Dechlorination of Ferric Chloride With Oxygen

A.W.

HENDERSON,

T. T. CAMPBELL,

AND

F. E. BLOCK

B e c a u s e of i n c r e a s i n g e c o l o g i c a l c o n c e r n , the B u r e a u of Mines is i n v e s t i g a t i n g the use of

c h l o r i n a t i o n technology in e x t r a c t i v e m e t a l l u r g y . A key p r o b l e m is the fact that f e r r i c
chloride i s c o m m o n l y g e n e r a t e d d u r i n g p r o c e s s i n g of a wide v a r i e t y of o r e s and m i n e r a l s .
T h i s p a p e r d e s c r i b e s s m a l l l a b o r a t o r y - s c a l e s t u d i e s d e s i g n e d to effect d e c h l o r i n a t i o n of
f e r r i c chloride by oxygen in a fluidized bed r e a c t o r to p r o d u c e a v i a b l e , n o n p o l l u t i n g i r o n
oxide p r o d u c t and c h l o r i n e gas, which could be r e c y c l e d in a c h l o r i n a t i o n p r o c e s s . T h e s e
s t u d i e s d e m o n s t r a t e d that c l o s e to 100 pct c o n v e r s i o n s of f e r r i c c h l o r i d e to f e r r i c oxide
and c h l o r i n e can be effected by r e a c t i o n with oxygen at t e m p e r a t u r e s r a n g i n g f r o m 500 ~ to
650~
The off-gas f r o m the s i n g l e - s t a g e r e a c t o r contained up to 95 pct c h l o r i n e . The
study a l s o d e m o n s t r a t e d that the p r e s e n c e of a s m a l l a m o u n t of NaC1 in the r e a c t o r c a t a lyzed the r e a c t i o n between f e r r i c c h l o r i d e and oxygen and p e r m i t t e d high c o n v e r s i o n s at
t e m p e r a t u r e s a s low as 500~

BECAUSEof pending w o r l d - w i d e

s h o r t a g e s of r u t i l e ,
t h e r e has been i n t e n s i f i e d i n t e r e s t in m e t h o d s of u t i l i z i n g i l m e n i t e as a s o u r c e of t i t a n i a e i t h e r for p i g m e n t
or for m e t a l p r o d u c t i o n . Although i l m e n i t e can be
t r e a t e d by s u l f u r i c acid attack, u n d e s i r a b l e q u a n t i t i e s
of f e r r o u s sulfate a r e g e n e r a t e d that c o n s t i t u t e a w a t e r
pollution p r o b l e m . Other a p p r o a c h e s being studied i n clude p y r o m e t a l l u r g i c a l p r a c t i c e s to p r o d u c e hight i t a n i a s l a g s , synthetic r u t i l e , or t i t a n i u m c a r b i d e . 1
T h e s e u p g r a d e d m a t e r i a l s can be c h l o r i n a t e d to p r o duce t i t a n i u m t e t r a c h l o r i d e and a s m a l l a m o u n t of i r o n
c h l o r i d e , which i s r e a d i l y r e m o v e d by f r a c t i o n a l cond e n s a t i o n and d i s t i l l a t i o n . After final p u r i f i c a t i o n the
r e s u l t i n g t i t a n i u m t e t r a c h l o r i d e can be u s e d for m e t a l
p r o d u e t i o n or c o n v e r t e d to p i g m e n t - g r a d e TiO2.
An a l t e r n a t e a p p r o a c h for r e e o v e r i n g t i t a n i a f r o m
i l m e n i t e i n v o l v e s d i r e c t c h l o r i n a t i o n ; however, in this
e a s e , e x c e s s i v e q u a n t i t i e s of f e r r o u s or f e r r i c c h l o r i d e
a r e g e n e r a t e d which constitute a l o s s of c h l o r i n e and
pose a s e r i o u s pollution p r o b l e m . The a p p l i c a t i o n of
c h l o r i n e in m e t a l l u r g i c a l p r o c e s s i n g is s e r i o u s l y h a m p e r e d from both an e c o n o m i c and an ecological s t a n d point by the g e n e r a t i o n of i r o n c h l o r i d e s .
Although we have e m p h a s i z e d the g e n e r a t i o n of f e r r i c
c h l o r i d e d u r i n g i l m e n i t e p r o c e s s i n g , it should be r e c o g n i z e d that the u s e of c h l o r i n a t i o n p r a c t i c e in p r o c e s s i n g
a wide v a r i e t y of o r e s and c o n c e n t r a t e s depends upon
the s u c c e s s f u l development of a method for d e c h l o r i n ating f e r r i c chloride. A c c o r d i n g l y , this study was u n d e r t a k e n to develop a n e c o n o m i c a l method for d e c h l o r i n a t i n g f e r r i c chloride to p r o d u c e a nonpolluting i r o n
oxide product and c h l o r i n e for r e c y c l e .
In g e n e r a l , t h e r e i s only l i m i t e d i n f o r m a t i o n in the
l i t e r a t u r e dealing with d e c h l o r i n a t i o n of f e r r i c c h l o r i d e .
The i n f o r m a t i o n that is a v a i l a b l e is m o s t l y r e s t r i c t e d
to p a t e n t s , which d i s c l o s e the d i s p l a c e m e n t of c h l o r i n e
by oxygen. T h e s e p a t e n t a b l e d i s c l o s u r e s differ p r i m a r i l y in the method used to i n t r o d u c e f e r r i c c h l o r i d e
A. W. HENDERSON and T. T. CAMPBELLare Metallurgistand
Supervisory Chemical Research Engineer, respectively, Albany
Metallurgy Research Center, Bureau of Mines, U. S. Department of
the Interior, Albany, Or. 97321. F. E. BLOCK is Research Director,
Reno MetallurgyResearch Center, Bureau of Mines, U. S. Department of Interior, Reno, Nev.
Manuscript submitted March 7, 1972.
METALLURGICALTRANSACTIONS

