Oxygen elimination

in the process of
non-catalytic
liquefaction
of brown coal
Jan Surygala,

Robert

Wandas

and Ewa Sliwka

Institute of Chemistry and Technology of Petroleum and Coal, Technical

Wroclaw, Gdariska 719, 50-344
Wroclaw, Poland
(Received 21 November
1997; revised 1 May 1992)

University

of

The effects of process temperature, pressure and reaction time on brown coal conversion rate and
accompanying degree and form of oxygen elimination were evaluated in a series of autoclave runs. The
degree of total oxygen elimination
faiours formation of H,O.

depends

mainly

on the process

temperature.

Increase

of temperature

(Keywords: liquefaction; brown coal; hydrogenation)

According to Curran the mechanism

of hydrogenating
depolymerization
of coal consists of: the thermolysis
of
C-O and C-C bonds into radical fragments
C+2R*
and successive reaction of hydrogen abstraction from

hydrogen donor solvent to the radicals, R* + T-+RH + T*.

The problems of bond thermolysis and resonance energy
for radical stabilization have been the subject of several
investigations 2m5 These found phenols, ethers, quinones
and other oxygen-containing compounds as the main
radical generating substances. Their presence in the
reaction medium initiates the sequence of radical
reactions leading to the low energetic brown coal
conversion. The occurrence of large amounts of various
oxygen groups6 makes the liquefaction of brown coal
possible under relatively mild conditions. H,O, CO and
CO, are the by-products of brown coal processing. It
has been established that the brown coal conversion rate
and the yield of oil components depend on the degree of
oxygen elimination.
In this work, an evaluation has been made of the effects
of process temperature, pressure and reaction time on
brown coal conversion rate and the accompanying degree
and form of oxygen elimination.

mixing. The description

of the methods used has been
given previously. Several series of runs were carried out
to determine the effect of process conditions; temperature
(200_45OC), pressure (4-31 MPa) and reaction time
(G-120 min) on the coal conversion and degree of oxygen
elimination.
The products were analysed for CO, CO,, C,-C,
hydrocarbons (by gas chromatography), H,O (by reflexive
azeotropic distillation), oil components and residual coal
(by selective solvent extraction).
Process efficiency was evaluated on the basis of coal
conversion to tetrahydrofuran
(THF) solubles and
components soluble in cyclohexane. The degree of oxygen
elimination was calculated from CO, CO2 and H,O
yields.

RESULTS

Total coal conversion (to THF solubles) varied in the

range of temperature tested from 2.4 to 96 wt%, while
the conversion to oil components (soluble in cyclohexane)

Table 1

EXPERIMENTAL

Characteristics

of raw material

Characteristics

Based on the results of earlier investigations7,8, brown

coal from Tur6w strip mine was selected for this
investigation (Table 1).
The heavier fraction (285-440C) of hydrogenated
anthracene oil was used as slurry oil. The sample
contained 8.3 wt% hydrogen, 0.5 wt% nitrogen, and 0.3
wt% oxygen. Its aromaticity index,f,, was 0.65 while the
average molecular weight, A, was 228.
Slurry containing 33 wt% (daf) coal was subjected to
hydrogenation.
Runs were carried out in a batch
autoclave of 200 ml capacity equipped with shaking-type
Presented at International
Conference
on Structure
and Properties
of Coals, 17-19 June 1991, Technical University of Wroclaw, Wroclaw,
Poland

001~2361/93/030409-03
ds 1993 Butterworth-Heinemann

AND DISCUSSION

Ltd.

Value

Ash (wt%)
Moisture (wt%)
Elemental analysis (wt% daf)
C
H
N
S
0 (by diff.)
Group composition
(wt% daf)
Bitumens
Humic acids (total)
Residue
Petrographic
composition
(~01%)
Huminite
Lyptinite (resinite)
Inertinite
Mineral matter

8.2
1.8
71.6
6.1
0.9
1.0
20.4
3.4
16.9
19.7
84.2
10.4 (9.2)
0.8
4.6
_

FUEL,

1993,

Vol 72, March

409

Oxygen elimination in liquefaction of brown coal: J. SurygaIa et al.

