t h o d w e r e a v a i l a b l e to c o n v e r t t h e S O 2
p r o d u c e d d u r i n g s o r b e n t r e g e n e r a t i o n to e l e m e n t sulfur, t h e e c o n o m i c s of
r e g e n e r a b l e FGD p r o c e s s e s w o u l d b e g r e a t l y e n h a n c e d . T h i s p a p e r d e s c r i b e s
t h e d e v e l o p m e n t of s u c h a m e t h o d .
president, Sorbent Technologies Corporation, 1935 East Aurora Road, Twinsburg, Ohio 44087
544
2. COnVERSIOM SULFUR COMPOUriDS TO ELEMEHTAL SULFUR
D u r i n g t h e p a s t 2 0 y e a r s , a l t h o u g h a n u m b e r of i m p r o v e m e n t s to t h e C l a u s
process h a v e b e e n suggested, the basic process h a s not chamged significantly.
H o w e v e r , in a d d i t i o n to t h e G l a u s p r o c e s s , seversd n e w direct sulfur m e t h o d s
have been proposed.
2 . 1 The Glaus a n d Modified Glaus Processes

T h e C l a u s p r o c e s s i s o n e of t h e b e s t k n o w n m e t h o d s of c o n v e r t i n g h y d r o g e n
sulfide (HgS) to e l e m e n t a l sulfur. T h e G l a u s p r o c e s s c a n b e carried o u t i n a
v a r i e t y of w a y s , d e p e n d i n g o n t h e H 2 S c o n t e n t in t h e g a s b e i n g treated. A
c o m m o n a p p r o a c h for c o n c e n t r a t e d H 2 S streauns i s to e m p l o y a v a p o r - p h a s e
reactor s y s t e m . T h e overall r e a c t i o n o c c u r r i n g in t h i s s y s t e m is:
2H2S O2 2S + 2H2O (1)
T h e Glaus s y s t e m t y p i c a l l y i n c l u d e s t h r e e or m o r e c o n v e r t e r s t a g e s to
a c h i e v e a 9 5 p e r c e n t c o n v e r s i o n of H 2 S to e l e m e n t a l sulfur. Most G l a u s p l a n t s
in t h e U . S . t o d a y p r o d u c e , n o t e l e m e n t a l sulfur, b u t sulfuric a c i d a s their finsd
product.
E l e m e n t a l sulfur i s g e n e r a l l y p r o d u c e d from H 2 S - r i c h s t r e a m s b y first
c o m b u s t i n g a portion of t h e H 2 S in t h e s t r e a m s to form S O 2 , w h i c h t h e n , i n turn,
r e a c t s w i t h t h e r e m a i n i n g H 2 S to form e l e m e n t a l sulfur. T h e c o n v e r s i o n of H 2 S
and S O 2 to e l e m e n t a l sulfur in a l i q u i d - p h a s e G l a u s r e a c t o r o c c u r s a c c o r d i n g to
t h e f o l l o w i n g reaction:
2H2S + SO2 > 38 + 2H2O (2)
For t h e c o n v e r s i o n of g a s s t r e a m s c o n t a i n i n g s i g n i f i c a n t l e v e l s of S O 2 , a n d
p e r h a p s n o HgS, a m o d i f i e d v e r s i o n of t h e G l a u s p r o c e s s i s c o m m o n l y u s e d . T o
utilize t h e G l a u s r e a c t i o n (2) a b o v e to c o n v e r t S O 2 into e l e m e n t a l sulfur, t w o -
thirds of t h e S O 2 m u s t first b e c o n v e r t e d to H 2 S , b e c a u s e t h e G l a u s r e a c t i o n
requires a feed g a s w i t h a p p r o x i m a t e l y a 2:1 m o l a r ratio o f H 2 S to S O 2 . T o
a c c o m p l i s h t h i s , a portion of t h e S O 2 in a c o n c e n t r a t e d S O 2 g a s i s often r e a c t e d
w i t h C8ubon m o n o x i d e or h y d r o g e n a s follows:
SO2 + 3 G O + H2O H 2 S -H 3 G O 2 (3)

SO2 + 3 H 2 H2S 2H2O (4)
After c o n v e r s i o n of t h e required portion of t h e S O 2 to H 2 S , t h e g a s e s are c o o l e d

a n d are s e n t to a liquid p h a s e G l a u s reactor.
B e c a u s e t h e Glaus-unit r e a c t i o n s g e n e r a l l y do n o t g o to c o m p l e t i o n , residuad
tail g a s e s are p r o d u c e d . T h e s e tail g a s e s h a v e b e e n an e n v i r o n m e n t a l p r o b l e m
in t h e p a s t . Five t y p e s of p r o c e s s i n g a n d control s y s t e m s , ARGO. B e a v o n , IFF-1,
S C O T , and W e l l m a n - L o r d , are p r e s e n t l y b e i n g u s e d in t h e U . S . to h a n d l e tail g a s
emissions.
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2.2 Direct SOj-to-Sulfur Processes

In r e c e n t y e a r s there h a v e b e e n efforts to d e v e l o p a s i m p l e r , direct p r o c e s s
to c o n v e r t S O 2 in g a s s t r e a m s to e l e m e n t a l sulfur. One of t h e s e p r o c e s s e s i s t h e
Direct Sulfur P r o c e s s d e v e l o p e d b y R e s e a r c h T r i a n g l e Institute (RTI). In t h i s
p r o c e s s , a r e d u c i n g g a s i s m i x e d w i t h t h e SOa-containing feed g a s and t h e
c o m b i n a t i o n i s p a s s e d a c r o s s a proprietary c a t a l y s t a t a t e m p e r a t u r e of 650C
a n d p r e s s u r e s of a b o u t 2 0 a t m . T h i s p r o c e s s r e s u l t s i n o v e r 9 0 p e r c e n t
c o n v e r s i o n a n d p r o d u c e s e l e m e n t a l sulfur directly, b u t i s effective o n l y a t h i g h
p r e s s u r e s . At 1.7 a t m , for exsunple, t h e c o n v e r s i o n rate i s o n l y a b o u t 18
p e r c e n t . Moreover, t h e m o l a r ratio of r e d u c i n g g a s to sulfur d i o x i d e i n t h e
p r o c e s s c a n n o t e x c e e d 2 : 1 , b e c a u s e a t ratios a b o v e 2 : 1 , t h e RTI c a t a l y s t
decomposes.
Additional p r o c e s s e s i n v o l v i n g t h e direct c o n v e r s i o n of S O 2 i n a SOa-rich g a s
to e l e m e n t a l sulfur i n c l u d e t h a t of E i s e n l o h r , in w h i c h h y d r o g e n i s a d d e d to t h e
g a s a n d t h e g a s is p a s s e d t h r o u g h a b e d of cobedt o x i d e , n i c k e l o x i d e ,
m o l y b d e n u m o x i d e , or t u n g s t e n o x i d e at 2 0 0 to 450*, a n d t h a t of Moss, in
w h i c h t h e SOa-rich g a s is p a s s e d t h r o u g h a fluidized b e d of s o l i d c a r b o n c h a r
particles a t 6 0 0 to 1200C. D i s a d v a n t a g e s of t h e E i s e n l o h r p r o c e s s are t h e h i g h
c o s t of t h e c a t a l y s t s , t h e p o s s i b i l i t y of h e a v y m e t a l p o l l u t i o n , a n d t h e a d d e d
r e q u i r e m e n t of a G l a u s p l a n t to p r o c e s s t h e g a s e x i t i n g t h e c a t a l y s t after t h e
e l e m e n t a l sulfur i s r e m o v e d . D i s a d v a n t a g e s of t h e M o s s p r o c e s s i n c l u d e t h e
relatively c o m p l i c a t e d n a t u r e of t h e e q u i p m e n t t h a t i s required, t h e i g n i t i o n
d a n g e r s i n e m p l o y i n g hot, r e a c t i v e char, a n d t h e reported l o w sulfur y i e l d s t h a t
occur.
3 . THE MAQSORBENT PROCESS
S e v e r a l y e a r s a g o , S o r b e n t T e c h n o l o g i e s Corporation (Sorbtech) r e s e a r c h e r s
d i s c o v e r e d t h a t a s o r b e n t c o n s i s t i n g of a c o m b i n a t i o n of t w o relatively
i n e x p e n s i v e industrial minergds, v e r m i c u l i t e a n d m a g n e s i a (MgO), c o u l d be
effectively u s e d dry to r e m o v e S O 2 a n d N O x from i n d u s t r i a l flue g a s e s .
V e r m i c u l i t e i s t h e naune g i v e n to a g r o u p of h y d r a t e d a l u m i n u m - i r o n -
m a g n e s i u m silicate m i n e r a l s t h a t r e s e m b l e m i c a i n a p p e a r a n c e . W h e n h e a t e d ,
f r e s h l y - m i n e d v e r m i c u l i t e d e m o n s t r a t e s t h e unusuad property of e x f o l i a t i n g or
e x p a n d i n g i n t o accordion-like s h a p e s , a s a r e s u l t of t h e i n t e r l a m i n a r g e n e r a t i o n
of s t e a m . In e x p a n d e d form, v e r m i c u l i t e p a r t i c l e s p o s s e s s a large m a c r o - s u r f a c e
a r e a a n d will a b s o r b a n d h o l d large cunounts of l i q u i d s or fine p o w d e r s w h i l e
r e m a i n i n g firee-flowing. T h e y are c l e a n a n d e a s y to h a n d l e , n o n - a b r a s i v e , a n d
o d o r l e s s , a n d h a v e l o w - l e v e l catalytic properties. E x p a n d e d v e r m i c u l i t e h a s
m a n y a p p l i c a t i o n s . A typical a p p l i c a t i o n i s u s e a s a soil c o n d i t i o n e r . M a g n e s i a ,
or m a g n e s i u m o x i d e , t h e s e c o n d c o m p o n e n t i n t h e s o r b e n t , i s a c o m m o n
m i n e r a l t h a t c o m m e r c i a l l y i s p r o d u c e d b y c a l c i n i n g m i n e d m a g n e s i t e (MgCOg)
or i s d e r i v e d from s e a w a t e r or b r i n e s .
S o r b t e c h r e s e a r c h e r s d e v e l o p e d p r o c e d u r e s to c o a t MgO effectively o n t o
e x p a n d e d v e r m i c u l i t e particles. T h e r e s u l t i n g p r o d u c t s w e r e r e l a t i v e l y s t r o n g
cmd d e m o n s t r a t e d a h i g h reactivity t o w a r d S O 2 a n d N O x i n a g a s streaun.
546
particularly if t h e y w e r e g i v e n a h i g h - t e m p e r a t u r e h e a t t r e a t m e n t before
e x p o s u r e . T h e p r o d u c t s , m o r e o v e r , e x h i b i t e d m o s t of t h e d e s i r a b l e p r o p e r t i e s
of v e r m i c u h t e . It w a s f o u n d p o s s i b l e to l o a d a s m u c h a s 6 0 p e r c e n t b y w e i g h t
of MgO o n t o v e r m i c u l i t e particles a n d still o b t a i n g o o d p e r f o r m a n c e i n t r e a t i n g
exhaust gases.
T h e u s e of MgO to treat flue g a s e s i s n o t n e w . In t h e W e t M a g n e s i a P r o c e s s ,
MgO is m i x e d w i t h w a t e r a n d t h e r e s u l t i n g slurry i s s p r a y e d i n t o t h e flue g a s to
r e m o v e SOg. T h e W e t M a g n e s i a P r o c e s s effectively r e m o v e s SOg. a n d t h e
r e s u l t i n g m a g n e s i u m sulfate i s r e g e n e r a b l e . H o w e v e r , r e l a t i v e l y l8U*ge a m o u n t s
of w a t e r are required in t h e p r o c e s s , a n d t h i s w a t e r in c o m b i n a t i o n w i t h MgO
a n d M g S 0 4 c a u s e s m a j o r h a n d l i n g a n d p r o c e s s i n g difficulties and r e s u l t s i n h i g h
c o s t s . T h e MgO-vermiculite c o m b i n a t i o n s in t h e n e w p r o c e s s , o n t h e o t h e r
h a n d , are e m p l o y e d dry or n e a r l y dry. A s s u c h , t h e c o m b i n a t i o n s w e r e f o u n d
to capture m o r e t h a n 9 0 p e r c e n t of t h e SOg, 3 0 p e r c e n t of t h e NOx, a n d m u c h
of t h e fine s o o t a n d a s h pguticles t h a t c o n v e n t i o n s d d u s t - c o l l e c t i o n s y s t e m s fail
to r e m o v e .
Like t h e W e t M a g n e s i a P r o c e s s s o r b e n t s , t h e M g O - v e r m i c u l i t e s o r b e n t s are
r e g e n e r a b l e . H o w e v e r , t h e MgO-vermiculite s o r b e n t s d e m o n s t r a t e s o m e u n i q u e
properties d u r i n g r e g e n e r a t i o n . W h e n r e g e n e r a t i o n i s p e r f o r m e d i n air, SO2 a n d
N O x are g i v e n off. W h e n r e g e n e r a t i o n i s carried o u t i n a r e d u c i n g e n v i r o n m e n t ,
t h e N O x i s d e s t r o y e d , i n s t e a d c o n v e r t e d to n i t r o g e n a n d w a t e r . A l s o , in a
r e d u c i n g e n v i r o n m e n t , a large fraction of t h e SO2 i s c o n v e r t e d directly to
e l e m e n t a l sulfur. T h e S o r b t e c h r e s e a r c h e r s n a m e d t h e n e w M g O - v e r m i c u l i t e
sorbents MagSorbents.
M a g S o r b e n t s C c m b e a p p l i e d to treat flue g a s e s a s a s i m p l e p r o c e s s . O n l y t w o
principal s t e p s , d r y - s c r u b b i n g a n d r e g e n e r a t i o n , are i n v o l v e d .
In t h e s c r u b b i n g s t e p , flue g a s , aifter e x i t i n g a n e x i s t i n g p a r t i c u l a t e d e e m i n g
s y s t e m , s u c h a s a n electrostatic precipitator, i s h u m i d i f i e d . T h e flue g a s t h e n
p a s s e s t h r o u g h a s p e c i a l radicd, psmel-bed filter t h a t contaiins a s l o w - m o v i n g b e d
of t h e dry, grcmular s o r b e n t , a s s h o w n in Figure 1. In t h e filter c h a m b e r , SO2,
NOx, a n d r e s i d u a l p a r t i c u l a t e s are s i m u l t a n e o u s l y s c r u b b e d or r e m o v e d from
t h e flue g a s . T h e t r e a t e d flue g a s t h e n g o e s to t h e s t a c k .
In t h e r e g e n e r a t i o n s t e p , s a t u r a t e d s o r b e n t i s c o n t i n u a l l y r e m o v e d from t h e
filter c m d c o n v e y e d to a t h e r m a l regenerator. D u r i n g r e g e n e r a t i o n , t h e r e l e a s e d
N O x i s c o n v e r t e d to n i t r o g e n a n d water, and t h e r e l e a s e d SO2 i s c o n v e r t e d to
e l e m e n t a l sulfur. After r e g e n e r a t i o n , t h e r e n e w e d s o r b e n t i s s c r e e n e d a n d
r e t u r n e d to t h e s c r u b b e r .
T h e d e v e l o p m e n t of t h e M a g S o r b e n t P r o c e s s h a s p r o g r e s s e d t h r o u g h a s e r i e s
of s t a g e s . M a g S o r b e n t m a t e r i a l s w e r e first e x p o s e d to actusd flue g a s e s i n 1 9 8 6
w h e n 4 - i n c h d i a m e t e r b y 8 - i n c h l o n g b e d s w e r e p l a c e d i n a t i n y s l i p s t r e a m of
flue g a s a t Ohio E d i s o n ' s Gorge p o w e r p l a n t i n A k r o n , Ohio. F o l l o w i n g t h e s e
r u n s , p r o g r e s s i v e l y larger b e d s w e r e e x p o s e d to larger s l i p s t r e a m s . D u r i n g
1 9 8 7 , a 0.1-MWe s l i p s t r e a m w a s treated b y e m p l o y i n g 8 - i n c h b y 8 - i n c h b y 4 - to
10-inch thick beds. D u r i n g 1 9 8 9 , a 0.5-MWe s l i p s t r e a m w a s t r e a t e d b y
e m p l o y i n g 3 6 - i n c h b y 3 6 - i n c h b y 4 - to 1 2 - i n c h t h i c k b e d s of m u l t i p l e -
r e g e n e r a t e d s o r b e n t . In all c a s e s , e x c e l l e n t SO2 r e m o v a l s w e r e o b s e r v e d .
547
Gas Flow
S o r b e n t Flow S o r b e n t Flow
Louvered Plate
or S c r e e n on
Inside and
Outside.
Gas Flow- Gas Flow
S o r b e n t Flow S o r b e n t Flow
Figure 1. Radial, p a n e l - b e d filter.
T h e r u n s e m p l o y i n g a 0.5-MWe flue-gas s l i p s t r e a m p r o v i d e d d a t a t h a t w e r e
i m p o r t a n t for t h e d e s i g n of a 2 . 5 MWe, c o n t i n u o u s l y - i n t e g r a t e d pilot-plant
facility, w h i c h w a s t h e l a t e s t s t a g e of d e v e l o p m e n t . In t h e 0 . 5 MWe r u n s , t h e
flue g a s p a s s e d h o r i z o n t a l l y t h r o u g h t h e fixed-bed filters cmd s o r b e n t w a s
e x p o s e d t o t h e flue g a s o n a b a t c h b a s i s . S a t u r a t e d s o r b e n t after e a c h r u n w a s
r e m o v e d from t h e filter, w a s t r u c k e d to S o r b t e c h ' s facilities i n T w i n s b u r g w h e r e
it w a s r e g e n e r a t e d in a rotary kiln, a n d t h e n w a s r e t u r n e d to t h e filter a t t h e
p o w e r plant. In t h e 2 . 5 MWe pflot plamt, a 1-foot thick, 4-1/2-foot d i a m e t e r
c o n t i n u o u s l y - m o v i n g p a n e l b e d filter w a s e m p l o y e d , a n d t h e s o r b e n t w a s c y c l e d
between the sorber and the regenerator during operation.
T h e initial d e v e l o p m e n t of t h e n e w t e c h n o l o g y w a s s u p p o r t e d b y S o r b t e c h
a n d b y t h e U . S . E n v i r o n m e n t a l P r o t e c t i o n A g e n c y (EPA). Later d e v e l o p m e n t
a n d d e m o n s t r a t i o n of t h e t e c h n o l o g y a t t h e 0 . 1 MWe s c a l e w a s s u p p o r t e d b y t h e
Ohio D e p a r t m e n t of D e v e l o p m e n t / O h i o Coal D e v e l o p m e n t Office (OCDO) a n d
Sorbtech. T h e U . S . D e p a r t m e n t of E n e r g y (DOE) f u n d e d t h e s u c c e s s f u l
d e m o n s t r a t i o n of t h e t e c h n o l o g y a t t h e 0 . 5 MWe l e v e l a t Ohio E d i s o n ' s Gorge
p o w e r p l a n t in Akron, Ohio. OCDO a n d S o r b t e c h s u p p o r t e d d e m o n s t r a t i o n w o r k
at t h e 2 . 5 MWe level a t Ohio E d i s o n ' s E d g e w a t e r p o w e r p l a n t i n Lorain, Ohio,
a n d OCDO, EPA, DOE a n d S o r b t e c h are f u n d i n g t h e SOg-to-elemental sulfur
r e s e a r c h c u r r e n t l y b e i n g performed.
548
4. IMPROVEMEWT OF SULFUR YIELDS THE MAQSORBEMT PROCESS
T h e M a g S o r b e n t r e g e n e r a t i o n p r o c e s s , a s p r a c t i c e d in 1 9 9 1 , r e s u l t e d i n a
c o n v e r s i o n of one-third to three-quarters of t h e sulfur r e l e a s e d d u r i n g
r e g e n e r a t i o n to e l e m e n t a l sulfur. T h e r e m a i n i n g sulfur s p e c i e s i n t h e
r e g e n e r a t o r g a s w e r e SO2 a n d HgS. For p r o c e s s i n g a n d e c o n o m i c r e a s o n s , it w a s
desirable to i n c r e a s e t h e c o n v e r s i o n rate, preferably to 1 0 0 p e r c e n t , a n d to
p r o d u c e a n e x i t g a s w i t h little or n o SO2 or H2S. D u r i n g t h e p a s t y e a r , S o r b t e c h
r e s e a r c h e r s h a v e e x a m i n e d w a y s to i n c r e a s e t h e elemented sulfur y i e l d s .
4.1 Experimental Program