into a r e a c t o r for c o m b u s t i o n with oxygen a c c o r d i n g to

the following equation:
3

2 FeC13 + -~O2 = FeeO3 + 3 C12

The p a t e n t s i n d i c a t e that the above r e a c t i o n o c c u r s
at t e m p e r a t u r e s r a n g i n g f r o m 500 ~ to 1000~
Dunn2
d e s c r i b e s the u s e of a s o d i u m c h l o r i d e - i r o n chloride
eutectic s a l t in a m o v i n g bed r e a c t o r . The e u t e c t i c s a l t
is d i s p e r s e d a s a liquid film on i n e r t s p h e r e s (alumina)
which a r e i n t r o d u c e d at the top of a v e r t i c a l r e a c t o r .
The coated s p h e r e s move downward through the r e a c t o r
c o u n t e r c u r r e n t to a flow of oxygen. As the coated
s p h e r e s move downward, i r o n oxide and C12 a r e p r o duced. Another method r e p o r t e d i n v o l v e s the d i r e c t
c o m b u s t i o n of f e r r i c chloride vapor with oxygen. 3 C a r bon or c a r b o n monoxide was i n t r o d u c e d n e a r the outlet
of the r e a c t o r to i n a c t i v a t e oxygen. This i n a c t i v a t i o n
p r o c e d u r e i s r e p o r t e d to p r e v e n t a c r u s t of i r o n oxide
f o r m i n g which would o t h e r w i s e c a u s e plugs. The u s e of
a f l u i d i z e d - b e d r e a c t o r was also r e p o r t e d . 4'5 P a r t i c l e s
of i r o n oxide a r e m a i n t a i n e d in a state of fluidization to
provide a l a r g e n u m b e r of s u r f a c e s for f e r r i c c h l o r i d e
vapor to r e a c t with oxygen. The fluidized p a r t i c l e s of
i r o n oxide a r e r e p o r t e d to catalyze the f o r m a t i o n of
i r o n oxide and c h l o r i n e .
After a p r e l i m i n a r y i n v e s t i g a t i o n of these p a t e n t a b l e
d i s c l o s u r e s , the c o m b u s t i o n of FeCls in a fluidized b e d
of iron oxide was chosen for m o r e e x t e n s i v e study.
A t t r a c t i v e f e a t u r e s of a fluidization p r o c e s s include
e x c e l l e n t heat t r a n s f e r , high throughput, good control
of p r o c e s s s t r e a m s , and continuous o p e r a t i o n .
P r e l i m i n a r y s t u d i e s on the d e c h l o r i n a t i o n of FeC13
quickly i n d i c a t e d that a c r i t i c a l feeding p r o b l e m is a s s o c i a t e d with the p h y s i c a l and c h e m i c a l c h a r a c t e r i s t i c s
of this compound and its r e a c t i o n p r o d u c t s with oxygen. At t e m p e r a t u r e s r a n g i n g f r o m 100 ~ to about 320~
stable compounds including Fe203, FeC12, and FeOC1
f o r m on the FeC13 feed inlet l i n e s leading into the
f l u i d i z e d - b e d r e a c t o r , c a u s i n g plugging and d i s r u p t i n g
operation.
EXPERIMENTAL PROCEDURES AND RESULTS
P r i o r to conducting r e s e a r c h in a fluidized bed r e a c t o r , s t u d i e s w e r e u n d e r t a k e n in a closed s y s t e m to
obtain a b e t t e r u n d e r s t a n d i n g of the FeC13-O2 s y s t e m .
VOLUME 3, OCTOBER 1972-2579