Table 2

Coal conversion

and degree of oxygen

elimination

Process
conditions

under different

conditions

Conversion
(wt%)

elimination
(wt%)

&Pa)

Time
(min)

200

23.0

60

2.4

1.3

4.7

0.0

4.7

240

23.0

60

5.7

2.5

9.1

0.0

7.1

2.2

280

23.0

60

14.7

4.6

16.9

0.0

12.5

4.4

310

23.0

60

30.7

5.3

19.6

0.2

15.0

4.4

340

23.0

60

57.1

29.9

32.2

0.9

23.0

8.3

370

23.0

60

75.8

41.4

48.1

1.1

24.0

23.5

400

23.0

60

92.5

54.0

57.9

2.6

22.5

32.8

430

23.0

60

95.8

66.6

71.3

4.6

21.6

45.1

450

23.0

60

96.4

76.0

76.9

5.9

18.1

52.9

430

4.3

60

78.5

46.5

63.7

1.5

22.5

39.7

430

10.7

60

91.6

59.5

69.1

3.9

23.5

41.7

430

31.0

60

95.9

73.6

70.4

5.7

21.1

43.6

430

23.0

92.6

44.6

48.8

2.7

21.6

24.5

430

23.0

30

96.2

52.8

72.6

4.0

22.5

46. I

430

23.0

120

96.8

70.2

70.4

5.2

19.6

45.6

200

240

280

THF
solubles

Oxygen

320

360

400

Cyclohexane
solubles

440

Temperature ("C)

Figure 1 Product yield as a function of liquefaction

temperature
(23 MPa, 60 min): A, oils (by diff.); n , asphaltene/preasphaltene;
v,
residue; A, hydrocarbon
gases; 0, CO; 0, CO,; x , H,O

changed from 1.3 to 76 wt% (Table 2). Taking into

account
the optimum
of total oil production
(oil
fraction + asphaltene/preasphaltene
fraction),
the data
showed that the maximum
of liquid product
yield
occurred at 400C (Figure 1). Above this temperature,
thermal cracking of primary products caused a decline
in the yield of the asphaltene/preasphaltene
fraction while
a corresponding
increase
in the yields of oil and
hydrocarbon
gas fractions was observed.
Some oxygen was evolved as CO, even at 200C (1.3
wt% daf coal basis) implying that the compounds
with
structures such as resorcinol2-carboxylic
acids might be
anticipated
in Turow
brown
coal. Decarboxylation
temperatures
of such compounds
are known
to be
below 200C. The probable source of a larger quantity
of CO, is the thermal decarboxylation
of carboxylic acid
groups in the coal, since these have been found*12 to
commence decomposition
at about 250C. The maximum
yield reached in this study of CO,, 4.7 wt% of the daf

410

FUEL,

1993,

Vol 72, March

Total

as CO

as CO,

as H,O
0.0

coal (23.5% of the oxygen in the daf coal), was lower

at 370C than that reported
for Hat Creek coal13.
Occurrence
of the CO, yield maximum may be due to
the equilibrium
reaction established between CO,, H,O,
CO and H, in the system l2 . Support for this comes from
the reduction
in CO, content above 370C which is
accompanied
by occurrence of CO and a rise in the level
of H,O (Figure I).
It is possible that some CO may be formed by thermal
disruption of carbonyl functional group compounds such
as cc-substituted ketones and aldehydes.
In the lower temperature
range (24&34OC), a small
amount of oxygen was eliminated
in the form of H,O
(0.5-2 wt% of the daf coal), probably
as a result of
dehydration
of the phenolic
hydroxyl
groups which
occurs14 at temperatures
above 300C. In the higher
temperature
range, water production
may result from
scission of dialkyl ethers and also by the intermolecular
condensation
of dihydric phenols3. In this study, the yield
of water increased continuously
to about 10.8 wt% of
the daf coal with increase in temperature
to 450C.
In the lower temperature
range, the process efficiency
was not high (Table 2) and this would suggest that CO,
was formed mainly from solid coal before or during
liquefaction.
Some H,O
was emitted
at the lower
temperatures
from undissolved
coal, but much more
H,O
came from further
hydrodepolymerization
of
primary liquid products. Similar observations
have been
reported previously.
The degree of total oxygen elimination
increased from
5 wt% at 200C to 77 wt% of the oxygen in the daf coal
at 450C. In the higher temperature
range (>37OC),
oxygen was eliminated mainly in the form of H,O.
From the point of view of process efficiency and
hydrogen consumption,
it would be preferable to remove
oxygen as CO, rather than H,O, but the content of
asphaltene/preasphaltene
fraction in the liquid product
would then be much higherr6.
Total brown coal conversion at 430C changed in the
pressure range tested from 79 to 96 wt%, while the