T o i n c r e a s e e l e m e n t a l sulfur y i e l d s , three a p p r o a c h e s w e r e i n v e s t i g a t e d .
T h e y were: (1) e m p l o y i n g t h e n e w RTI catalyst; (2) p e r f o r m i n g r e g e n e r a t i o n a t
e l e v a t e d p r e s s u r e s ; a n d (3) r e c y c l i n g t h e r e g e n e r a t o r g a s . T h e a p p a r a t u s
a r r a n g e m e n t s t h a t w e r e d e s i g n e d a n d c o n s t r u c t e d to perform t h e s e
i n v e s t i g a t i o n s are s h o w n s c h e m a t i c a l l y i n F i g u r e s 2 a n d 3 . S i n g l e - p a s s l o w a n d
h i g h p r e s s u r e r u n s w e r e carried o u t in t h e s y s t e m s h o w n in Figure 2 . For RTI
catalyst runs, this s y s t e m w a s modified by adding a s e c o n d heated pressure
v e s s e l i m m e d i a t e l y adTter t h e v e s s e l h o l d i n g t h e s a t u r a t e d s o r p t i o n s a m p l e s . T h e
s y s t e m d e s i g n s h o w n i n Figure 3 w a s u s e d for r e c y c l i n g r u n s . All r u n s w e r e
performed o n a batch basis.
A 5 0 - g ssunple of s a t u r a t e d s o r b e n t w a s u s e d in e a c h t e s t r u n . S a m p l e s w e r e
t a k e n from M a g S o r b e n t h a v i n g t h e c o m p o s i t i o n : 6 0 w t % M g O - 4 0 w t %
v e r m i c u l i t e t h a t w a s e x p o s e d to flue g a s e s at Ohio E d i s o n ' s E d g e w a t e r p o w e r
plant. T h e c o m p o s i t i o n of t h e s a t u r a t e d s o r b e n t i s g i v e n in T a b l e 1.
Table 1
C o m p o s i t i o n of e x o o s e d s o r b e n t
44.7% MgO
13.7% HaO
8.9% SO3
4.2% SO2
28.5% Vermiculite
T h e step-by-step p r o c e d u r e s g e n e r a l l y f o l l o w e d in s i n g l e - p a s s e x p e r i m e n t s
c o n s i s t e d of:
1. I n t r o d u c i n g a s a t u r a t e d s o r b e n t s a m p l e into t h e r e g e n e r a t o r v e s s e l a n d
sealing the system.
2. Initiating a flow of a p u r g e g a s (nitrogen) t h r o u g h t h e s y s t e m a n d c h e c k i n g
for l e a k s a n d t a k i n g corrective a c t i o n , w h e n n e c e s s a r y .
3 . T u r n i n g o n t h e g a s preheater, r e g e n e r a t o r h e a t e r , h e a t i n g t a p e s , a n d o t h e r
h e a t e r s i n t h e s y s t e m , w h i l e initiating t h e flows of t h e d e s i r e d carrier/reaction
gases.
549
Flowmeter
Balston
Mass Flow Filter^
Controller -Vent
Back
Pressure
Other Regulator
Gas
Additives
Heated Sulfur and Water
Mass Flow Pressure Condenser Gas
Controller Vessel Sample
Port
Saturated
Mass Flow Sorbent
Controller Bed
Methane
Gas
Preheater
OQ
Flowmeter
CO,
' N2
Mixture
Figure 2. Single-pass test s y s t e m .
Mass Flow Balston

Controller ^ Filter
other
Gas
Additives
Mass Flow Heated Sulfur and Water
Controller Reactor Condenser
System
Mass Flow "Saturated

Controller Sorbent
CH, Bed
|Gas
H^H0^ Preheater
Flowmeter Vent
Gas
CO, Sample
Port
Mixtures
Gas
Storage
Tank
Flowmeter Recycle Pump
Figure 3. Recycle test s y s t e m .

550
4 . R a i s i n g t h e t e m p e r a t u r e of t h e s a t u r a t e d s o r b e n t s a m p l e v e r y s l o w l y .
5. R e c o r d i n g a s a f u n c t i o n of t i m e , t h e t e m p e r a t u r e s a t v a r i o u s l o c a t i o n s i n t h e
s y s t e m , t h e flow r a t e s of t h e g a s e s e n t e r i n g a n d e x i t i n g t h e s y s t e m , a n d t h e
s y s t e m pressure.
6. C o l l e c t i n g s y r i n g e Scunples of g a s e s e n t e r i n g a n d e x i t i n g t h e s y s t e m a t
regulcu- intervals a n d a n a l y z i n g t h e s e Scunples w i t h a g a s Chromatograph.
7. After a p r e - s e l e c t e d t i m e (about 2 hours) or w h e n SOg w a s n o l o n g e r d e t e c t e d
i n t h e e x i t g a s , t h e s y s t e m w a s a g a i n p u r g e d w i t h n i t r o g e n a n d a l l o w e d to
cool to r o o m t e m p e r a t u r e .
8. W h e n a t r o o m t e m p e r a t u r e , t h e r e g e n e r a t o r cmd sulfur c o n d e n s e r w e r e
dismantled, a n d t h e r e g e n e r a t e d s o r b e n t Scunple a n d s u l f u r t h a t w a s
c o l l e c t e d in t h e c o n d e n s e r s w e r e w e i g h e d .
R e c y c l i n g e x p e r i m e n t s w e r e performed in a s i m i l a r m a n n e r , e x c e p t t h e g a s e s
e x i t i n g t h e s o r b e n t b e d after p a s s i n g t h r o u g h t h e sulfur a n d w a t e r c o n d e n s e r s
cmd B a l s t o n filter w e r e r e c y c l e d b a c k to t h e g a s preheater. Before t h e g a s e s
w e r e a l l o w e d to c y c l e b a c k to t h e preheater, h o w e v e r , t h e y w e r e r e t a i n e d
t e m p o r a r i l y in a s p e c i a l s t o r a g e v e s s e l p l a c e d i n t h e r e c y c l e l i n e . O n c e g a s e s
b e g a n r e c y c l i n g , t h e feed g a s e s from g a s c y l i n d e r s w e r e s h u t off. A r e c y c l e
p u m p in t h e r e c y c l e line k e p t t h e g a s e s c i r c u l a t i n g t h r o u g h t h e s y s t e m . U p to
s i x c o m p l e t e c y c l e s w e r e u s u a l l y carried o u t in r e c y c l i n g r u n s .
4.2 Experimental Results

A total of 3 0 t e s t r u n s w e r e performed, e a c h of t w o to four h o u r s duration.
Twenty-one were single-pass runs; nine were recycling runs. Methane w a s
e m p l o y e d a s t h e r e d u c i n g g a s in m o s t r u n s , cdthough CO a n d h y d r o g e n w e r e
cdso excunined. All g a s e s p e r f o r m e d satisfactorily. T h e r e s u l t s of t h e t e s t r u n s
s h o w e d t h e following:
RTI Catcdyst R u n s . O w i n g to t h e b a t c h n a t u r e of t h e t e s t a p p a r a t u s e s , t h e
level of sulfur s p e c i e s r e l e a s e d b y s a t u r a t e d s o r b e n t s a m p l e s v a r i e d w i t h t i m e .
B e c a u s e t h e r e d u c i n g g a s e s i n t r o d u c e d to t h e s y s t e m w e r e s u p p l i e d a t a
relatively c o n s t a n t rate, there w e r e t i m e s w h e n t h e r e d u c i n g g a s : s u l f u r s p e c i e s
ratio e x c e e d e d 2 : 1 . W h e n t h i s o c c u r r e d , t h e c a t a l y s t d e c o m p o s e d a n d n o
e l e m e n t a l sulfur w a s p r o d u c e d . D e c o m p o s i t i o n of t h e c a t a l y s t o c c u r r e d d u r i n g
all b a t c h r u n s . H o w e v e r , o n e 2 0 a t m p r e s s u r e r u n w a s p e r f o r m e d i n w h i c h t h e
c a t a l y s t b e d w a s o m i t t e d from t h e s y s t e m , a n d SOg w a s s u p p l i e d c o n t i n u o u s l y
a t a c o n s t a n t rate. D u r i n g t h i s run, e l e m e n t a l sulfur w a s p r o d u c e d , a n d t h e SO2-
to-elementcd sulfur c o n v e r s i o n w a s a b o u t 9 0 p e r c e n t .
High-Pressure R u n s . In addition to t h e 2 0 a t m RTI c a t a l y s t r u n , four o t h e r
h i g h - p r e s s u r e t e s t r u n s w e r e performed o n b a t c h q u a n t i t i e s of s a t u r a t e d s o r b e n t
a n d n o RTI c a t a l y s t . T h e r e s u l t s of t h e s e r u n s s h o w e d t h a t t h e e l e m e n t a l sulfur
y i e l d s i n c r e a s e d s l i g h t l y w i t h i n c r e a s e d s y s t e m p r e s s u r e . For e x a m p l e , t h e
elementad sulfur y i e l d a t 1 a t m w a s 7 7 . 0 percent; a t 2 a t m , it w a s 7 8 . 1 percent;
a n d a t 2 0 . 7 a t m , it w a s 8 6 . 0 p e r c e n t .
R e c y c l i n g R u n s . R e c y c l i n g of t h e r e g e n e r a t o r g a s a t a t m o s p h e r i c p r e s s u r e
g a v e t h e m o s t attractive r e s u l t s . It w a s f o u n d p o s s i b l e to c o n v e r t e s s e n t i a l l y all
sulfur r e l e a s e d d u r i n g r e g e n e r a t i o n to e l e m e n t a l sulfur w i t h t h i s a p p r o a c h .
551
T y p i c a l r e s u l t s are s h o w n g r a p h i c a l l y in Figure 4 . F o u r or five c y c l e s w e r e

n e c e s s a r y to a c h i e v e c o m p l e t e c o n v e r s i o n . Aflier four or five c y c l e s , t h e r e w a s
n o SO2 or H2S p r e s e n t in t h e r e g e n e r a t i o n g a s , a l t h o u g h a s m a l l a m o u n t of
methane generally remained.
100%
99.5%
93%
87.5%
% Sulfur
77% Converted to
Elemental
Sulfur
1st 2nd 3rd 4th 5th

Cycle Cycle Cycle Cycle Cycle
Figure 4 . Total c u m u l a t e d e l e m e n t a l sulfur r e c o v e r e d a s a p e r c e n t a g e of sulfur

r e l e a s e d d u r i n g r e g e n e r a t i o n for p r o g r e s s i v e c y c l e s .
T h e overall r e a c t i o n b e l i e v e d to h a v e o c c u r r e d d u r i n g r e g e n e r a t i o n and
e x p o s u r e to m e t h a n e is:
CH4 + 2SO2 ' > 2 S + CO2 + 2H2O (5)
W h e n CH4:S02 m o l a r ratios of 0.5:1 or h i g h e r w e r e e m p l o y e d , e l e m e n t a l

sulfur w a s p r o d u c e d a n d SO2 disappeeu-ed from t h e p r o c e s s g a s s t r e a m . S o m e
SO2 r e m a i n e d in t h e p r o c e s s g a s e x i t i n g t h e s o r b e n t b e d w h e n m o l a r ratios
l o w e r t h a n 0.5:1 w e r e u s e d .
5. E X T E n S I O H o r T H E HEW T E C H H O L O Q Y T O ALL S O j - R I C H O A S S T R E A M S
T h e i n t e r e s t i n g r e s u l t s o b s e r v e d in r e c y c l i n g e x p e r i m e n t s p r o m p t e d S o r b t e c h
r e s e a r c h e r s to e x p l o r e t h e u s e of M a g S o r b e n t s a s c a t a l y s t s for t h e direct
c o n v e r s i o n of a n y g a s s t r e a m c o n t a i n i n g SO2 to e l e m e n t a l sulfur. T h e y a l s o
s u g g e s t e d t h a t o t h e r m e t a l o x i d e - v e r m i c u l i t e c o m b i n a t i o n s m i g h t perform i n a
similcu* mgmner.
A s a c o n s e q u e n c e , a project w a s u n d e r t a k e n to d e t e r m i n e if fresh
MagSorbent, a n d / o r s i m i l a r m a t e r i a l s , c o u l d y i e l d a p p r e c i a b l e e l e m e n t a l sulfur
552
in a s i n g l e s t e p , a s s h o w n b e l o w in Figure 5. T h e e q u i p m e n t a r r a n g e m e n t t h a t
w a s e m p l o y e d to carry o u t t h i s project is s h o w n in Figure 6.
Methane
Elemental
SO: Catalyst Sulfur
t
CO2. H2O. (H2S)
Figure 5. S i n g l e - s t e p p r o c e s s for e l e m e n t a l sulfur p r o d u c t i o n .
Gas
Sample
Port
Mass Flow
Controller Quartz
Reactor
Methane
Mass Flow Catalyst

Controller
SO2 - R i c h
Feed Gas
Vent
Figure 6. A p p a r a t u s e m p l o y e d to e v a l u a t e potential c a t a l y s t m a t e r i a l s .
553
T h e r e s u l t s of t e s t s e m p l o y i n g fresh M a g S o r b e n t s a s a c a t a l y s t w e r e
e x c e l l e n t . T y p i c a l l y , u s i n g M a g S o r b e n t w i t h t h e c o m p o s i t i o n : 6 0 w t % MgO-40
wt% V e r m i c u l i t e o n a g a s s t r e a m c o n t a i n i n g 5 p e r c e n t SO2 a n d 1 0 p e r c e n t
m e t h a n e y i e l d e d 7 7 p e r c e n t e l e m e n t a l sulfur c o n v e r s i o n a t 6 9 0 C a n d
atmospheric pressure a n d yielded essentially 100 percent conversion at slightly
h i g h e r t e m p e r a t u r e s . T h e u s e of M a g S o r b e n t s c o n t a i n i n g l e s s e r a m o u n t s of
MgO a n d t h e u s e of MgO a l o n e a l s o r e s u l t e d i n e l e m e n t a l sulfur, b u t y i e l d s w e r e
s l i g h t l y lower.
Ten other metal oxide and metal oxide-vermiculite combinations were also
e x a m i n e d a s potential c a t a l y s t s for t h e direct c o n v e r s i o n of SO2 to e l e m e n t a l
sulfur. T h e s e o x i d e s i n c l u d e d titcinium o x i d e (TO2), s i l i c o n d i o x i d e (SO2),
v a n a d i u m p e n t o x i d e (V2O5), c a l c i u m o x i d e (CaO), c o p p e r o x i d e (CuO), cobalt
o x i d e (C03O4) cmd s o d i u m o x i d e (NaÔ). Of t h e s e o x i d e s , o n l y o n e , TO2.
d i s p l a y e d a n ability, s i m i l a r to MgO*s, to a c t a s a c a t a l y s t for t h e c o n v e r s i o n of
SO2 to e l e m e n t a l sulfur.
BIBLIOGRAPHY
1. S.G. N e l s o n , "Toxic G a s S o r b e n t a n d P r o c e s s e s for M a k i n g S a m e , " U S

Patent No. 4 7 2 1 5 8 2 .
2. M. S a t r i a n a (ed.), N e w D e v e l o p m e n t s i n F l u e - G a s D e s u l f u r i z a t i o n
T e c h n o l o g y . N o y e s D a t a Corporation, Park R i d g e , N J , ( 1 9 8 1 ) 1 4 0 - 1 5 1 .
3 . S. G a n g w a l , et al, "The Direct Sulfur R e c o v e r y Process," 1 9 9 0 S u m m e r
N a t i o n a l Meeting, A m e r i c a n Institute of C h e m i c a l E n g i n e e r s , A u g u s t 1 2 - 2 2 ,
1990.
4 . K. E i s e n l o h r , e t al, "Process for R e c o v e r i n g E l e m e n t a l S u l f u r from G a s e s
H a v i n g a H i g h Carbon D i o x i d e C o n t e n t a n d Contcdning S u l f u r C o m p o u n d s , "
US Patent No. 4 0 6 0 5 9 5 .
5. G. Moss, "Production of E l e m e n t a l Sulfur," U S P a t e n t N o . 4 0 4 1 1 4 1 .
6. B.W. N e l s o n , "Regeneration P r o c e s s for S p e n t SO2-NOX S o r b e n t s , " U S P a t e n t
No. 4 8 2 9 0 3 6 .
7. B.W. N e l s o n , et al, "Study of t h e R e g e n e r a b i l i t y of a U n i q u e N e w Sorbent,"
Final Report, E P A Contract 6 8 - D 8 0 0 6 6 , March 3 0 , 1 9 9 0 .
8. S.G. N e l s o n a n d B.W. N e l s o n , "Field T e s t i n g of a N e w SO2 a n d N O x
Sorbent," EPA/EPRI SO2 Control S y m p o s i u m , N e w Orleans, May, 1 9 9 0 .
9. S . N e l s o n Jr. a n d R. Bolli, "Waste-free SO2/NOX Control a t Ohio E d i s o n ' s
E d g e w a t e r Plant w i t h a R e g e n e r a b l e M a g n e s i a - B a s e d Sorbent," P o w e r - G e n
' 9 2 C o n f e r e n c e T r a n s a c t i o n s , Orlando, FL, N o v e m b e r 1 7 - 1 9 , 1 9 9 2 .
10. S.G. N e l s o n a n d R.C. Littie, "Direct Sulfur Recovery," P h a s e I Final Report,
E P A Contract 6 8 - D 2 0 0 7 5 , February 2 6 , 1 9 9 3 .
554
ACKNOWLEDGEMENT
T h e a u t h o r w i s h e s to r e c o g n i z e cOid to thauik t h e Ohio D e p a u t m e n t of