*Referenceto trade namesis madeto faclhtateunderstandingand does not

implyendorsementby the Bureauof Mines

Table I. Physical Properties of Iron Chlorides 7

Chloride

Meltmg
Point, ~

Boihng
Pomt, ~

Thermal Decomposition
Reactions6

FeCI3
FeC12
FeOCI

304
677
Decomposesabove

319
1,026
Decomposesabove

FeC13 = FeC12 + ~ C12

None
3FeOCI= Fe2 O3 + FeCla

200~

200~

Selected p h y s i c a l p r o p e r t i e s of these i r o n c h l o r i d e
compounds a r e given in T a b l e I.
R e a c t i o n r a t e s w e r e d e t e r m i n e d by p r e s s u r e d i f f e r e n c e s a s a function of t i m e and t e m p e r a t u r e s . Studies
w e r e conducted at 1 to 2 arm p r e s s u r e and t e m p e r a t u r e s r a n g i n g f r o m 50 ~ to 300~
R e s u l t s show two
s i m u l t a n e o u s , f i r s t - o r d e r r e a c t i o n s , n e i t h e r of which
went to completion, p r o b a b l y b e c a u s e of i n t e r f e r e n c e
by a product l a y e r on the u n r e a c t e d c h l o r i d e . G r i n d i n g
the r e a c t i n g solid i n c r e a s e d the a m o u n t of FeC13
r e a c t e d , but the r e a c t i o n was s t i l l not complete, and
the r e a c t i o n g a s e s had a low c h l o r i n e content.
L o w - t e m p e r a t u r e (below 300~ r e a c t i o n of oxygen
with f e r r i c c h l o r i d e has b e e n c h a r a c t e r i z e d by t h r e e
g e n e r a l t e m p e r a t u r e r e g i o n s . Below 100~ no s u b s t a n tial r e a c t i o n o c c u r s . Between 100 ~ and 200~ the
reaction
2 FeC13 = 2 FeC12 + C12

[1]

o c c u r s , along with some oxidation to FeOC1 a c c o r d i n g

to the r e a c t i o n :
2 FeC12 + 02 = 2 FeOC1 and C12
At t e m p e r a t u r e s g r e a t e r than 200~
p o s e s a s shown in Eq. [3]
3 FeOC1 = FeC13 + Fe203
3

2 F e C l s +-~O2

_-

Fe203+3C12

[2]
FeOC1 d e c o m [3]
[4]

and f u r t h e r r e a c t i o n with oxygen o c c u r s slowly. The

r a t e of r e a c t i o n b e t w e e n FeC13 and 02 to f o r m Fe203
and C12 is somewhat slow at 300~ but is a l m o s t i n s t a n t a n e o u s at 600~
Equipment
Several fluidized-bed reactor designs were tested
for the d e c h l o r i n a t i o n of FeC13. The m a j o r p r o b l e m
e n c o u n t e r e d was that caused by plugging of feed inlet
l i n e s by FeC12, FeOC1, and FeC13. T h i s p r o b l e m was
l a r g e l y o v e r c o m e by p a s s i n g both cold fluidizing gas
and FeC13 through a U - s h a p e d feed tube. F e r r i c oxide
bed p a r t i c l e s o s c i l l a t e d in the feed tube owing to p r e s s u r e f l u c t u a t i o n s and tended to s c o u r the feed i n l e t . The
c o m b i n e d effects of u s i n g a cold fluidizing gas and the
s c o u r i n g action of the bed m a t e r i a l tended to keep the
line open and p r e v e n t e d p r e m a t u r e r e a c t i o n in the feed
i n l e t to the r e a c t o r . The r e a c t o r shown in Fig. 1 p r o v e d
effective and allowed a t t a i n m e n t of s t e a d y - s t a t e condi t i o n s in a few m i n u t e s of operation with only i n f r e q u e n t
plugging of feed l i n e s . M a j o r f e a t u r e s of the a p p a r a t u s
include a feed m e c h a n i s m , f l u i d - b e d r e a c t o r , c o n d e n s e r ,
dust t r a p , and C12 a n a l y s i s unit. Heat to the fluidized
bed was supplied by a 2 in. d i a m , 24 in. long, t w o - z o n e
r e s i s t a n c e - h e a t e d tube f u r n a c e . The 2 in. d i a m r e a c t o r
was c o n s t r u c t e d of Vycor.* The c o n d e n s e r and dust
2580-VOLUME 3, OCTOBER 1972