Oxygen

elimination

conversion to oil components

altered from 46 to 74 wt%
(Table 2).
The amount of oxygen emitted in the form of CO, was
half that removed in the form of H,O. However, these
amounts varied little, so that the degree of total oxygen
elimination
did not depend on pressure.
The Turow brown coal used in this study is highly
reactive (Table I); a high degree of conversion ( - 93 wt Oh)
to THF solubles takes place as early as the preheating
period. A further 30 min residence time at 430C brings
about 96 wt% conversion
with no further conversion
during the next 90 min of reaction time (Table 2). A total
of 0.5-l wt% oxygen (daf coal basis) was eliminated in
the form of CO. No significant changes in the amount
of oxygen removed in the form of CO, were found. The
quantity of the oxygen eliminated
in the form of H,O
increased during the first 30 min of the reaction time and
it then remained at the same level (Table 2).
The chemical analysis of oil, asphaltene/preasphaltene
and residual fractions separated
from 430C product
showed 3.2,9.3 and 33.3 wt% of oxygen in these fractions,
respectively.
At 430C 72 wt% of the oxygen present in the parent
coal was eliminated, 46 wt% in the form of H,O, 22 wt%
as CO, and 4 wt% as CO. A total of 28 wt% oxygen
remained
in the liquid products
and in the residue
with 7 wt% in the oil fraction,
13 wt% in the
asphaltene/preasphaltene
fraction and about 8 wt% in
the residual fraction.

of brown

coal: J. Surygah

et al.

Sciences in Gliwice,
through
the Central
Research
Programme
on Structure,
Reactivity
and Conversion
Methods of Coal (No. 01.16).

REFERENCES
1
2
3
4
5
6

8
9
IO
11
12
13
14
15
16

ACKNOWLEDGEMENT
17

The authors acknowledge

the financial support of the
Institute of Coal Chemistry
of the Polish Academy of

in liquefaction

Curran, G. P., Struck, R. T. and Gorin, E. Am. Chem. Sot. Dir.

Fue[ Chem. 1966, 10 (2) 130
Shinn, J. H. Fuel 1984, 63, 1187
Benjamin, B. M., Raaen, V. F., Maupin, R. H. and Brown, L. L.
Furl 1978, 57, 269
Schlosberg,
R. H., Szajowski,
P. J.. Dupie, G. D. and
Danih, J. A. Fuel 1983, 62, 690
King, H. H. and Stock, L. M. Fuel 1984, 63, 810
Martyniuk,
H. and Tomkbw,
K. Ugrupowania
tlenowe w
weglach brunatnych:
Pr. Nauk. Inst. Technol. Nafty P. Wr.. no.
40, Wroctaw, 1981 (in Polish)
Surygala.
J. and Wandas.
R. Proceedings
of Sixth Annual
International Pittsburgh Coal Conference. University of Pittsburgh,
Pittsburgh,
1989, Vol. 2, pp. 689-697
Surygala, J. and Wandas, R. Chem. Stos. 1986, 30, 327
Wandas, R. and Surygala, J. Chem. Stos. 1988, 32, 409
Roberts, J. D. and Caserio, M. C. Basic Principles of Organic
Chemistry, Benjamin, New York, 1965
Murray, J. B. and Evans, D. G. Fuel 1972, 51, 290
Charlesworth,
J. M. Fuel 1980, 59, 859
Kimber. G. M.. Panic. M. M. and Hvdro. B. C. CIM Bulletin
1985, 78 (880) 60
Ouchi, K. and Honda, H. Fuel 1959,38. 429
Surygala, J. Koks Smola Gaz 1988, 33, 68
Ouchi, K., Shiraishi, K., Itoh, H. and Makabe, M. Fuel 1981.
60, 471
Surygala, J. and Wandas, R. Uwodornienie
wegla brunatnego
do syntetycznej ropy weglowej, Report SPR no. 353, Wroclaw.
1985 (in Polish)

FUEL, 1993, Vol 72, March

411