D e v e l o p m e n t / O h i o Coal D e v e l o p m e n t Office a n d t h e U . S . E n v i r o n m e n t a l
P r o t e c t i o n A g e n c y for their s u p p o r t of r e s e a r c h to i m p r o v e t h e sulfur y i e l d s in
the MagSorbent Process.
Coal grinding wîth water jets
A. Bortolussi, P. Carbini, R. Ciccu and M. Ghiani
Department of Mining and Mineral Engineering and

Mineral Science Study Centre
University of Cagliari
Piazza d'Armi 09123 Cagliari, Italy
The paper refers on the results of ongoing research intended to assess the potential of
waterjet for disintegrating a variety of rocks and ores. Regarding coal, the technical results
so far obtained (in terms of product fineness, size distribution, particle features and
specific energy) are presented and discussed as a function of the relevant operational
variables (feed rate, feed size, pressure, collimator diameters, stand-off distance). A rough
estimate of the economic aspects of processing is also given.
1. INTRODUCTION
Grinding of coal down to very fine sizes is a challenging problem of nowadays, from
both the technical and economic points of view, calling for suitable methods and
commercially available equipment.
Comminution of coal for cleaning generally avoids the production of excessive fines.
However the future may well see the development of coal cleaning techniques involving
the deliberate production of finer sizes.
On one side, fine grinding is required for achieving better liberation, thus allowing
ultra-cleaned products to be obtained under the pressure of environmental protection
measures; on the other, accurate comminution is needed for using coal in the form of
water slurries as a possible substitute of oil in oil-fired power stations. A futher field of
interest is the long-distance pipeline transportation of coal in the form of a slurry.
Unlike coarse crushing, where the energy used per tonne is small, reduction of coal to
fine sizes consumes substantial energy and grinding efficiency is of considerable
importance.
A new revolutionary method of coal comminution consists in using high velocity water
jets, capable of producing a thorough fragmentation with negligible wear and reasonable
energy consumption.
Waterjet can be used either for assisting mechanical grinding in conventional mills (1)
or as the only fracturing agent in specially designed apparatus. Very intersting
micronization results have been obtained by applying a waterjet to a disk mill (2).
556
2. EXPERIMENTS
2 . 1 . Apparatus
The new waterjet mill for coal grinding designed and built at the Mining and Mineral
Engineering Department of the University of Cagliari is shown in Figure 1.
Basically the system consists of:
- a Triplex High Pressure plunger pump capable of delivering a 54 l/min flowrate under
a pressure of 250 MPa. The prime mover is a Diesel engine provided with the
control facilities for adjusting the speed and thence the pumping pressure;
flexible connecting hose and a lance provided with a single nozzle for the
generation of a high velocity waterjet;
1 - Waterjet lance
2 - Nozzle holder
3 - Feed inlet
4 - Mixing chamber
5 - Collimator tube
6 - Jet catcher target
7 - Slurry chamber
8 - Slurry collector device
9 - Fine product outlet
10 - Coarse product outlet
11 - Air pressure relieve
Figure 1. Sketch of the laboratory waterjet mill
- the waterjet mill;

- a vibrating feeder;
- collecting boxes for the grinding products.
557
The waterjet mill is divided in two distinguished parts:

- the mixing chamber and the collimator tube;
- the slurry vessel hosting the jet catcher device, where a rough size classification of the
ground material also occurs.
The jet is directed along the axis of the collimator tube and crosses vertically the mixing
chamber over a stand-off distance of about 10 cm to the tube inlet. The jet core diameter is
lower than the inner diameter of the collimator so that there is no attrition on the wall.
The feed material enters at the top of the mixing chamber and falls towards the
collimator tube at the bottom of the funnel-shaped part. Material flow is helped by the air
draft produced by the jet itself.
Individual grains are hit by the water jet as they approach the collimator and are broken
into smaller fragments to a top size allowing them to pass through the hole.
A further comminution takes place into the slurry vessel, as the fragments are projected
at high velocity against the jet catcher consisting of a hard metal plate.
Fragmentation is completed as a result of the mutual collision between the incoming
slurry and the particles bouncing away from the target; finally the slurry flows radially
from the impingement point, spreading across the metal surface and reaches the metal wall
of the slurry collecting device.
The slurry is then driven towards the centre and enters the lower part of the vessel:
coarse grains readily settle at the bottom and can be recirculated to the mixing chamber
while finer particles overflow and leave the vessel through a series of peripheral apertures.
2.2. Material
Grinding tests have been carried out on a sample of a low-rank coal coming from the
Gardanne Mine (France), after washing. The ash content of the coal air-dried is 7.51.
Bond index according to the standard procedure resulted to be 11.23, for a reference size
of 250 micrometres.
The average maceral composition (by volume) is the following: Vitrinite 60-65%,
Exinite-Liptinite 8-15%, Inertinite 15-20%, Mineral matter 8-14%.
The sample was screened into three size classes, namely:
- Coarser fraction: -15 + 1 0 mm;
- Intermediate class: -10-1-5 mm;
- Finer fraction. -5 + 1 mm.
Each class was treated separately according to the grinding test plan.
2.3. Experimental plan

With the goal of disclosing the role of the different jet parameters and experimental
conditions, the following variables have been included in the experimental plan:
-jet pressure: 40, 80 and 120 MPa;

- diameter of the collimator tube: 4.5 and 7.5 mm;
- feed rate: 50 and 80 g/s.
Experiments were extended to all the three size classes, giving a total of 36 grinding
tests. Each test consisted of a single pass through the waterjet mill without recirculation of
the coarse fraction. Moreover the effect of stand-off distance was explored.
Water flowrate was that corresponding to the jet velocity generated through a 1.25 mm
nozzle under the different pressures adopted.
558
mm MPa mm MPa ;
1
4.5 80
4.5 80 ' ^ '
;--^4.5 120

; o 7.5 80
; -- 7 . 5 120
6
D
4
20 h
(-15 +10) mm
80 g/s
-mm MPa
1 100
-^4.5 80 ^y^'
-*-4.5 120 ; i i ^ i ^ '
J 80 h
o 7.5 40 / / /
60
UJ 40
3
<E
20 h
d ^ ( - 1 0 + 5 ) mm
^ 80 g/s
100 h 100 h
CO
q:
UJ
:>
0.01 0.1 10 0. 01 0.1
S I Z E Cmml S I Z E Cmm]
Figure 2. Size distribution of waterjet comminution products for the different size classes
under variable experimental conditions (collimator diameter [mm] and pressure [MPa])
and feed rate [g/s].
559
3. RESULTS
Results of wet screening of the comminution product are shown by the curves of Figure
2.
They are also summarized in Tkble 1 in terms of d^^. Specific energy is calculated as
the ratio between the input power of the jet and the feed rate. However data have been
corrected by a suitable factor R = (^^'^-^ - Dgo'^'^^^^socm)"^'^ " ^8o"'^) comparison at
equal product fineness, according to the most credited theory of rock comminution
(Bond's model). Size dg^^^^ is the minimum value obtained for each class, underlined in
the Tkble and D^^ is the reference size of the feed.
4. DISCUSSION
The following considerations can be suggested by the above results:

A - Size distribution of the comminution product
- Feed size
The reference size d^^ of the comminution product is affected by the size of the feed
material: the coarser the feed, the coarser the product, experimental conditions being
the same.
- Diameter of the collimator tube

The larger the collimator tube, the coarser the product. For the size class -5 + 1 mm,
directly passing through the 7.5 mm tube, the effect of pressure above 80 MPa is
negligible, irrespective of feed rate.
- Length of the collimator tube

This aspect has not yet been explored though is may be of a certain importance since
final velocity of particles impinging against the target plate is dependent thereon.
- Distance of the target plate

Tests have been made in order to disclose the contribution of the target plate on mill
performance; however the elimination of the plate introduced some important
disturbances in the material flow (clogging of the mixing chamber) making the results
unsignificant.
- Feed rate
Generally an increase in feed rate from 50 to 80 g/s produces a little significant effect
on product fineness: this means that the real capacity of the mill is much higher than the
explored range.
Indeed, grains are rapidly evacuated as soon as they are broken due to the very high
velocity of the jet (several hundred of meters per second) so that the permanence time
into the mixing chamber is very small.
- Pressure
As pressure increases, product fineness improves.
However, beyond a certain pressure the effect becomes progressively negligible.
560
Table 1. Experimental results of waterjet grinding.

Experimental conditions Results
Test Collim. Feed rate Flowrate Size class Pressure ^80

mm g/s 1/s mm MPa mm MJ^kg
1 4.5 50 0.217 -5 + 1 40 0.99 0.56

2 0.305 80 0.50 0.87
3 0.375 120 .0.22 0.90
4 0.217 -10 + 5 40 1.86 0.61

5 0.305 80 0.51 0.62
6 0.375 120 0.35 0.90
7 0.217 -15 +10 40 _ -

8 0.305 80 0.72 0.66
9 0.375 120 0.48 0.94
10 80 0.217 -5 + 1 40 0.86 0.31

11 0.305 80 0.35 0.42
12 0.375 120 0.35 0.77
13 0.217 -10 + 5 40 _ -
14 0.305 80 0.65 0.46
15 0.375 120 0.42 0.63
16 0.217 -15 +10 40 - -

17 0.305 80 0.78 0.40
18 0.375 120 0.45 0.56
19 7.5 50 0.217 -5 + 1 40 0.95 0.54

20 0.305 80 0.75 1.22
21 0.375 120 0.68 2.06
22 0.217 -10 + 5 40 2.26 0.75

23 0.305 80 1.00 1.09
24 0.375 120 0.78 1.55
25 0.217 -15 +10 40 - _
26 0.305 80 1.37 1.04

27 0.375 120 0.94 1.46
28 80 0.217 -5 + 1 40 1.26 0.45

29 0.305 80 0.86 0.86
30 0.375 120 0.72 1.35
31 0.217 -10 + 5 40 2.42 0.50

32 0.305 80 1.00 0.63
33 0.375 120 0.75 0.94
34 0.217 -15 +10 40 - -

35 0.305 80 1.68 0.76
36 0.375 120 1.54 1.31
especially for the larger collimator tube (the curves at 80 and 120 MPa are almost
overlaying).
The pressure of 40 MPa is insufficient for the coarser classes with the smaller
collimator tube, working at high feed rate, since the material tends to accumulate into
the mixing chamber until clogging occurs. Maybe the drawback can be overcome by a
561
better design.
The gradient of the size distribution curves is generally greater as pressure increases.
Stand-off distance
- Although this variable is likely to be of a certain importance, it has not be included in
the experimental plan. Preliminary tests have been made in order to find a suitable
adjustement which was maintained constant throughout the experiments. A distance of
10 cm from the nozzle to the inlet of the collimator tube seemed the most appropriate
for assuring a regular flow of the feed material
.
- Specific energy
Specific energy is a measure of the efficiency of a grinding operation and depends on
the material properties, the fragmentation mechanism, the setting of operational variables
and the reduction ratio.
As already pointed out, experimental data have been corrected for comparing the
technical results as a function of experimental conditions at equal reduction ratio. From
the data of Table 1, it emerges that minimum specific energy is always encountered for
the pressure of 40 MPa. Increasing feed rate positively affects energy efficiency until
optimum is achieved well beyond the range explored.
Minimum specific energy attained in the tests is around 0.3 MJ/kg, roughly
corresponding to 87 kWh/t, quite higher than that normally required by traditional
grinding mills.
Actually, as shown by Table 2, a ball mill would give a similar size reduction with an
energy consumption of about 15 kWh/t (6 times lower).
Table 2 - Reported avarage energy requirements for several comminution devices (3).
Machine Feed size Product size Spec. Energy
[mm] [mm] [kWh/t]
A - Crushing
Jaw crusher 1000 30 1.8
Gyratory crusher 800 20 0.5
Rotary Impactor 400 10 0.4
Roll crusher 80 6 4
- Grinding
Autogenous mill 200 0.1 25
Roller mill 90 0.1 10
Hammer mill 50 1 1
Rod mill 70 0.8 5
Ball mill 1 0.01 15
Pin mill 0.5 0.001 16
C - Micronization
Attrition mill 0.06 0.0004 800
Fluid energy mill 0.04 0.001 600
Calculation based on Bond Index for the particular coal studied gives a theoretical
energy consumption even lower (around 5 kWh/t).
However, a substantial increase in throughput capacity (at least ten-fold) by resorting to
a rotating angled jet over a circular slot would bring down specific energy to competitive
levels, on the assumption that capacity is proportional to the area of the discharge
562
aperture, which seems very likely to occur.

It is believed that the increase in throughput will not affect mill performance since coal
grains are individually hit by the rotating jet and forced through the slot without interfering
with each other. Tests are in course to confirm this prediction.
If this is achieved, waterjet grinding has the potential of representing a very interesting
new approach to the problem of coal comminution.
5. CONCLUSIONS
Waterjet represents a very interesting way for ore and coal comminution down to very
fine sizes from both the technical and economic points of view, though performance data
are not yet available being the research at its early stage.
Among the potential advantages of waterjet in mineral grinding, the following are
worth consideration:
- high feed rate can be achieved due to the very rapid breaking action of the jet; capacity
can be increased by feeding the material through a circular slot over which the jet is
traversed with a suitable velocity;
- the size of the mill is very small in relation to its potential capacity;
- wear is greatly reduced due to the absence of frictional contacts; the only part subjected
to wear is the collimator tube which can easily be replaced with minor cost incidence;
- noise level is low since the jet is completely encased into the mixing chamber;
- size classification can take place in the mill itself.
On the other hand a waterjet mill requires a considerable amount of power for pumping
the water to the desired pressure. However, in the case of coal which can be ground at
relatively low pressure ( < 8 0 MPa) specific energy can be reduced making waterjet
competitive with traditional mills. In addition, the capital investment for a pumping system
in that range is not very high.
6. ACKNOWLEDGEMENTS
Suggestions and advice given by professor M. Mazurkiewicz of the University of

Missouri-Rolla are greatly appreciated. The research is being carried on with the financial
support of EMSa (Sardinian Mining Body) according to the programmes approved by
CNR (National Research Council) and MURST (Italian Ministry of Scientific Research).
The cooperation provided by Eng. Wan-Mo Kim is recognized.
GENERAL BIBLIOGRAPHY
- L.G. Austin, J. McClung: Size reduction of coal, in: Coal Preparation, J.W. Leonard
(Ed.) AIME, New York (1979), Ch. 7, 1-34
- A.A. Griffith: The phenomena of rupture and flow in solids, Phil. Trans. R. Soc.
Series A, 221-163-198 (1920-1921)
- I. Evans, C D . Pomeroy: The strength, fracture and workability of coal, Pergamon
Press Ltd. (1973)
563
REFERENCES
1. . Mazurkiewicz, J. White, R Karlic: Effect of feed rate during comminution of coal

by high energy waterjet, Coal Preparation (1988), Vol. 6.
2. M. Mazurkiewicz: High pressure liquid jet as a tool for disintegrating organic and non
organic materials. Invention disclusure 85-UMR-(X)9.
3. Comminution and Energy Consumption, Publication NMAB-364 National Academy
Press, Washington, D.C., 1981.
Microstructural characterization of morphological changes

and grain-boundary fractures in coal comminution
Q i n Guo% X.H. Wang^^ and B.K. Parekh''
a. Department of Mining Engineering

b. Center of Applied Energy Research
University of Kentucky, Lexington, KY 40506, U.S.A
ABSTRACT
A novel coal comminution process has recently been developed in our laboratory, by
which both the liberation of pyrite and ash-minerals from coal and the energy efficiency of
coal grinding can be significantly increased. In this paper, the change of coal particle
morphology and grain-boundary fracture induced by swelling pretreatment has been studied
by Scanning Electron Microscope. The SEM studies demonstrate that after the coal specimen
was soaked in the swelling agent for a certain time, intensive cracking and fracturing were
developed, as compared with the original surfaces that had only a few pre-existence cracks.
In some cases, the coal particles were even fractured into small pieces and had little
resemblance to their original samples. The intensity of fracture propagation depends on the
specific swelling agent and contact time. The EDX-SEM analyses also show that cracks and
fractures were induced preferentially along the inherent fractures and/or along the boundaries
between the mineral/pyrite particles and the coal matrix. The relationship between the coal
swellability and enhancement of liberation as well as grinding energy reduction has been
investigated.
INTRODUCTION
Utilization of high-sulfur coals has been confronted with serious problems due to the
increasing stringent environmental protection regulation^ The 1990 Clean Air Act
^ To whom all correspondence should be addressed.

566
Amendments have new standards for controlling sulfur dioxide emissions from burning high-
sulfur coals. In order to produce clean coal to comply with the new regulations, chemical,
biological and physical coal clean technologies have been developed. In physical coal
cleaning, removal of pyritic sulfur and mineral-matter from coal requires that the feed coal
be pulverized to fine sizes in order to adequately liberate pyrite and ash-mineral particles
from coal, especially for the most eastern coal with a high sulfur content. Existing coal
grinding techniques, however, are very inefficient due to extremely high energy consumption
and low liberation selectivity. Therefore, there is an immediate need to develop efficient coal
comminution technologies for the coal industry. Recently, a new method of enhancing the
coal grinding efficiency and the mineral-matter liberation has been developed at University
of Kentucky^ This novel approach utilizes the solvent-swelling property of coal. It has been
shown that coals swell when they are brought into contact with organic solvents^ It is
expected that swelling would result in fragmentation of the coal structure and preferential
development of cracks and fractures along the grain boundaries. The studies in our
laboratory have shown that treating coal with swelling agents prior to the grinding can
considerably reduce the grinding energy consumption and promote the liberation of pyrite
from the coal matrix. In this paper, morphological changes of coal particle induced by the
swelling process are investigated by Energy-Dispersive-X-ray-Scanning Electron Microscope
( EDX-SEM ) to understand the microfracturing process. The swelling kinetics of coals has
been quantitatively determined. The relationship between the swellability and enhancement
of liberation, as well as grinding energy reduction is discussed.
EXPERIMENTAL
1. Materials
KY. No.9 coal samples were selected for this study. The ultimate analysis of this coal
sample is shown in Table 1. Note, that the coal used contains a high pyritic sulfur ( about
3.65 weight percent).
Table 1 Representative Analysis of KY. No.9 Coal

Analysis Dry basis, Wt%
Ash 13.52
Moisture 8.03
Carbon 45.0
Volatile Matter 33.4
Pyritic Sulfur 3.65
Organic Sulfur 2.24
Total Sulfur 5.98
All the swelling agents used in this investigation were purchased from Aldich
567
Chemicals Company and were of technical grade.
2. SEM Analyses
The morphological changes of coal particles due to swelling treatment were studied
by EDX-SEM. Samples in coarse lump form were polished by 400 grit polishing paper using
water as the lubricant. The polished surfaces were examined with EDX-SEM. Next the
specimens were placed in the swelling agent. The fracture characteristics induced by swelling
was then examined on the same polished surface. The influence of chemical type and
treatment time on the morphological changes of the surface was studied.
3. Determination of Swellability of Coal
The swellability of the coal induced by different organic solvents was determined by
volumetric method"*. This method is simpler and more accurate than other methods^'^. In this
technique, about 5 grams representative dry coal sample with the size of -100 mesh is placed
in a 25mm Pyrex tube. It is first centrifuged for 5 minutes at 1725 RPM. The height of the
coal bed is measured as hg. Then, the coal bed is loosen by shaking and taping the tube, and
access amount of the organic solvent is added into the tube and is vigorously shaken to ensure
complete mixing. The coal is again centrifuged and height is measured as hi. The degree
of swelling ( Q ) is defined as relative volumetric increment on a dry basis:
where
V q = volume of dry coal; = volume of the coal bed after swelling;
The relative volumetric increment reported below is the average value of at least two
measurements at room temperature.
1. Effect of Swelling Time on the Coal Fracture Behavior
Figure 1 shows the morphology of a typical coal particle without swelling treatment.
It can be seen that there exist only a few cracks across the examined surface. Figs.2A and
2B present the SEM photographs of particle after swelling treatment using reagent CSR-01
for 3 and 5 minutes. Dramatic changes in the appearance of KY. No. 9 coal occurred. In
contrast to the untreated coal surface, extensive fracturing in the coal structure were clearly
developed. It is observed that the intensity of fracture propagation depends on the swelling
568
Figure 1 Original Surface Without Swelling Treatment
A: Swelling Treatment by Agent CSR-01 for 3 Minutes

569
: Swelling Treatment by Agent CSR-01 for 5 Minutes

Figure 2 Effect of Swelling Time on the Coal Fracture Behavior
time. For Ky. No. 9 coal treated by agent CSR-01, reaction time less than 3 minutes is
sufficient in effecting coal morphological changes. Fracturing resulting from swelling of coal
can be attributed to the high stresses produced by the uneven swelling of the coal structure^.
Intensive development of such cracldng in the coal specimens can definitely improve the
grindabiltiy of coal. This conclusion has been proven by grindability tests conducted in our
laboratory^ It was shown that swelling treatment increases the Hardgrove grindability index
( H G I ) of Ky. No.9 coal from 41 to 60-90, depending on the swelling pretreatment. In the
stirred ball mill grinding tests, it has been shown that after the pretreatment, the specific
energy consumption of producing less than 10 ^m product can be reduced to 60% of that of
the untreated coal feed. The observations from SEM analyses provide a strong direct
evidence for supporting the grinding energy reduction after swelling treatment.
2. Effect of Chemical Type on the Fracture Characteristics
Figures 3A and 3B show the SEM micrographs before and after swelling treatment
using agent CSR-04. It can be seen that morphological change in the coal surface treated by
reagent CSR-04 is not very significant. After pretreatment by CSR-04 for 10 minutes, the
inherent cracks are widened and only a few cracks are developed in the specimen during the
expansion, compared with the original cracks.
570
A: Original Surface Without Swelling Treatment
B: Swelling Treatment by Agent CSR-04 for 10 Minutes

Figure 3 Comparison of the Coal Samples Before and After Treatment With CSR-04 for 10
Minutes
571
A: Original Surface Without Swelling Treatment
B: Swelling Treatment by Agent CSR-01 for 10 Minutes

572
C: Magnified A
D: Magnified
Figure 4 Comparison of the Coal Samples Before and After Treatment With CSR-01 for 10
Minutes
573
Typical cracking produced on the polished surface of specimen using agent CSR-01
for 10 minutes is shown in Fig. 4. Massive cracking of the coal structure during swelling
is clearly revealed by SEM. The entire swollen surface is highly distorted. It shows little
resemblance to the original surface of Fig.4A. Figs.3 and 4 demonstrate that Ky. No.9 coal
has a different swelling behavior for the different solvent. Swelling treatment suggests that
agent CSR-01 is more effective for Ky. No.9 coal than agent CSR-04.
Figure 5 shows EDX-SEM spectra of Ky. No.9 coal that is a part of surface shown
in Fig.4. Of particular significance is the fact that cracks and fractures are developed around
the pyrite grain boundary, as can be seen in Fig.4. It is clearly evident that the solvent CSR-
01 preferentially penetrates throughout the inherent cracks in coal or the boundaries between
the mineral/pyrite particles and coal matrix, and thus weakens the bonding forces between
them. Figs.4 and 5 demonstrate that the intergranular fracture occurs along the pyrite and
coal matrix. The selective fracturing in coal, as a result of swelling treatment, can enhance
the selectivity of liberation. This suggests that more efficient removal of pyritic sulfur from
coal can be achieved by swelling pretreatment. The direct observation of intergragular
fracture due to swelling is consistent with our liberation studies, in which the selective
liberation with swelling treatment prior to grinding produces a better recovery at a given
sulfur value comparing to that of the unpretreated coal^
1250 cts C0AL1

C
C O A L A 2 C H E M I C A L C O M P O S I T I O N ( A R E A 1)
FE
U AL
FESI
A.
0.0 4.0 8.0 12.0 16.0
E N E R G Y (KEV)
A: Corresponding to the Area 1 in Figure 4D

574
200 cts C0AL3

C
COAL A2 CHEMICAL COMPOSITION (AREA 2)
Sl
0.0 2.0 4.0 6.0 8.0

ENERGY (KEV)
B: Corresponding to the Area 2 in Figure 4D
500 cts C0AL4
c
CA
COAL D2 CHEMICAL COMPOSITION (AREA 3)
CA
cu ZN
4.0 6.0 8.0 1O0

ENERGY (KEV)
0 : Corresponding to the Area 3 in Figure 4D
Figure 5 EDX-SEM Spectrum of a Typical Ky. No. 9 Coal Sample
575
100
a
cu
o
80d
.
Q)
(
c 60H
CD

CD
40H
a
'S
> 20H -100 mesh
CD Agent CSR-01
>
Agent CSR-02
CD
0^ 0 * " I I I I I I I I I I I I I I I I I I I I [ I I I n I I I I I I I I I I I I I I [ I I
10 20 30 40 50 60
Treatment Time, min.
Figure 6 Effect of Treatment Time Using Agent CSR-01 and CSR-02

On the Swellability of Ky. No.9 Coal
20-
- 1 0 0 mesh
Water
Agent C S R - 0 4
0 Agent CSR-Od
iO 20 30 40
F r e a t m e n t T i m e , Min.
Figure 7 Effect of Treatment Time Using Water, Agent CSR-01 and CSR-02
On the Swellability of Ky. No.9 Coal
576
3. Swellability of Coal
The swelling of coal is understood an increase in volume of the coal as a result of

imbibing a reagent. Figs. 6 and 7 show the degree of swelling of Ky. No. 9 coal as a
function of the swelling time in various agent. It can be seen that swelling takes place very
rapidly and the degree of swelling increases with increasing time. The maximum swelling
is achieved after a short time. The maximum swelling strongly depends on the chemicals.
For example, with CSR-04, the maximum relative volume increase is only about 12%,
whereas for CSR-02, the maximum value can reach to 80%. For almost all the chemicals
used, the swelling reaches a steady-state within five or ten minutes. Afterwards, relative
volume increase remains practically unchanged, except for CSR-02 and CSR-05. The slight
decrease in swelling using agent CSR-02 or CSR-05 is probably due to dissolution of coal
after the prolonged reaction, instead of further swelling.
4. Relationship Between the Degree of Swelling and Grindability
From the grindability tests^ and the above swelling data, the relationship between the
HGI and the degree of swelling induced by the chemicals can be established, as shown in
Fig.8. It can be seen that the HGI first increases with increased swelling, reaches a
maximum about 50 percent, and then decreases with further increase in swelling. These
results demonstrate that very strong swelling chemicals will not be good reagents for coal
grinding. Intermediately strong chemicals are most effective in enhancing coal grinding.
100
0 20 40 60 80 100
Swelling V o l u m e ( p e r c e n t )
Figure 8 The Relationship Between HGI and the Degree of Swelling for KY.No.9 Coal
12
577
CONCLUSIONS
The micromechanism of fracture propagation in coal particles during swelling

treatment can be studied through SEM anyses. SEM studies show that the intensity of
fracture propagation depends on the specific agent and swelling time. Preferential
cracking/fracturing is observed from EDX-SEM studies. All these results provide direct
proofs for enhancement of both the selectivity of liberation and the grinding efficiency. The
degree of swellability of KY. No. 9 coal is determined, between 12 and 80, depending on the
swelling solvents and swelling time. This study also demonstrates that there exists a
relationship between the degree of swelling and the coal grindability. Optimum improved
grindability occurs around 50 percent degree of swelling (relative volume increase).
ACKNOWLEDGEMENT
The authors wish to express appreciation to Institute of Mining and Mineral Research
for support this research. Thanks are due to several other researchers and technicians at
Center for Applied Energy Research, especially to H. Ni and R. Gonzalez with SEM
examination.
REFERENCES
L Bom, ., 1992, Aluminum, Coal: current weakness, bright future, AMC Journal, Vol.
78, No.3, p 9 9 - l l l .
2. X.H. Wang, Qin Quo and B.K. Parekh, "A New Approach To Enhance the Selectivity of
Liberation and the Efficiency of Coal Grinding, 1993, 18th International Technical
Conference on Coal Utilization & Fuel System.
3. Flory, P. J. J. Chem. Phys., 1942 10, 5 1 .
4. Dryden, I.C.C., 1951, Fuel, 30:145.
5. Liotta R. and Brown, G., 1984, Fuel, 63:935.
6. Green, T.K., Kovac, J. and Larsen, J., 1984. Fuel, 63:935.
7. Brenner, D, 1983. Fuel, 62:1347-1354.
8. Qin Guo, X.H. Wang, B.K. Parekh, Enhancement of Pyrite Liberation By Swelling
Pretreatment, 1994, SME Annual meeting.
13
ESCA studies o n surface p r o p e r t i e s and oxidation of c o a l - p y r i t e s
Xuxin Shao Yuegang Tang
Beijing Graduate School, China University of Mining and Technology,

Beijing 100083, China
Surface properties of different genetic coal-pyrites have been studied using ESCA(
Electron Spectroscopy for Chemical Analysis). The results indicate that the sulfur
oxidativities of protogenetic, epigenetic and diagenetic coal-pyrites are different from iron
oxidativities and pyritic oxidativities of these pyrites. The pyritic oxidativity increases from
protogenetic col pyrite, diagenetic coal-pyrite to epigenetic coal-pyrite, and oxidation
occurs within very thin layers of coal-pyrite. The studies also show that protogenetic coal-
pyrite is poor in iron.
l.INTRODUCTION
According to statistics, high sulfur coal in China is about 1/6 of the total production of
coal, and organic sulfur associated with maceris is about 1/3 of the total sulfur. Most of
the sulfur exists in the form of inorganic sulfurpyrite. Therefore, the removal of coal-
pyrite from coal is the main problem of coal desulfurization.
Since heavy medium separation, jig, cyclone and table have been successfully used in
coal preparation plants, the removal of coarse coal-pyrite from coal has been solved.
Although density separation for fine coal and other methods, such as high gradient magnetic
separation, have been rapidly developed"'^^ the separation of fine coal can not be
accomplished well without flotation. The main problem for current coal desulfurization is
the removal of coal-pyrite from - 0. 5mm fine coal using the fiotation method.
Recently,a lot of depressants for ore-pyrite have been put forward. However, studies
have indicated that these depressants were not suitable to depress coal-pyrite. One of the
reasons is due to the obvious difference in surface properties between coal- pyrite and ore-
pyrite. The compositions of both pyrites deviate from their chemical formulas(FeSj).
Another reason lies in that coal-pyrite contains a little carbon material which makes it
show different responses to different collectors. Coal- pyrite floats better than ore-pyrite
if fuel oil is used as collector. This phenomenon results in the separation difficulty of coal-
pyrite from coal. By using xanthate as the collector a little coal-pyrite fioats. The dosage of
xanthate for coal-pyrite is 50 times as high as that for ore-pyriteP'. Hence, studies of the
surface properties of coal-pyrite are important for the selection of depressants for coal-
pyrite.
Based on above points, this paper stresses the study of the surface properties of coal-
580
pyrite using ESCA(Electron Spectroscopy for Chemical Analysis).
2.MINERAL, EVSTRUMENT AND MEASUREMENT METHOD
2.1. Mineral
All coal-pyrites were from Longyuan coal,Nantong coal mine, Sichun province.
Analytical samples were selected according to genesis. As a comparison, a sample of coal-
pyrite from Nantong coal preparation plant is also analyzed.
2.2.Instruinent and measurement method

Each sample is prepared using an agate mortar before measurement in order to keep
coal- pyrite from oxidation. The width of half peak selected for curves fitting is 2 eV. A
KRATOS.XSAM 800 with distinguishability 0.9eV, and AlKa stimulation x-ray(1486.6eV)
is used in the research.The analytical error is less than 0.4%.The spectra of coal-pyrites
and their S(2p), C (Is), 0 ( l s ) and Fe(2p)spectra were recorded, and the binding energies
were corrected on the basis of impurity carbon C(ls)(284.6eV) to eliminate the effects of
charging. At meantime, curve fitting for each spectrum was accomplished using the
computer program integral to the instrument.
Etching analysis was performed under middle distinguishability, using Ar ion etching at
4 KV. the etching depth for one minute of is about 50.
3.1.Analysis on Natural Surface Layer

From the point of ESCA principle, ESCA analysis reflects the properties of inner
electrons of measured material. These properties are quite characteristic, and can be used
as atom analysis. Because these characters are affected by outer environmental, they can
be used to analyze the valence and existing form of material et al. Here, natural surface
layer means the surface between 0 and 50 of the sample. S, Fe and O spectra are
collected to study the surface property and oxidation of coal-pyrites.
Table 1
Sulfur and iron analyses of different genetic and different form coal-pyrites
Sample S, s,
P(eV) C(%) P(eV) C(%) P(eV) C(%)
protogenetic 162.85 75.49 165.05 15.74 168.20 8.77

epigenetic 162.85 82.67 165.15 13.63 168.30 3.70
diagenetic 162.40 79.25 164.85 12.41 167.70 8.34
Nantong 162.40 72.07 0.0 0.0 168.60 29.93
581
(continued Table 1)(P: position C: content)
Sample Fe, Fe, Fe,
P(eV) C(%) P(eV) C(%) P(eV) C(%)
protogenetic 707.25 56.06 709.75 29.56 712.35 14.38

epigenetic 707.25 53.09 709.05 28.90 711.75 18.01
diagenetic 706.75 55.72 708.80 25.02 711.15 19.26
Nantong 707.70 21.11 711.30 61.21 716.15 17.68
Table 1 lists the combining energy (B.E.) data of sulfur and iron peaks of various coal-
pyrites. In general, sulfur combining energies show small change. According to the
reportsf*'i,Sulfur peak of pyrite occurs from 162.3 to 163.0eV, and sulfur peak of sulfate is
168.6eV. Therefore, it can be inferred that the fourth valence or divalence sulfur peak is at
the range of 164.50 to 165.15eV. Table 1 also shows that Nantong coal-pyrite is short of
the fourth valence or divalence sulfur peak, which indicates exposure outside for one day
can make coal -pyrite oxidized strongly since the sample of Nantong coal-pyrite was
prepared the day before measurement day. Sulfate content on its surface is biggest. About
24.5% sulfur(Table 1, S^+S,) of protogenetic coal-pyrite is oxidized. Thus, non-pyrite
sulfur in epigenetic coal- pyrite is about 17. 3 3 % . Non- pyrite sulfur in diagenetic
coal-pyrite is about 20.75%.Therefore, from the distribution of sulfur forms the
oxidation degree of sulfur in different genetic coal- pyrites can be concluded as follows:
Protogenetic coal-pyrite > diagenetic coal-pyrite > epigenetic coal-pyrite.
Table 2
Oxygen analyses of different genetic and different form coal-pyrites(P: position C: content)
Sample 0. 0. O 3 0. O 3
c c c c c
(eV) (%) (eV) (%) (eV) (%) (eV) (%) (eV) (%)
0.0 0.0 530.35 19.1 531.70 45.4 533.24 26.1 534.85 9.2
protogenetic
epigenetic 528.35 6.6 530.05 12.8 531.45 20.9 532.85 59.1 0.0 0.0
diagenetic 0.0 0.0 529.55 13.5 531.15 35.8 532.85 28.1 534.65 22.6
Nantong 528.80 2.5 530.35 14.4 531.80 67.7 533.50 15.4 0.0 0.0
In iron spectrum 707(eV), 711(eV) and 713(eV) are correspondent to FeS,; F e p , ; FeOH
and FeSO/, Fe^SOJ, separately^. Table 1 shows that non-pyrite iron in protogenetic coal-
582
pyrite is 43.94%. But epigenetic coal-pyrite contains 46.91% non-pyrite iron, and non-
pyrite iron in diagenetic coal- pyrite is 44.28% of total iron which is between
protogenetic coal- pyrite and epigenetic coal-pyrite. However, 78.89% iron in Nantong
coal-pyrite is oxidized due to the overexposure in air. Hence,iron oxidation degree of coal-
pyrites is as follows: epigenetic coal-pyrite > diagenetic coal-pyrite > protogenetic coal-
pyrite, which is different from sulfur oxidation of coal- pyrites.
Table 3
Oxidation analyses of different genetic and different form coal-pyrites
Sample Oxidativity Atom content(%) S/Fe ratio
Sulfur Iron Pyrite Fe S 0
protogenetic 24.2 43.1 1.78 10.53 66.86 22.62 6.35

epigenetic 17.5 46.9 2.68 9.76 53.94 36.31 5.53
diagenetic 21.2 45.0 2.12 11.15 62.36 26.49 5.59
Nantong 27.5 79.0 2.87 8.52 34.43 57.05 4.04
diagenetic
protogenetic
epigenetic
538 536 534 532 530 528 526
Figure 1. Oxygen spectra of different genetic coal-pyrites

583
diagenetic coal-pyrite
535
protogenetic Coal-pyrite
Figure 2. Releasing analyses of oxygen of different genetic coal-pyrites

584
Furthermore, if oxygen spectra are analyze(l,the whole knowledge about the oxidation
of coal- pyrite will be obtained. Figure 1 is the oxygen spectra of different coal-pyrites.
Figure 2 is the releasing analysis of oxygen spectra. Figure 1 and Figure 2 show that the
main oxygen peak of protogenetic coal- pyrite is 531.7eV(Table 2), which proves that
FeSO^ is formed on the surface of coal- pyrite. Oxygen peak of epigenetic coal-pyrite
moves toward long wave, mainly 532.85eV(Table 2), lack of 534.5eV peak. This result
shows that the oxidation of epigenetic coal-pyrite is heavy. The oxygen peaks of diagenetic
coal-pyrite are wider.The contents of 531.15eV, 532.85eV and 534.65 eV peaks are close
to each other, which shows the surface properties of diagenetic coal-pyrite (such as
oxidation) are between that of protogenetic coal-pyrite and epigenetic coal-pyrite.
Sulfur oxidativity can be calculated from Table 1 using the ratio of non- pyrite sulfur
and pyrite sulfur. Accordingly, the iron oxidativity can also be calculated using the same
method as sulfur oxidation. The results are listed in Table 3(column 2, 3). Based on the
report f xidativity of coal-pyrite is the ratio of iron oxidativity and sulfur oxidativity (Table
3 column 4). Quantitative analyses of different genetic coal-pyrites and S/Fe ratios are also
listed in Table 3(column 5-8).
Obviously,oxidation order of coal-pyrites is epigenetic coal- pyrite > diagenetic coal-
pyrite > protogenetic coal-pyrite. This order coincides with the variation rule of oxygen
contents on the surface of coal-pyrites.
Because the information about iron can not be collected completely in ESCA studies.
The contents of iron from quantitative analysis are often lower than normal contents. Even
so, the information about iron change of different coal-pyrites can still be examined.
Therefore, one conclusion can be obtained from Table 3,i.e.protogei\etic coal-pyrite is
poor in iron since S/Fe ratio of protogenetic coal-pyrite is biggest.
As stated above,oxidativity and oxygen content of protogenetic coal-pyrite are smaller,
and main peak of oxygen is 531.7eV; Its S/Fe ratio is biggest. On contrary, oxidativity
and oxygen content of epigenetic coal-pyrite are bigger, and main peak of oxygen is
532.85eV; Its S/Fe ratio (5.53) is smaller. The surface properties of diagenetic coal-pyrite
are between above two kinds of coal-pyrites.
On the other hand , the analyses also show that the oxidation of Nantong coal-pyrite is
very heavy. Most parameters(except S peak analyses) are similar to epigenetic coal-
pyrites's.
3.2. Etching Analyses

Etching analyses are carried out in order to get the variation rule of S and Fe as
depth. Etching times are 5, 15 minutes separately. The results are drawn in Figure 3. It is
found that the S/Fe ratio becomes constant as the increase of etching time ( i.e. as the
increase of measurement depth). Oxidation is heavier on the surface of coal-pyrite than
inner part of coal-pyrite. Oxidation phenomenon vanishes gradually as the depth direction.
Versatile forms of sulfur companying with the occurence of oxygen peaks on the natural
surface layers are also found in the etching analyses. The intensity of oxygen peak is
reduced and high energy peaks of sulfur(165,169eV) vanish gradually as the increase of
etching time, which means that oxidation of coal- pyrite only occurs on very thin surface
layers of coal-pyrite.
585
00
5 10 15
Etching time(Minute)
Figure 3. Etching analyses of Nantong coal-pyrite
4.CONCLUSION
Surface properties and oxidation of three kinds of coal-pyrites(protogenetic, epigenetic

and diagenetic coal-pyrite) have been studied using ESCA. Three conclusions have been
obtained.
1. oxygen peaks of different genetic coal-pyrites differ largely.The oxygen peaks of
epigenetic coal-pyrite move toward high energy direction with main peak 532.85eV.
The main oxygen peak of protogenetic coal-pyrite is 531.7eV. The oxygen peaks of
diagenetic coal-pyrite are wider, and the intensities of the peaks are less than that of
above two kinds of coal-pyrites.
2. The variation rule of the sulfur oxidativity of different genetic coal-pyrites is different
from the variation rule of iron oxidativity and pyrite oxidativity. The order of sulfur
oxidativity is as follows: protogenetic coal-pyrite > diagenetic coal-pyrite > epigenetic
coal-pyrite. Otherwise, the iron oxidativity and pyrite oxidativity are opposite to sulfur
oxidativity order, i.e.epigenetic coal-pyrite > diagenetic coal- pyrite > protogenetic
coal-pyrite.
3. Quantitative analyses and etching analyses show that protogenetic coal-pyrite is poor in
iron and epigenetic coal- pyrite is rich in iron relatively. The oxidation of coal-pyrite
just occurs on the very thin surface layers of coal-pyrite. Oxidation will vanish gradually
and S/Fe ratio becomes constant increase of depth.
REFERENCES
1. Xuxin Shao, "Recent Developments of coal preparation in USA", Express Information

on Mineral Processing Abroad, No.9, 1992.
2..Chenggang Fan , Mengxiong Guo, "Desulfurization of Fine Coal Using HGMS"
586
Proceedings of the Sixth National Coal Preparation and CWF Conference, China,
1991.
3. T. Zhong, Q. Huang, W. B. Hu, M. E. Wadsworth, D. W. Bodily, "Flotation Behavior
of Mineral and Coal-pyrite", Proceedings of Eighth Pittsburgh Coal Conference, 1991.
4. Wagner C D . et al, "Handbook of X-ray Photoelectric-spectroscopy", Perkin Elsmer
Corporation, MN, USA, 1978.
5. Kelemen. S. R. et al, Fuel, Vol.69, P.939, 1990.
6. Khan. S. N. et al. Applied Surface Science, 47(4), P.355, 1991.
Effect o f furnace atmosphere on the calcination TG curves o f

natural limestones and dolomites
Ayegl Ersoy-Merigboyu, Sadriye Kkbayrak
Istanbul Technical University, Chemical and Metallurgical

Engineering Faculty, 80626, Maslak, Istanbul, TRKYE
/. ABSTRACT
Two different gaseous atmospheres were employed to examine the changes of calcination
TG curves of 20 natural limestone and 6 dolomite samples from various parts of Trkiye.
Calcination TG curves of these samples were obtained in atmospheres of 1) pure nitrogen;
and 2) 15% by volume C O 2 in dry air, and they were recorded under non-isothermal
conditions. It was found that, initial and final calcination temperatures were effected by
flimace atmosphere. Also, the shape of TG curves of both limestone and dolomite samples
were strongly effected from CO^ partial pressure.
All samples were sulfated in a tube furnace at a constant temperature of 1173 K. The
composition of the gaseous mixture used in the sulfation experiments was 15 vol % CO^, 0.35
vol % S O 2 and balance of dry air by volume. Total sulfation capacities of the calcines
prepared from limestone samples range from 0.381 to 0.686 (mg SOj/mg sorbent) and those
from dolomite samples range between 0.321-0.498 (mg SOj/mg sorbent).
2 INTRODUCTION
Natural limestones and dolomites are usually considered as sorbents for the removal of
sulfur dioxide resulting from the combustion of fossil fuels. Sulfur dioxide pollution from coal
combustion can be reduced by burning the coal in a fluidized bed of limestone or dolomite
[1,2].
The reaction between sulfur dioxide and limestone or dolomite is assumed to occur in two
steps: 1) Calcination and 2) Sulfation. Previous studies indicated that the rate of the sulfation
reaction of calcines is influenced by the partial pressure of carbon dioxide in which the
calcination reaction occurs [3],
The stoichiometric expression for the calcination reaction of limestone is
CaCOJ (s) + heat <=====> CaO (s) + CO^ (g) (1)
However, the calcination of dolomite occurs in two stages
MgCOj.CaCOj (s) + heat < = = = = > MgO.CaCOj (s) + CO^ (g) (2)
MgO.CaCOj (s) + heat <=====> MgO.CaO (s) + CO^ (g) (3)
Because of the reversible nature of these reactions, their decomposition temperature and rate
are dependent upon the C O 2 partial pressure.
588
This study discusses the effect of furnace atmosphere on the calcination TG curves of 20
limestone and 6 dolomite samples from various parts of Trkiye.
J. EXPERIMENTAL
Thermogravimetric experiments were performed using a Shimadzu TG 41 thermal

analyser. 100 mg samples after grounding to pass a 0.25 mm sieve were spread uniformly on
the bottom of a cylindrical crucible. Constant total flow of gases was maintained at a rate of 40
cc per minute. Partial pressure of carbon dioxide in the furnace atmosphere was obtained by
mixing dry air and carbon dioxide in appropriate ratios. These ratios were maintained as 15 %
carbon dioxide and 85 % dry air by volume. The temperature was detected with a Pt-Rh
thermocouple fixed in a position near the sample pan.All samples were heated up to 1223
and the programmed heating rate was 10 K.min-1. Calcination TG curves of the samples were
recorded with a chart speed of 2.5 mm.min"^.
Sulfation capacities of the samples were determined by reacting their calcines with a synthetic
gaseous mixture consisting of carbon dioxide 15 vol %, sulfur dioxide 0.35 vol% and a
balance of dry air at a total flow rate of 350 cc per minute. Samples with a particle size of
<0.25 mm, were fully calcined in a tube furnace at 1173 in a gaseous atmosphere consisting
of carbon dioxide 15 vol % and dry air 85 vol % before sulfation. Calcined samples were
exposed for 150 min to the sulfating gaseous mixture in the furnace at the constant
temperature of 1173 K.
The chemical analyses of the limestone and dolomite samples (Table 1) were also done
according to ASTM standards [4],
Figures 1-2 show four examples of the thermal decomposition curves of the limestone and
dolomite sample which were calcined in two different furnace atmospheres. The TG curves
showed, typically, weight decreases due to the loss of C O 2 from the original sample
(Eqns.1-3).
On the TG curves of limestones recorded in two different atmospheres, generally, only one
decomposition step can be seen (Eqn. 1). However, on the curves of three limestone samples
which were recorded in the mixture of dry air and CO^, there is a weight loss step which
represents the MgCOj decomposition reaction, as well [Figure 3]. Though, this step was not
seen on their TG curves recorded in nitrogen atmosphere.
On the TG curves of dolomite samples two different decomposition steps can be
distinguished. The explanation of this behaviour could be the high MgCOj content of
dolomites, thus their decomposition occurs in two stages (Eqns. 2,3). The first step
corresponds to the decomposition of MgCOj (Eqn.2) and the second step represents the
decomposition of CaCOj (Eqn.3). This distinction became clearer on the TG curves of the
calcination in the mixture of dry air and CO^.
As can be seen from Figures 1-2, the shape of TG curves of both hmestone and dolomite
samples is very sensitive to C O 2 partial pressure which was found in the furnace atmosphere.
Initial and final temperatures of the calcination reactions of the sorbent samples were
determined from their TG curves. It was found that, these temperatures are effected by CO^
589
100
\ \
\ \
90 h- \ \
\ \
\ \
J 80
\ \
- \ \
\ \
(9 \ \
2 70
\ \
\ \
\ \
60 _ \ \
\\ \V
50 I 1
773 1173K
Temperature CK]
Figure 1. Thermal Decomposition Curves of the Limestone Sample L04 in Two Different
Furnace Atmospheres ( ( ) Nitrogen; ( ) 15 % by Volume CO^ in Dry Air).
100
\\
_
\\ \\
\ \
\ \
_ \ \
\\
\\ \ \
\ \
\ \
\\ \\
\ \
\ \
\ \
\ V
50 1 1
773K 1173
Temperature CK]
Figure 2. Thermal Decomposition Curves of the Dolomite Sample D06 in Two Different
Furnace Atmospheres ( ( ) Nitrogen; ( ) 15 % by Volume CO^ in Dry Air).
590
100
90
S 80
70
60 JL
773 1173
Temperature []
Figure 3. Thermal Decomposition Curves of the Three Limestone Samples in the Mixture of
Dry Air and 15 % by Volume CO^. ( ( ) L12; (- - -) L13; ( L 1 5 ).
100
90
80
i 70
60
50 J
773 1173K
Temperature [K]
Figure 4. Thermal Decomposition Curves of the Dolomite Sample D05 in Two Different
Furnace Atmospheres ( ( ) Nitrogen; (- - -) 15 % by Volume CO^ in Dry Air).
591
Table 1
Chemical composition and total sulfation capacities of the sorbent samples
Sample CaO MgO Fe203 SO2 AI2O3 Sulfation

code (%) (%) (%) (%) (%) (mg SO^/mg Sorbent)
LOl 55.23 0.28 0.21 0.59 0.628

L02 54.98 0.13 0.14 0.50 0.581
L03 54.09 0.40 0.58 0.55 0.592
L04 54.03 0.26 0.12 0.11 0.60 0.658
L05 53.65 0.26 2.12 0.42 0.653
L06 53.39 0.26 0.38 1.35 0.54 0.655
L07 52.48 1.27 0.57 2.05 0.39 0.619
L08 52.17 1.05 0.08 0.61 0.21 0.381
L09 51.90 2.50 0.34 0.94 0.66 0.554
LIO 50.60 1.53 0.75 3.10 2.20 0.589
Lll 49.21 0.79 0.47 6.49 1.21 0.583
L12 43.13 1.78 0.16 8.64 4.60 0.515
L13 37.45 4.65 3.54 12.64 6.70 0.384
L14 54.05 0.52 0.25 0.40 1.14 0.561
L15 47.91 1.82 0.44 6.80 2.58 0.488
L16 53.56 0.26 0.08 0.35 1.27 0.664
L17 54.48 0.26 0.02 0.22 0.54 0.459
LIS 54.29 0.04 0.02 1.02 0.686
L19 54.08 0.76 0.10 0.02 1.20 0.432
L20 49.91 2.70 0.46 3.66 2.04 0.642
DOl 36.02 14.66 0.60 2.67 1.40 0.430
D02 32.50 16.87 0.17 4.97 0.97 0.329
D03 31.85 19.21 0.36 1.16 0.36 0.498
D04 31.52 19.87 0.12 0.64 0.26 0.443
D05 20.30 22.60 0.25 13.30 1.90 0.399
D06 30.04 19.22 0.32 1.23 0.321
L : Limestone ; D : Dolomite
592
concentration in the gaseous atmosphere. Generally they are different for each sample too.
Initial calcination temperature of the limestone samples ranges from 893 to 965 in nitrogen
atmosphere and from 1071 to 1109 in the mixture of dry air and CO^; on the other hand
final calcination temperature ranges from 1148 to 1169 in nitrogen and from 1184 to 1216
in the mixture of dry air and CO^.
For dolomite samples initial and final calcination temperature ranges were determined
as;813-922 and 1125-1160 in nitrogen; 858-978 and 1158-1177 in the mixture of
dry air and C O 2 , respectively.
It should be pointed out here that the initial and final decomposition temperatures of both
limestone and dolomite samples, because of the reversible nature of their decomposition
reactions, are shifted to higher temperatures in the presence of high partial pressure of CO2 in
the ftirnace atmosphere (Fig. 1-2). Also, the temperature range of the decomposition of the
stones became narrower due to the high CO2 partial pressure Thus, the total decomposition
time intervals of the stones (especially for limestones) are shorter in the mixture of dry air and
C O 2 atmosphere than in nitrogen. Decomposition time intervals of limestones ranged from
20.3 to 26.8 min in nitrogen atmosphere and from 9.6 to 13.3 min in the mixture of dry air
and CO2 Total weight loss of the samples was changed depending on their carbonate content.
According to their chemical analyses the CaCOj content of the limestone samples varies
between 66.88-98.63%; the MgCOj content between 0-9.77% . Although, the CaCOj
content of dolomites varies between 36.25-64.32% ; the MgCOj content varies between
30.79-47.46% .
On the TG curve of a dolomite sample which contains a high percentage of impurities there
are four different weight loss steps, because of decomposition of the impurities beside MgCOj
and CaCOj components [Fig. 4]. These steps can be distinguished more clearly on the TG
curves of the calcination experiments carried out in the mixture of dry air and CO2
The total amount of SOj absorbed by the calcined sorbents was found different for each
sample as summarized in Table 1. Measured sulfation capacities of limestone samples range
from 0.381 to 0.686 (mg SOj/mg sorbent) and those of dolomites range between 0.321-0.498
(mg SOj/mg sorbent).
REFERENCES
1. B.Bonn and H.Mnzner, Proc. of the Institute of Energy's Int. Conf in London, 1-7 Nov.,
(1980).
2. A.Lallai, G.Mura, A.Viola and F.Giogia, Int.Chem.Eng., 19 (1979) 445.
3. E.P.O'Neill, D.L.Keairns and W.F.Kittle, Thermochimica Acta, 14 (1976) 209.
4. Annual Book of ASTM Standards, 13, Method C25-72 (1977).
The Ohio coal testing and development facility
Edward R. Torak
ICF Kaiser Engineers

Pittsburgh, Pennsylvania 15222
1. BACKGROUND
On June 14, 1987, the Ohio Coal Development Office executed a grant
agreement with ICF Kaiser Engineers for the planning and design services for a
demonstration advanced technology coal preparation facility. American Electric Power
Service Corporation (AEPSC) was a co-sponsor and designated its site at the Central
Ohio Coal Company's Unionville Coal Preparation Plant for locating the test plant. The
new facility provides a location for testing of current, or future, advanced processes
for cleaning Ohio coals to reduced sulfur levels in an economical manner.
The design of the facility was completed in early 1989, including engineering
drawings of the new facility and purchase specifications for all equipment, fabricated
steel and construction work. The flow sheet design includes a two-stage conventional
heavy media cyclone circuit to preclean the plus 28M raw coal and generate three
products - a low sulfur clean coal, a high ash and high sulfur refuse, and a middlings.
The natural minus 28M is combined with the middlings (also crushed to minus 28M),
sized at 150M and cleaned in two advanced processes. An advanced heavy media
cyclone circuit cleans the 28M 150M fraction and a three-stage froth flotation circuit
cleans the 150M O fraction. Various size combination options also can be
accommodated. During design of the facility the Electric Power Research Institute
tested the flotation circuit at its Coal Quality Development Center. ICF Kaiser
Engineers, using that information and the raw coal's washability data, predicted
expected cleaning performance from the plant for three Ohio Coals - Pittsburgh #8,
Middle Kittanning and Meigs Creek. Significant sulfur reductions were predicated at
economical energy recoveries to indicate that the process should be demonstrated.
Ohio Power Company, a subsidiary of AEPSC, elected to implement the
construction and testing of the facility under the OCDO Grant No. COD/D-86-61 (B).
Ohio Power subcontracted the work to ICF Kaiser Engineers, Inc. who utilized the
drawings and specifications as a basis for the construction package. Ohio Power had
requested ICF KE to add a coarse coal cleaning circuit so the size of the final product
would be more easily handled by typical power plant systems.
594
The purpose of the project is to provide practical design data for the construction
or modification of full scale commercial plants. Coals of three different seams will be
tested, and the key coal properties which might have an impact on equipment
performance, plant design, plant economics, or plant operation will be compared. The
project expands coal cleaning technology by demonstrating novel process equipment,
coal sampling methods, process instrumentation, and the use of computer control for
plant operation. The facility, in the future, can be used for the practical training of
engineers and operating personnel in cooperation with universities and industry in the
belief that unique operating experience can be gained through familiarization with the
diverse equipment, processes, and test procedures employed at the facility. The
facility will therefore provide numerous educational functions which will become an
asset helping with the development and operation of future commercial coal cleaning
plants in Ohio.
The construction of the facility began in the first quarter of 1991. Engineering was
completed on the addition of the coarse coal circuit and all equipment or fabrication
items were procured. After all construction permits were issued, and construction
subcontracts were awarded, field work actually began in mid-summer of 1991 and
was completed by April of 1992. Shakedown and testing activities and process
equipment performance verification work were completed in September 1992.
2. FACILITY DESCRIPTION
2.1 Raw Coal Handling

Raw coal (6" 0) is conveyed to a single stage, double roll crusher via a 24" belt
conveyor. The belt conveyor is fed by one of three vibrating feeders in the reclaim
tunnel under the raw coal stockpile. Each feeder is capable of supplying the designed
50 TPH to the raw coal crusher. The crushed 2 " raw coal is then stored in a 200 ton
bin for further processing.
2.2 Coarse Heavy Media Circuit

Raw coal which is crushed from 6 inch top size to 2 " O is separated on a
double deck raw coal screen into two size fractions, 2" 1/4" and 1/4" 0. The 1/4"
X 0 size fraction reports to the raw coal sump. The 2" 1/4" size fraction reports to
a two-stage 6' diameter 10' long Wemco Drum (Figure 1). The 2" 1/4" raw coal
first reports to the low gravity section of the drum. The clean coal float material from
this section of the drum reports to the Coarse Clean Coal D & R Screen where
magnetite is removed from the product. The clean coal then discharges to the plant
clean coal collection conveyor as product. The sink material in the first stage
compartment is conveyed via the rotating drum refuse lifters to the high gravity section
of the drum. The sink material from this section of the drum reports to the refuse
section of the Coarse Refuse/Middlings D & R Screen where magnetite is removed.
The refuse then discharges to the plant refuse collection conveyor. The middlings float
material from this section of the drum reports to the middlings section of the Coarse
595
Figure 1. Wemco Drum Heavy Medium Separator.
Refuse/Middlings D & R Screen where magnetite is removed. The middlings are then
crushed to 3/8" O and report to the raw coal sump.
2.3 Intermediate Heavy Media Cyclone Circuit

Raw coal from the raw coal screen underflow, 1/4" 0, combines with the 3/8"
X 0 crushed middlings from the coarse heavy media circuit. This combined material
(3/8" X o) reports to the deslime screen via the raw coal pump. The deslime screen
separates the material at 28M. The 28M 0 reports to the Primary Classifying Cyclone
Sump for further processing. The 3/8" 28M material reports to the First Stage Heavy
Media Sump where it is combined with a magnetite slurry and then pumped to the
First Stage Heavy Media Cyclone (Figure 2). Clean coal and reject from the cyclone
report to the split first stage drain and rinse screen where magnetite is recovered. The
clean coal from the first stage drain and rinse screen reports to a basket centrifuge
for dewatering and then to the plant clean coal collection conveyor. Reject from the
first stage drain and rinse screen reports to the second stage heavy media sump
where it is combined with a second magnetite slurry and is pumped to the Second
Stage Heavy Media Cyclone. Middlings and refuse from the cyclone report to the split
second stage drain and rinse screen where magnetite is removed. The middlings from
the second stage drain and rinse screen report to a cagepactor where it is crushed
to 28M X 0. The refuse from the second stage drain and rinse screen reports to a
basket centrifuge for dewatering and then to the plant refuse collection conveyor.
596
Figure 2. Heavy Media Cyclone
2.4 Fine Heavy Media Cyclone Circuit

Natural 28M 0 raw coal from the Deslime Screen Underflow combines with
crushed (28M 0) middlings from the Second Stage Heavy Media Cyclone. The
combined 28M O material then reports to the Primary Classifying Cyclones (Figure
3) where it is separated at approximately 325M. The 325M O material can either
report to the flotation cells or to the refuse thickener. The 28M 325M reports to the
Secondary Classifying Cyclone (Figure 4) where it is separated at approximately
150M. The 150M 325M can either report to the froth flotation circuit or to the refuse
thickener. The 28M 150M reports to one of two circuits. The first option is the froth
flotation circuit. The second option is the Fine Heavy Media Cyclone Circuit. In the
second option, the 28M 150M reports to the fine raw coal screen for dewatering.
The discharge from the fine raw coal screen reports to the Fine Heavy Media Cyclone
(Figure 5) after magnetite slurry addition via the Fine Heavy Media Cyclone Pump. The
clean coal and refuse products report to a split Fine Heavy Media Circuit D & R
Screen. After magnetite is removed, refuse and clean coal from the circuit are
dewatered in separate basket centrifuges. The refuse then reports to the plant refuse
collection conveyor while clean coal reports to the plant clean coal collection
conveyor.
597
Figure 3. Primary Classifying Cyclones.

598
Figure 4. Secondary Classifying Cylcones.

599
Figure 5. Fine Heavy Media Cyclone.
3. TESTING AND OPERATION
The primary objective of the facility is to demonstrate the ability of the advanced
preparation facility to remove ash and sulfur from Ohio coals to a greater extent than
is possible with conventional coal preparation plants. Three Ohio coals will be tested
and documentation prepared describing the test results and benefits achieved with
the advanced process. Meigs Creek seam coal was obtained from the Central Ohio
Coal Company's Muskingum Preparation Plant Feed. The Pittsburgh seam coal will
be obtained from AEP's Windsor Mine while the Middle Kittanning seam coal will be
obtained from a source to be determined just prior to starting the test work in early
1994. The test work on the Meigs Creek, Pittsburgh, and Middle Kittanning coal seams
will be identical. All three coals will be obtained from producing mines in the state of
Ohio and all will have operating preparation plants. A representative sample of the
operating preparation plant's feed, clean coal, and refuse will be obtained. These
three streams will be subjected to extensive analytical tests so that the performance
of these existing commercial preparation plants can be determined in detail and then
later compared to the performance of the advanced plant. Specifically, each sample
will be analyzed for the following:
600
Figure 6. Froth Fiotation Cells.

601
1. Size Consist
2. Washability (Float/Sink)
3. Proximate
4. Ultimate
5. Sulfur Forms
6. Ash Constituents
Performance tests were completed on the conventional test facility circuits in July
1992. Testing on the Meigs Creek Seam was completed in January 1993, on the
advanced fine heavy media cyclone circuit and the advanced flotation configuration
circuits (Figure 8). Specifically, the froth cells were operated in two (2) configurations
as follows:
1. Rougher Only
2. Rougher, Scavenger and Cleaner
For the rougher, scavenger and cleaner configuration, all of the following eight
(8) advanced configurations were tested. For the rougher only configuration,
configurations 3, 4, 7, and 8 were tested. The eight configurations were as follows:
1. 28M X 0 Froth
2. 28M X 150M Froth, Refuse 150M 0
3. 28M X 325M Froth. Refuse 325M 0
4. 28M X 325M and 325M 0 Froth
5. 2 8 M X 1 5 0 M H M C . Refuse 150MxO
6. 2 8 M X 1 5 0 M H M C . 150MxO Froth
7. 28M X 150M HMC, 150M 325M Froth, Refuse 325M 0
8. 28M X150M HMC and 3 2 5 M x O Froth
The froth cells (Figure 6) were monitored for reagent addition, percent solids in
the feed, and cell level while the heavy media cyclone was monitored for circulating
gravity. During the test runs the reagent dosage rate and type of reagent was varied
on the frothcell circuit. The heavy media cyclone circulating gravity was for the most
part held constant. Results from the Meigs Creek test program are still being analyzed
as of April 1993. Test work on the Pittsburgh Seam and Middle Kittanning Seam Coals
will be conducted during early 1994.
1993 Elsevier Science Publishers B.V. AH rights reserved.
The magnetic circuit calculation and technical propertiesof a nev^ly de

signed commercial sized metal-belt-type high gradient magnetic separator
Prof.M.X.Gou",JianZhong Zheng^ M.Zeng^ H.Q.Qu', G.R.Jia'
^Dept. of Mineral Processing

Beijing Graduate School
China University of Mining and Technology, Beijing, 100083
^Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences

P.O.Box 2871
Beijing, 100085
'Shenyang Mining Machinery Manufacturer
P.R.China
ABSTRACT
Having analysed both the advantages and disadvantages of traditional vertical and
horizontal ring HGMS(High Gradient Magnetic Separator) the authors finally put for
ward a new concept of metal-belt-type H G M S . N o w , with a magnetic field intensity of
17,000 Oe,belt width of 600mm, and capacity of 5t coal or 1 0 - 15t minerals per hour,
the newly designed machine can not only be used in coal pyrite desulfurization but also
in Kaolin purification ,hematite recovery and other mineral processing practices .The
paper demonstrates in details the magnetic circuit calculation , mechanical design and
technical characteristics of the machinis new washing system which makes it possible to
forestall b l o c k - ups while processing. The comparison of the technologcial characteris
tics with that of convenfionl H G M S separators are presented . The technological pros
pect is discussed when it is used in commercial practices.
THE ORIGIN OF THE PROJECT
High Sulfur Coal is heavily distributed in Southwest of China. As an example, with

total sulfur above 3 % , the high sulfur coal in Chongqing district, Sichuan Province is
composed of nearly 1 / 3 organic sulfur and 2 / 3 inorganic sulfur, mainly pyrite. The
organic sulfur exisfing in the complex organic compounds is evenly distributed in coal
matrix and cannot be removed from coal except chemical and biotechnological pro-
cssing;but the coarse pyrite can be readily removed with physical separation technolo
gy. Because direct use of high sulfut coal by Chongqing power plants and local
604
residents, heavy acid rain pollution has been caused. The current situation is representa
tive of the areas suffered from acid rain pollution. The development of high sulfur coal
separation technology before combustion is the key to alleviate acid rain pollution in
China.
Flotation as a conventional separation technology has high efficiency to process coal
both in Btu recovery and ash removal, but the sulfur removal ratio is very
low.^Kamegaya, H.^carried out an experiment to explore the efficiency of deashing and
desulfurization of an U. S. coal by continuous microbubble column flotation. In the ex
periment froth clean coal is obtained with recovery of 79.2%, ash content 6.5%, total
sulfur content 2.9%, contrasted with raw coal with ash content, organic, and pyrite sul
fur 9.2%, 1.4% and 1.7% respectively. This means pyrite removal from coal is also very
difficult under normal column flotation process. But the H G M S separation result of the
froth product is quite fascinating with the final product Btu recovery 69.9%, ash and to
tal sulfur content 3.9% and 1.8% respectively.
The present research work now undertaken by the authors indicates that coal pyrite
and ore pyrite have quite different charateristics in surface chemistry and certain physi
cal properties owing to the erosion of coal matrix on the pyrite surface during the coal
formation period. As a result, pyrite and coal surfaces are both hydrophobic resulting in
the low efficiency of coal and pyrite particle separation in flotation. This supports the
laboratory and practical results in coal preparation plants in Sichuan Province. Al
though there are many reports on pyrite depressants, ^'"^'^'^commercial use hasn^t been
seen.
Although desulfurization by chemical, agglomeration,and biological processing has
high desulfurization efficiency, commercial use of these technologies in coal preparation
plants is hampered because of their processing capacity and economic problems. At
present, a poly technical desulfurization process by H G M S and traditional flotation is
undertaken in China to cope with the high sulfur coal desulfurization before combus
tion.
THE DEVELOPMENT OF HGMS
Nearly 30 years have passed since the first H G M S separator was invented in the
U.S.A.. Since then various kinds of H G M S have been invented to meet the demand of
specific separation process in mineral processing and filtration. The first commercial
scale solenoid H G M S separator was invented by Sala Corporation in 1969. With diam
eter 2.1m, height 0.5m, magnetic intensity 2T, the machine had a capacity of processing
115 ton minerals per hour. The solenoid H G M S separators are mainly used in kaolin
purification and sewage treatment.
In order to cope with the problem of low separation efficency in processing feed with
high ratio of magnetic product. Sala coporation designed a continuous carousel-type
H G M S unit. Of the reported series, such as Sala H G M S 120, 185, 240, 350, 480, 480
605
type has the highest capacity 800T / h. The carousel type H G M S Unit is mainly used in
processing kaolin, wolframite, etc.
At the 15th, 16th International Mineral Processing Confernces, Czechoslovakia and
USSR introduced their H G M S Separators VMS and V M K S - 1 respectively. Both
separators have a vertical ring.With the magnetic circuit sitting on the upper part of the
ring for VSM and lower part for V M K S - 1 . VSM has a capacity of 3 0 T / h, and mag
netic intensity of 1.7 , With a magnetic intensity of 2.0T, the V M K S - 1 separtor is
mainly used to process kaolin.
According to the study on the susceptibility of coal pyrites and Sichuan Coals by Dr.
J. Z. Zheng, the average mass susceptibility of coal pyrites is 1 .58 x 10"^cmV gm, but
the bituminous coal in Nantong ranges from -1.74 x 10"^to - 3 . 0 5 x 10"^cmVgm. Al
though the relative difference is quite great,their absolute values are rather small.
Theoretically, in case of high magnetic intensity and field gradient, minerals with oppo
site sign suseptibilities can be separated efficiently because one is attracted to the mag-
nefic matrix while the other is not. But practically,the H G M S separators now available
for commercial use in preparation plants are mainly designed for hematite recovery and
kaolin purification. When they are directly used for coal / pyrite separation, the Btu re
covery and pyrite desulfurization ratio are not so successful as the minerals mentioned
above. This is because the low mass susceptibility of coal and pyrite calls for a high uni
formed external magnetic field and high gradient magnetic matrix where the feed can be
exposed to a mighty and stable separating force environment. The successful coal and
pyrite separation also calls for a better water flushing system, which enables the magnet
ic matrix free from blocking up.
Because of the urgent demand of environmental protection China University of Min
ing and Technology invented the belt form H G M S separator in April, 1992 to meet the
specific need for low susceptibility minerales separation such as C o a l / P y r i t e ,
Copper / Lead,Copper / Molybdenum, and Copper / Bismuth.
T H E M E C H A N I C A L AND T E C H N I C A L P R O P E R T I E S O F C D A D - 6 0 0 H G M S
SEPARATOR
1. Main parameters
As shown in F i g . l , C D A D - 6 0 0 belt form H G M S separator is mainly composed of a
saddle solenoid magnet,a separation belt consisting of 33 compartments, a flushing and
rinsing system,and 2 tumbling cylinders which power and backup the compartments
.With a size of 3.200 x 2.366 x 2.950 m,the separator weighs 18.9 ton and can process 5
ton coal or 10 - 1 5 minerals per hour. The highest magnetic intensity is 1.7 Tesla. The
rating poweer is 65 kw.
2. Separation principle
After being filtered by the electromagnetic vibration screen 1, the qualified slurry is
606
Paramagnetic
Paramagnetic
minerals
minerals
Fig.l. C D A D - 6 0 0 metal-belt-type H G M S separator

1 .electromagnetic vibration screen 2.magnetic system 3.driving tumbling cylinder
4,4^ rinsing and flushing vessels S.frameworks 6.flushing networks
7.nonmags(coal) S.high pressure flushing 9.rinsing
10.vacuum chuck 11 .rinsing 12.separation compartment
13.reduction gear
607
introduced into the matrix of the compartments 12 through the upper part of iron case
2. The paramagnetic particles( pyrite and some coal minerals )are captured and adhere
to the matrix while the diamagnetic coal particles pass through the lower part of case 2
and are collected as clean coal in 7. When the compartments leave the magnetic field
and arrive at the rinsing and flushing system the paramagnetic particles are washed off
the matrix into the flushing vessles 4 and 4\ from the lower parts of which the pyrite
and coal minerals are collected.
3. Continuous separation in a uniform magnetic feld

The 33 separation compartments connected to each other form a continuous separa
tion belt which is supported by the 2 tumbling cylinders in opposite sides of the
separator. The driving cylinder 3 is powered by reduction gear 13 which makes available
a series of belt velocity. Different from the traditional carousel-type u n i t , C D A D - 6 0 0
H G M S separator employs a continuous separation belt in place of the rotating ring ,
and its straight saddle solenoid coils (Fig.3)can excite a more uniformed magnetic field
than that of the arc solenoid of the carousel type separator.
4. Washing system
The separator's washing system is expected to solve the problem of particle blocking
up as existing in the carousel type H G M S separators. The newly designed washing sys
tem employs 4 stages of alternative flushing or rinsing for the cleaning of the compart
ments. As shown in Fig.l, after turning their direction the compartments are bottom up
making the coarse particles trashed in the matrix of the lower part of the compartments
easier to be washed off contrasted with the washing system of traditional carousel type
H G M S . The compartments experience high pressure flushing at 8 in the washing vessels
4 removing most of the paramagnetic particles, then, they are rinsed at 11,followed by
vacuum pumping at 10,and before returning to feed zone in the upper part of the
separator they receive the last stage rinsing at 9 offering relatively cleaning compart
ments for the next separation cycle .
Because part of the rinsing water collected in the vessels is recycled for the flushing
system clean water is saved.
CD AD 600 H G M S M A G N E T I C CIRCUIT C A L C U L A T I O N
l.Dctcrmination of the AmpereTurns of the Magnetic Circuit

The following empirical formula is used to determine the total ampere turns of the
magnetic circuit.
IN = yH^L^ X lo' (1)
Where INampere turns;

608
yempirical constant, y = 1.27;

H q m a g n e t i c field intensity,Tesla, H q = 1.7Tesla;
L q h e i g h t of separation space,cm, Lo= 10.2cm.
Then (1) becomes
I N = 1.27x 17000x 10.2
= 220218(ampere turns)
2.0ptimization of current density, intensity, and arrangement of the coils

Because the dimension of the excitation power is determined by the current density,
the current intensity, the cross dimension of the copper wire,and the arrangement of the
coil,a computer program is used to optimize the excitation power in a broad entent of
parameters mentioned above. The domain of the parameters adoped here are:
Current density
= 3, 3.1, 3.2, ...7.9, 8.0 ampere / mm^
Cross dimension of the copper wire
A = 12,13,14, ...,19,20mm;
= 6,6.5,7.0,... 9.5,10mm
Where A,B are the side dimension of the outside and inside square.
The optimized size of the wire is A = 14mm,B = 7mm, as is shown in Fig.2.
Fig.2. Cross section of the wire
To save copper, we evenly distribute the saddle coil to the upper and lower saddles
with 1 9 x 1 2 turns in each part.
Optimized parameters are listed as following:
^ = 3.30 ampere / mni^
I = 3.30 X (14 X 1 4 - 7 x 7 )
485 ampere
Actual ampere turns

609
IN = 2 x 19x 1 2 x 4 8 5
= 221160
> 220218 (ampere turns)
The upper and lower saddlers cross dimensions are both arranged with width 19 turns
and height 12turns so as to saftisfy the demand of the cooling system and wire connec
tion.
3.Volume ratio of copper in the solenoid space

In case of satisfying the demand of the coil cooling system, high volume ratio of
copper is suggested to minimize the dimension of the solenoid. Considering that coil
winding error and layer insulation between layers exsit, 1mm gap is selected for gap be
tween coil layers.
_ Sjwire) _ 1 9 x 1 2 x 147
^ Sitotal) (289 x 180)
= 64.43% (2)
Where volume ratio of copper in the solenoid space ;

S(wire)area of copper in the cross section of the solenoid;
S(total)area of the cross section of each solenoid.
4.The length and weight of the coil.

Shown in Fig.3 is the sketch of the solenoids.
= 2 X ( 8 1 5 - 6 0 ) 4 - 2 X ( 6 8 0 - 60)
+ 4 x 1 / 4 2 ( 3 0 + 180/2)
+ 4 x 1 / 4 2 ( 3 0 + 285/2)
= 4.588(m) (3)
= 19 12 X 4.588
= 1046(m) (4)
W=U1 X 1 0 " ' X 2092 8.8

= 2.71() (5)
Where Ljthe average length of each turn, M;

L2total coil length of each saddle, M;
Wtotal weight of the 2 saddles,Metric ton.
610
V 12 turns
J
12 turns
19 turns
Separation sapee
3
5-.
CS
815x680
19 turns
Fig.3.Sketch of the straight saddle solenoid coils
5. Determination of excitation power, excitation voltage, and total coil resistance

Select electric use copper as the coil's hollow core conductor and the resistance
coefficient is determined by formula 6
a=a Cl+(r-20)1 (6)
Where a^copper resistivity at 20 t : , 1.79 x 10"^(D.m);

the average working temperature of the coils. Supposing the initial tempera
ture of the cooling water passing through the coils is 20 <C, and final tempera
ture is 5 0 t : , t h e n T = 3 5 t ; ;
agspecific resistance of copper, 0.00385.
Therefore:
a35t = 1.79 X 10-^[-(35-20) x 0.00385]

= 1.893 - m )
R^=ay. L 2 / 5 = 1.893 1 0 " ' 1 0 4 6 / C147 (10 " '

= 0.1347(Q-m)
(7)
R = R^ 7 2 = 0 . 1 3 4 7 / 2
611
= 0.06735() (8)
i? = 1.79 1 0 " ' 1 0 4 6 / Cl47xl0~'x2:

= 0.0637() (9)
For P = f-><R
(10)
= ( 4 8 5 x 2 ) ' 0.0637
= 60(;fcw) (11)
= (485 1 0.06735
= 63.4(/cw) (12)
Select = 65^:^ (13)
F = 485 2 0.0637
= 61.79() (14)
V = 4 8 5 x 2 x 0.06735
= 65.33() (15)
Where Rjthe resistance of the upper or lower saddle coils;

Rtotal resistance of the saddle coils at 35 <C;
Rqinitial total resistance of the saddle coils;
Pqinitial excitation power;
P^normal excitation power;
Vqinitial excitation voltage;
V^normal excitation voltage.
6. Cooling system calculation

The amount of cooling water needed for the coils is determined by the following
equation
P = cxmx{t^-t^) (16)
Where normal excitation power,W;

mthe mass of cooling w a t e r , g / h;
tjinlet temperature, tj = 20 <C;
t2exit temperature , t2= 50 <C;
612
cspecific heat of water,c = 4 . 1 8 J / g.
Therefore:
m = p/[cx {t^ - /j)]
= 65 X 3600 X lO' / [4.18 (50 - 20)]

= 1.87(//0
The cooling system consists of 12 separate cooling passages with 2 layers of coils or
1 9 x 2 turns of coils forming one water passage.
Hence:
2 = 1.87/12
= 0.1558(mV/0
= 4.328 X 10 " ' ( m V ^ ) (17)
L =\9x2x La

= 19 X 2 X 4.588
= 174.344(M) (18)
U=Q/S
= 4.328 X 10 V C49 10
= 0.883(M/^) (19)
R^=D^ X U X p/
= 7 X 1 0 " ' X 0.883 X 9 8 9 . 5 3 / C60.8 10"':]

= 10059.7 (20)
Where Q the amount of cooling water passing through one passage per
secondjM^/ S;
Lpthe length of one cooling passage,M;
Lâverage length of each turn of coil,M;
Uvelocity of water passing through the passage,M / S;
Ssection area of the cooling passage,M^;
Rereynolds number of the cooUng water in the passage;
Dj,equivalent diameter of the cross section of the coohng passage, M ;
pthe density of water at 35 <C;
Viscosity of water at 35 <C;
The total pressure reduction of cooling water through the passage consists of 3 types
613
of pressure reductions P,, P2, P 3 c a u s e d by bend pressure, inlet and outlet,and straight
pipe pressure reduction in the cooling passage respectively.
=(xpx /2xN^
= 0.175 X 989.53 0.883' 7 2 x 2 x 1 9 x 8
= 20522.582(Pfl) (21)
,=(,-^^) 2 /2xp
= (0.5 + 0.5) X 0.883 V 2 X 989.53
= 385.763(P) (22)
^={^^)(/2) U' (23)
Here = \ (0.02/ + 6S /R^^'
= 0.11 X (0.02 7 7 + 6 8 / 10059.7)'

= 0.0344 (24)
And P3 = A X ( L y D J X (p/2) X C/'

= 0.0344 X 174.344/ (7 10 " ' ) (989.53 / 2) 0.883'
= 330512.42(i^) (25)
= 20522.582 + 385.763 + 330512.42

= 351420.77(Pz)
= 3.45fl/m (26)
Where drag coefficient caused by each bend in an individual cooling passage ;

Nptotal bend in each cooling passage. In each turn of coils there are 8 bends,
thus 2 x 1 9 x 8 bends in an individual cooling passage;
(^jdrag coefficient caused by inlet of water in the passage;
^2drag coefficient caused by outlet of water in the passage;
Adrag coefficient in the straight cooling passage.
REFERENCE
1. Comprehensive Report, Nantong coal preparation plant,Oct.,1990.

2. Kamegaya,H.etal,l 1th International Coal Preparation Congress, 1990,P287-292.
3. T.D.Wheelock and R.Markuszewski,Coal Preparation and Cleaning, In: The Science
and Technology of Coal and Coal Utilization,Plenum,New York,1984,47-123.
614
4. H.F.Yancey and J.A.Taylor.''Froth Flotation of Coal: Sulfur and Ash

Reduction'',Report of Investigation No.RI3263,U.S. Bureau of Mines(1935).
5. C.E.Raleigh and F.F.Aplan/'The Effect of Feed Particle Size and Reagents on
Coal-Mineral Matter Selectivity During the Flotation of Bituminous Coals'',SME
Annual Meeting, Salt Lake City,Preprint No.90-118(1990).
o
6. Klimpel,R.R.; Hansen,R.D. Pyrite Depressants Useful in Separation of Pyrite from
Coal. US 4830740 to Dowchemical Co. Mildland,MI(US).
The S t u d y o n t h e susceptibihties of coals,coal a n d ore pyrites and

coal m i n e r a l s
Dr. J. Z. Zheng^Dr Y.G.Tang^ Prof.M.X.Guo',Prof D.Y.Ren^
^Research Center for Eco-Environmental Sciences

Chinese Academy of Sciences
P.O.Box 2871,Beijing 100085, P.R. China
^Dept. of Geology, ^Dept.of Mineral Processing

Beijing Graduate Sohool
China University of Mining and Technology
Beijing,100083, P.R.China
ABSTRACT
In doing research work of pyrite desulfurization of high sulfur coals by

HGMS separation, mass susceptibilities of different kinds of coal pyrite
crystal forms,coals,and coal minerals are determined by VSM(vibration
sample magneometer with superconducting magnet manufactured by
Oxford Instrument Limited). The test results show that the average suscep
tibility of coal pyrite is 13 times that of ore pyrite; susceptibilities of differ
ent crystal forms of coal pyrites vary with their own crystal depositing envi
ronments. Susceptibilities of coal minerals are fathomed and coal minerals
are classified into 2 categories according to their sign of mass susceptibility.
INTRODUCTION
In China,direct combustion of coal in high sulfur coal districts has

caused heavy environmental pollution and economic loss. Shown in table 1
is the coal sulfur distribution of main high sulfur coal fields in China.
Chinaos high sulfur coals are mainly found in Sichuan,Guizhou Provines
where they were formed during the Late Permian period,and
Shannxi,Shanxi,Shandong,Hebei,and Inner Mongoha Provinces where
they were formed during the Late Carboneous period.Morever,the output
of high sulfur coal is now steadily increasing because of deep mining to
ward coal mines.
Because of the pressure on enviromental pollution China has been under-
616
taking step by step desulfurization research work. Traditionally,high sulfur

coal is processed by jigs, cyclones and shaking tables which are very effi-
cient for +0.5mm coal pyrite desulfurization. To improve the technolgy de-
velopment of - 0.5mm high sulfur coal pyrite desulfurization China Mining
University is now employing a polytechnical procedure including
flotation,HGMS, and other physical methods.
Table 1
Sulfur distribution of main high sulfur coal fields in China
Age of coal Name of coal field Average, S^^ (%)
Lepin 2.10
Nantong 3.30
Tianfu 3.17
ZhongLiangShang 2.65
Late Permian Songzao 3.35
Lindong 4.68
Heshan 7.92
Huayinshan 3,36
Wongan 4.08
Jingjing 1.37
Xuangang 1.43
Xishan 1.97
Luan 1.66
Late Carboneous Fengfeng 3.03
Zibo 3.50
Zaozhuang 2.92
Tiluo 2.98
Yongchuan 4.18
The work belongs to the subproject of one of the main projects of Coal
Ministry during the 8th five-year-plan.The project is named Fine Coal
HGMS Desulfurization.The objective of the subproject is to find the prop-
erties of the mass susceptibilities of different coal ranks,lithotypes,coal min-
erals,and coal and ore pyrites in their natural exsisting state.
l.SampIes
the 8 crystal type pyrites are carefully selected from coal mines in order
617
Figure 1. Cube crystal pyrite in clay
Figure 2. Matrix type pyrite

618
Figure 3. Snow flake type pyrite
Figure 4. Nodular type pyrite

619
to make them carry the representitiveness of coal pyrites in China. Ore

pyrites ,kaolin,quartz and other minerals are obtained from China Mineral
Research Institute. Coals and pyrite samples are collected from Nantong
No.4, No5, No6, Wuyi mine, and Hongyan mine, Sichuan Province. To
prevent oxidation samples are kept in glass bottles filled with nitrogen un
der room temperature. Fresh piece of sample is selected for VSM test after
the sample is broken by a wooden hammer. Fig. 1-4 are the photographs of
four of the eight coal pyrite crystals. The total mumber of samples tested is
50.
2.EXPERIMENTAL
2.1 Operating principles

VSM is an induction technique in which the sample is attached to the
lower end of a rigid rod and made to oscillate vertically, typically over
l-2mm. If the sample is magnetized ( either permanently or in response to
an external applied field) the oscillation will induce an AC signal in a set of
suitably placed pick-up coils. The amplitude of this signal is proportionale
to the magnetic monent of the sample. In this paper mass susceptibility is
defined as:
1 ^ 1 r e m i t .
Where the susceptibility of the sample,Cm^ / gm;

the intensity of the magnetic field applied,Oe;
m^the mass of the sample,gm;
mmagnetic moment of the sample,emu.
Table 2
VSM key features and experimental condition
Motorised sample centering S^m
Motorised rotation option 0 . 1 with cahbration facility
Horizontal magnetic field intensity 3 Tesla
Vertical magnetic field intensity ISTesla
Noise base 5xlO"êmu
Full scale ranges 0.0003 emu to 300 emu
Temperature range 4-lOOOK
Mass of samples lmg-200g
620
2.2 VSM key features and experimental condition

See table 2
3.RESULTS AND ANALYSES
3.1 Relationship between mass susceptibility of pyrites and their crystal types
As shown in table 3 the mass susceptibility of coal pyrite is determined by
its crystal type. Of the 8 crystal types, Zniax = 5.84 x 10"^CmVgm,
^ = 1.11 X 10"^CmV gm. The average susceptibility of coal pyrite is 1.58
X 10~^Cm^ / gm. The order of the mass susceptibility of coal pyrites accord
ing to their crystal forms is as following. Here the crystal forms are
macoappearance of pyrites.
Nodular type < cube-octahedral type < cube type < sand laminar
< pectinate type
< polycrystal type < snow flake type < matrix type
Table 3
The mass susceptibility of coal and ore pyrites
Origin Pyrite crystal type , C m V g m x l O ^
nodular 1.11
snow flake 30.91
Coal matrix 58.40
cube-octahedral 1.64
cybe in clay 2.63
pyrite sand laminar 8.26
pectinate 10.86
polycrystal 12.77
Ore hydrothermal 0.92*
sedimentral from Dashu 2.16
pyrite in skarn deposit from Chengmenshan 0.56*
* dynamic suxceptibility
According to the theory of Ligand Field, pure pyrite is diamagnetic min
eral, thus the explanation of pyrite^s paramagnetism can only be trace
ferromagnetic and paramagnetic minerales contamination during coal and
pyrite formation, a n d / o r partial oxidation of pyrite to F e 2 0 3 ,
621
Fe2(S04)3 and Fe 3S4 on the mineral/s surface after deposition.

The author1s study on the relationship between pyrite deposition and
trace elements indicates that trace element environment influences pyrite/s
deposition and crystal form. Since pure pyrite crystal in coal is difficult to
separate coal pyrite classification here is based on its deposited form or
macroappearane. It is found that close relationship exsits between pyrite
deposited form and its mass susceptibility.Table 4 is the analyses of trace
elements in 3 coal pyrites.
The results show that close relationship exists between the magnitude of
coal pyrite/s mass susceptibility ( table 3) and its concentration of
Ti,V,Cr,Mn,Co and Ni. The higher the concentration of trace elements in
pyrite the higher the mass susceptibility of the pyrite. Thorough explana-
tion of table 3 is diffcult. The author1s interpretation is that trace
ferromagnetic materials including Cr0 2 and magnetite containing V,to-
gether with paramagnetic mineral ilmenite and minerals containing Mn is
the cause of paramagnetism of coal pyrite.
Table 4
Neutron activation analyses of trace elements in some coal pyrites (ppm)
Ti V Cr Mn Co Ni As Sb Se Cu Zn
Nodular type / 2.04 6.04 48.3 6.3 / 38.2 0.32 32.7 47.8 19.6
matrix type 1030 67.1 31.6 1350 48.7 / 20.6 0.29 3.74 / /
snow flake type 145 3.02 8.6 405 18.9 77.9 120 0.29 4.54 67.4 /
3.2 Differences of ma~netic characteristics of coal and ore pyrites

In the experiment,3 kinds of ore pyrites are tested. They are skarn pyrite
from Chengmenshan, sedimentral pyrite from Dashu, and a hypothermal
pyrite. Fig.7-8 are the m-H curves of 2 ore pyrites.Many kinds of coal
pyrites are tested.Fig.5-6 are the m-H curves of 2 Samples representing
nodular and matrix type pyrite respectively.
As illustrated in Fig.5,6,8 the magnetic moment of sedimentral ore pyrite
and coal pyrites is proportional to the intensity of the magnetic field ap-
plied, thus the mass susceptibility is constant.The m-H curves of other ore
pyrite including hypothermal and skarn pyrites are quite different from
those of the above minerals. Their mass susceptibilities Vary with the inten-
sify of the magnetic field.
The m-H curve of skarn pyrite is quite different from those of the typical
coal pyrites which are all paramagnetic materials. From 0 to 0.6 Tesla, its
magnetic moment is approximately proportional to the field intensity. At
H = 0.6T, the curve changes quite a lot after which m-H curve becomes a
622
F i g u r e 5. m - H curve o f n o d u l a r type coal p y r i t e ,

T = 3 0 0 K , m ^ = 0.21634g
Magnetic field intensity
<

o

<
t
X)
Ca
F i g u r e 6. m - H curve o f m a t r i x coal p y r i t e , = 3 0 0 K , m ' = 0.4332()z

623
-m e
gM5-19?2113:34:28JeS2 39K
Figure 7. m - H curve of skarn ore pyrite from Chengmenshan,

T = 300K, m' = 0.30220g
-4E+4
09-15-r792!li;22:32JeS2 NO.10 308K
Figure 8. m-H curve of sedimentral ore pyrite from Dashu,

T = 300K,m' = 0.33058g
624
linean line.It is suggested that skarn pyrite contains a very small amount of
ferromagnetic substances with high mass susceptibility. Although their con
centration is very low they control the samplers mass susceptibility before
they are saturated around H = 0.6T.As shown in Fig.7, after H > 0 . 6 Tesla
m-H curve becomes:
m= mQ+ (3)
where mmagnetic moment of the sample,emu;

mosaturated magnetic moment at 0.6 tesla;
^dynamic mass susceptibility of the sample, Cm^ / gm;
m^mass of the sample,gm.
when divided by m^(3) becomes
= ^ + ^ (4)
where ^ = ^ ,magnetic moment per mass unit,emu / gm;

^ 0
= ,magnetic moment per mass unit at 0.6 Tesla,emu / gm.
And static mass susceptibility is defined as:
X , = f (5)
Thus m-H curve of skarn ore pyrite after 0.6 Tesla is expressed as
= 5.67+9.20 X 10"^H
It is calculated that the arithmatic mass susceptibility of coal pyrites is
about 13 times of that of ore pyites including sedimentral, skarn, and
hypothermal type.
XJcoalpyrite) _ 1.58 10 ~^ _
X(orepyrite) ] 21 10"' ^
3.3 M a s s susceptibilities o f coal minerals

Pure coal minerals are rare. Althouth the study here is based on pure
minerals offered by China Mineral Research Institute it is of theoretical
625
meaning for coal HGMS deashing.

As shown in table 5, coal minerals can be classified into 2 categories-part
A(X> O),and part B(X < O).Thus,when the minerals in part A are exposed
to ununiformed magnetic field they will be attracted to the magnetic
matrix, finally removed with pyrite from coal slurry; but minerals in part B
will be expelled from the magnetic matrix, resulting in unsuccessful separa-
tion of ash components from coal slurry. Although the components and
their amount may vary greatly with difference of coal resources it is found
in analysing coal mineral/s composition that main coal minerals are
kaolinite, quarts, illinite, montmorillonite, and calcite.Kaolinite,
montmorillonite and calcite can be separated with coal with a relatively
high efficiency but illinite and quartz will increase the ash content of
HGMS clean coal.
Table 5
Categories of the mass susceptibility of coal minerals
Part A X>O PartB x<O
Sample x,Cm 3 /gm x 10 6 Sample
Kaolinite 0.33 Illinite -1.34
Bauxite 0.43 Kaolin -0.35
Calcite 0.67 Gypsum -3.24
No.7 claY,Hongyan 0.38 Anhydrite -2.39
Mica 4.05 Quartz -2.81
Montmorillonite 2.40 Orthoclase -2.64
Glauconite 6.16 Graphite -21.30
Dolomite 15.53
3. 4 The relationship between coal ranks, lithotypes, and their susceptibilities

in Sichuan Province, China
Coal ranks have great influence on the mass susceptibility of coal. Ac-
cording to the analyses of Sichuan coallisted in table 6, X( anthracite) > 0 ,
x(bituminous) <0, Thus theoreticallY,HGMS can/t be used to desulfurate
coal in case of Muchuan anthracite because of the low separation
efficience.Of the 3 lithotypes of Nantong bituminous coal tested difference
is limited. It is suggested that susceptibilities of different lithotypes of the
same coal rank in a designated coal mine are in the same order of magni-
tude.
626
Table 6
Relationship between mass susceptibility and coal ranks and lithotypes
Lithotype Coal rank Cm^3 // gm x 10^
Mass susceptibility, Cm 10 7
Vitrain,Nantong
Vitrain,Nantong -2.46
Clarain,Nantong bituminous
Clarain,Nantong bituminous -1.74
-1.74
Durain,Nantong coal
Durain,Nantong -2.60
Clarain,Wuyi
Clarain,Wuyi -3.05
-3.05
Durain,Muchuan
Durain,Muchuan -4.21
Vitrain,Songzao anthracite
Vitrain,Songzao 13.2
Fusain,Muchuan
Fusain,Muchuan 34.3
According to Huckel
Hckel Molecular Orbit Theory pure coal is diamagnetic
author^s interpretation of
fossil.The author1s of the paramagnetism of
of Muchuan an-
thracite is that it was also caused by the contamination of
of paramagnetic
minerals during its formation. Analyses of of Nantong and Songzao coal is
listed
hsted in table 7.
Table 7
Analyses of
of Nantong and Songzao coal
rank
Coal rank Vdaf
Vâf C daf
C^.f Hâf (O+S)daf
(0+S),r N daf
^.r
Nantong No.5 bituminous
Nantong bituminous 22.95 87.51 4.79 6.39 1.31
1.31
Sonzao M6-1
Sonzao M 6 - 1 anthracite
anthracite 11.43-8.28
11.43-8.28 91.29-89.29
91.29-89.29 3.95-3.70
3.95-3.70 5.48-3.57
5.48-3.57 1.60-1.33
1.60-1.33
** daf for dry ash free
4. CONCLUSIONS
CONCLUSIONS
(1) 8 kinds ofof coal pyrites are tested and their mass susceptibilities are illus-
trated in table 3.
(2) Coal pyrites are paramagnetic minerals, and their average mass suscep-
tibility is about 13 times of
of that of
of ore pyrites.
(3) Coal minerals can be classified into 2 different
different categories according to
the sign ofof their mass slsceptibility.TheoreticallY,it
slsceptibility.Theoretically,it is deduced that min-
erals in part A will be separated more successfully
successfully than those in part B
which tend to be repelled from the matrix during HGMS separation.
(4) According to the analyses of of some Sichuan high sulfur coals, it is
found: x(bituminous)<o,x(amthracite)
X(bituminous) < o,x(amthracite) > 0 . The anthracite here is ex ex-
efficiency
pected to have low separation efficiency because of
of pulling force acting
on it from the magnetic matrix during HGMS separation.
627
5.ACKNOWLEDGMENTS
The authors express thanks to superconduct laboratory of Institute of

Physics,Chinese Academy of sciences for the help in the research work of
mass Susceptibility by VSM .Thanks also to the engineers in Sichuan coal
mines for their help in collecting the samples. We also wish to acknowledge
Miss X.Y.Qu who types the paper and Coal Ministry from which the re
search work is funded.
M A I N REFERENCES
1. S. Ergun and E. H. Bean,U.S. Dept. of the Interior, Bureau of Mines,

Report of Investigation 7181(September,1968).
2. P. Burgardt and M. S. Seerha,Solid State Communications 22,pp.
153-156(1977).
3. G. P. Huffman and F. E. Huggins, Fuel 57,592-604(1978).
4. R. R. Oder and R. J. Gray, ''Dry Magnetic Separation of Coal,'' Proc.
Interational Conference on Coal Science,Tokyo,Japan (October 2 3 - 27,
1989) pp. 995-998.
5. S. C. Trindade, J. B. Howard, H. H. Kolm, and G. J. Powers, Fuel 53, P.
178 (1974).
6. John A. Tossell, David J. Vaughan, Theoretical Geochemistry: Applica
tion of Qantum Mechanics in the Earth and Mineral Sciences, Oxford
University Press, 1992.
7. J. Z. Zheng, Ph.D dissertation: Fine Coal Desulfurization, P.36-41,
April, 1993.
629
AUTHOR INDEX
A h m e d , M.S. 3 7 9 F i n s e t h , D. 9 1
Akhtar, S.S. 283, 3 4 5 F u n g , A. 2 6 3
A m i c k , P. 5 1 1
A p i a n , F.F. 7 1 , 1 1 9
A m o l d , B. 1 6 1 . 1 8 9
Attia, Y.A. 2 6 3 , 3 7 9 , 4 6 7
G h i a n i , M. 5 5 5
G o d f r e y , R.L. 2 5 1
G u o , M.X. 6 0 3 , 6 1 5
G u o , Q. 5 6 5
B a b u , M. 4 8 5
B a n e r j e e , D.D. 149
B o l l i , R.E. 4 3 7
Borio, D.C. 4 5 1
Booras, G.S. 361 H a c k l e y , K.C. 15
Bortollussi, A. 5 5 5 H e r b s t e r , R.E. 5 1 1
H o g g , R. 1 6 1 , 1 8 9
H u f f m a n , G.P. 1
H u g g i n s , F.E. 1
Humphrey, A.E. 331
Cao, J. 15
C a r b i n i , P. 5 5 5
C h a n d e r , S. 1 6 1 , 1 8 9
C h a t t e r j e e , K. 2 9 1
C h e n , S.F. 3 1 7 Jia, G.R. 603
C h o , H. 2 3 7 Jiajin, Lei 2 7
Chou, C.L 15 J i a n g , C. 171
C h o u d h r y , V. 1 4 9 J o h n s o n , H. 4 8 5
Chriswell, C D . 283
C i c c u , R. 5 5 5
Clark, T.R. 3 2 5
C l i f f e , K.R. 2 9 7
Collings, M.E. 4 1 9 K a w a t r a , S.K. 139
C o r f m a n , D.W. 437 Khan, L 149
K i l l m e y e r , R. 2 3 7
Kingston, W.H. 451
Krawiec, S. 3 3 1
K g k b a y r a k , S. 5 8 7
D e y i , R. 2 7 , 3 7
Drenker, S.G. 361
D u b y , P.F. 4 7
L a n i , B. 4 8 5
Leonard, J.W. 171
L i u , D. 4 7
Eisele, T.C. 139 Long, W.H. 403
E l s t r o d t , R. 9 1 L u , F. 1
L u o , S. 5 5
Luttrell, G.H. 2 1 9
630
Stencel, J.M. 393

Strevel, S.D. 519
Stock, L M . 291
M a d d e n , D.K. 437 S y e d , M.M. 297
M a n n , M.D. 419
M c C l e l l a n d , J.F. 5 5
M c K i n s e y , R.R. 3 6 1
Meffe, S. 9 9
Mericboyu, A.E. 587 T a n g , Y. 3 7 , 5 7 9
M e y e r s , R.A. 305 Tang, Y.G. 615
T a o , D.P. 219
T o r e k , . 5 9 3
Trass, O. 9 9
N e a t h e r y , J.K. 3 9 3
Nelson, S.G. 543
N e w b y , . 91
N o w a k , M.A. 305 V a n B e m m e l , W.R. 207
Olson, G.J. 3 2 3 W a n g , P. 3 3 1
W a n g , X.H. 171, 565
Wen, W.W. 237
Wheeldon, J.M. 361
W h e e l o c k , T.D. 55, 2 0 7
P a r e k h , B.K. 1 7 1 , 5 6 5 W o o d s , M.C. 437
P e r k s o n , A. 9 9
Polat, M. 1 6 1 , 1 8 9
Q Y a n g , D. 1 4 9
Yang, J. 393
Q u , H.Q. 603 Y a n g , J.K. 3 1 7
Y o o n , R.H. 2 1 9
Y o u n g , B.c. 419
Raleigh, C.E. 71
R e n , D.Y. 615
R e y , P.A. 119 Z e n g . M. 603
R i c h a r d s o n , P.E. 2 1 9 Zhao. J. 1
Z h e n g , J.Z. 603. 615
Z h o u . R. 1 6 1 . 1 8 9
Z u p a n , D. 5 1 1
S c h a e f e r , J.L. 3 9 3
Schlorholtz, S.M. 345
Seth, A.G. 519
S h a h , N. 1
Shao, Xuxin 579
Somasundaran, P. 4 7
631
SUBJECT INDEX
anion e x c h a n g e resin 519 flocculation 119

asphalt emulsion 241 float-sink 2 8 4
flotability, pyrite 171
flotation 237
fracture 565
bacteria 139 flotation kinetics 161
base desulfurization 293 fluidized b e d c o m b u s t i o n 345, 419
biodepyritization 323 fly a s h 3 4 6
bituminous coals 71
blackwater 119
gasification 118
geochemical 27
cake hardening 237 grain-boundary 565
calcination 542
calcium based sorbents 386
cascading bed combustion 403
carbon dioxide 467 heavy liquid separation 267
carefree coal 252 high gradient magnetic separator 603
caustic leaching 283 hydrothermal treatment 283
chemical desulfurization 263
chemical oxidation 274 I
coal flotation 237
coal grinding 554, 565 induction time 47
coal pyrite 180, 219, 579 i n d u c e d flotability 171
c o l u m n flotation 149
cyclic voltammetry 505
limestone 587
low-rank coals 419
Destec process 511 low temperature oxidation 393
dewatering 239, 494
dibenzothiophane 331
dibenzosulfone 331
d i s p e r s a n t - d e p r e s s a n t s y s t e m s 71 magnetohydrodynamics 519
dolomite 587 magsorbent process 545
dty-scrubbing coal 257 methanol 99
dust index 240 microbial desulfurization 331
dust reduction efficiency 2 4 0 microwave irradiation 3 1 7
microorganism 139
mild temperature gasification 393
mineral pyrite 219
molten caustic leaching 305
electrochemical 47, 219
electrostatic s e p a r a t i o n 91
elemental sulfur 543
ESCA studies 579
632
sulfur release profile 15

sulfur speciation 1
nitric o x i d e 4 1 9 surface reaction 23
nitrogen dioxide 419 s u s c e p t i b i l i t i e s of c o a l s 6 1 5
nitrous oxide 419 swelling 565
437, 467
NOXSO process 437
t e m p e r a t u r e p r o g r a m m e d pyrolysis 15
thermogravimetric 588
Ohio coal testing 593 thiobacillus ferrooxidans 139, 3 2 3
organic desulfurization 291 thioclear process 500
organosulfur coal 27 thioglycolic acid 55
orimulsion 239 thio process 503
oxidants 297 thiosorbic lime 4 8 5
triboelectric c h a r g i n g 91
two stage leaching 321
packed column 149 U

perchloro ethylene 5
petrological 27 Upper Freeport s e a m coal 75
phosphoric acid 393 Upper Permian coal 27
polyethylene oxide 207
potassium permanganate oxidation 263, 298
pressurized fluidized b e d 361
pyrolysis 15 varsol 302
voltammetry 23, 505
W
q u a d r u p o l e g a s analyzer (QGA) 15
water stream treatment 149
R w a t e r jet g r i n d i n g 5 5 5
wet scrubbing 487
reconstitution 282
resids 1
rhodococcus rhodochrous 5
rubber 1 XAFS 1
XANES 1
xanthate flotation 180
saccharomyces cerevisiae 139

selective catalytic r e d u c t i o n (SCR) 451
selective flocculation 207
self-scrubbing coal 255
SEMISTM 37
single electron transfer 292
sink-float analysis 189
SNOX (de-SOx/de-) process 451
sol-gel 467
solution electrode potential 47
sorbents 379
sorbent, aerogel 467
sorbent, dry 468
sulfur c a p t u r e 3 7 9

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COAL SCIENCE AND TECHNOLOGY

Vol. 1: Geochemistry of Coal (Bouska)

B.K. PAREKH and J.G. GROPPO

ELSEVIER, Amsterdam London ^ New York Tokyo 1993

1993 Elsevier Science Publishers B.V. All rights reserved.

This book is printed on acid-free paper.

Printed in The Netherlands

T H E FIFTH INTERNATIONAL CONFERENCE

O N PROCESSING A N D UTILIZATION OF HIGH-SULFUR C O A L S ,

Center for A p p l i e d Energy Research

T H E FIFTH INTERNATIONAL CONFERENCE

ORGANIZING AND ADVISORY COMMITTEE

Dr. Y o s r y A . A t t i a Clark Harrison

Prof. R a i m o n d o C i c c u Mel Laurila

Dr. P.R. D u g a n Dr. R. M a r k u s z e w s k i

regulations being imposed around the world. T o m e e t t h e c h a l l e n g e of utilizing h i g h sulfur c o a l s

a b o u t five billion d o l l a r s in s u p p o r t of d e v e l o p i n g t e c h n o l o g i e s t h a t will allow s a f e u s a g e of h i g h sulfur

with papers o n physical a n d chemical cleaning as well as post-treatment a n d fluid-bed c o m b u s t i o n

technologies. Of t h e 4 5 p a p e r s submitted, 15 p a p e r s deal with physical cleaning a n d s e v e n with

Finally, w e w i s h t o e x p r e s s o u r g r a t i t u d e t o t h e a u t h o r s a n d t h e r e v i e w e r s for p r o v i d i n g their

Further sulfur speciation studies by sulfur K-edge XANES

G.P. Huffman, N. Shah, F.E. Muggins, F. Lu, and J. Zhao

University of Kentucky, Lexington, KY 40506-0107

Sulfur K-edge XANES spectroscopy has been shown to be an excellent

The experimental XAFS spectroscopy procedures have been discussed in detail

RESULTS AND DISCUSSION

Inorganic Elemental Organic Thiophenic

BASE-treated coal 18 - unk. 0 13 49 7 8 5

SET, then BASE 21 - unk. 0 24 21 11 13 10

BASE, then SET 0 9 26 36 7 9 13

. .. 111111 77:: t i ; *. llt^i:ttifn*/J*0^sm^m^.

Biologically Desulfurized Samples: Previously, we have used XANES to

Coals Subjected to Molten Caustic Leaching: A molten caustic leaching

Treatment with perchloroethylene(PCE):The forms-of-sulfur present in a

Figure 2. Percentages of organic functional forms of sulfur in control and biotreated

Figure 3. KY # 9 coal cleaned by gravimelt process.

Pittsburgh # 8 Gravimelt Pgh # 8 Gravimelt KY # 9

Sulfur speciation in coal liquefaction resids

Comparison of sulfur K-edae and L-edge results

Sulfur form percentage

0 = below detection limit, approximately 5% for oxidized sulfur forms.

Figure 5. Least-squares fitted sulfur K-edge XANES spectrum of Mequinenza Lignite

Sulfur Form % of Total Sulfur Wt% S in Lianite^

Pyritic Sulfur nd (<0.5)

^ Based on 10.0 wt% (dry) non-pyritic sulfur in lignite, nd - Not determined

Sulfur speciation in other types of materials

SUMMARY AND CONCLUSIONS

This research was supported by the Office of Exploratory Research of the

1. George, G.N.; Gorbaty, M.L JAm.Chem.Soc. 1989, 111, 3182.

11. Kilbane, J.J.; Proceedings: 1991 Second International Symposium on the

Release of organic, pyritic, elemental, and sulfate sulfur during

C.-C Chou, ICC. Hackley and J. Cao

Sulfur release profiles (variation of sulfur dioxide in pyrolysis/combustion gases with

2.2. Determination of forms of sulfur

2 3 . Temperature-programmed pyrolysis-gas combustion technique

3. RESULTS OF PYROLYSIS-GAS COMBUSON EXPERIMENTS

3.1. Replicate determinations of sulfur evolution

100 200 300 400 500 600 700 800

3.2. Pyrolysis of fresh samples of coal IBC-109

33. Weathered coal samples

3.4. Pyrolysis of mixtures of coal plus elemental sulfur

Sample Sulfate Elemental S Pyritic S Organic S Sum Total S*

Sample % total sulfur % total sulfur % char

. .. 111111 77:: t i ; . llt^i:ttifn/J*0^sm^m^.