t r a p s w e r e c o n s t r u c t e d of 2 in. diam d o u b l e - t o u g h
P y r e x pipe followed by two s a t u r a t e d NaC1 b u b b l e r s
which i n c o r p o r a t e d the gas s a m p l i n g unit and a c o n t i n uous u l t r a v i o l e t C12 a n a l y z e r .
Iron compounds (FeC13, Fe2Oa), NaC1, and 02 w e r e
technical-grade materials purchased from commercial
s u p p l i e r s and used a s r e c e i v e d . It was found n e c e s s a r y
to p r e t r e a t the Fe2Oa b e c a u s e of i t s e x t r e m e l y fine p a r t i c l e s i z e . The method adapted for p r e p a r i n g a s u i t a b l e
bed of Fe203 for f l u i d i z a t i o n i n v o l v e d b l e n d i n g Fe203
with a n h y d r o u s FeC13 in a 10 to 1 r a t i o , followed by
adding w a t e r , baking, and ignition at 600~
A suitable
p a r t i c l e size was obtained by s c r e e n i n g this m a t e r i a l
through a s t a n d a r d 2 0 - m e s h T y l e r s c r e e n . The FeC13
was a l s o s c r e e n e d to m i n u s 20 m e s h ; h o w e v e r , c a r e
was e x e r c i s e d to p r e v e n t e x c e s s i v e pickup of m o i s t u r e
by the highly h y g r o s c o p i c c h l o r i d e s a l t .
The FeC13 was c o n t a i n e d in a m i l d s t e e l hopper and
s c r e w - f e d into a U - s h a p e d P y r e x tube. Oxygen was i n t r o d u c e d along with the FeC13 to a s s i s t t r a n s p o r t of the
c h l o r i d e salt into the b a s e of the fluidized bed. The U shaped feed tube was kept free of plugs by the s c o u r i n g
action of Fe203 p a r t i c l e s which o s c i l l a t e d up and down,
along with FeC13, at the b a s e of the fluidized bed. The
b a s e of the t a p e r e d fluidized bed was j o i n e d to a w a t e r cooled 1 2 - m m P y r e x feed a s s e m b l y by a ball joint c o n n e c t i o n . A s h o r t length of p i a n o w i r e was i n s e r t e d into
the U - s h a p e d feed line which extended into the fluidized
bed. O c c a s i o n a l r o t a t i o n of this w i r e c a u s e d a flicking
m o t i o n which was p a r t i c u l a r l y effective in m a i n t a i n i n g
a smooth flow of r e a c t a n t s and a l s o helped p r e v e n t
c r u s t f o r m a t i o n at the b a s e of the FluoSolids r e a c t o r .
C h l o r i n e was c o n t i n u o u s l y a n a l y z e d by s p l i t t i n g the
off-gas s t r e a m , and p a s s i n g the 02 and C12 m i x t u r e
through a s y s t e m of f i l t e r s and then into a c h l o r i n e
a n a l y s i s u n i t . The c h l o r i n e a n a l y s i s u n i t i n c o r p o r a t e s
an u l t r a v i o l e t light s o u r c e and p h o t o c e l l . A b s o r p t i o n
of u l t r a v i o l e t light by c h l o r i n e p e r m i t s d e t e r m i n a t i o n
of c h l o r i n e c o n c e n t r a t i o n . Light which p a s s e s through
a s p e c i a l filter falls upon a p h o t o e l e c t r i c cell which
c o n v e r t s the light e n e r g y into a m i c r o a m p c u r r e n t .
T h i s c u r r e n t is then r e l a y e d to a c o n t i n u o u s r e c o r d i n g
i n s t r u m e n t for r e a d o u t . I n c r e a s e d c h l o r i n e content of

TOanalyzerUltrovlochlorine~
let

To vent

Therrnocouplep r o b e ~
Fluldlzed-bed reactor~
Pressure
release

,CI

-~
=

Flow- r ~
meter

?
Oxygen
Manometer.-/
Feederj

-Water-cooled jacket

Piano wlre-~.rE
Fig. 1--Fluidized bed for conversion of FeC13 to Fe20~ and C12.
METALLURGICAL TRANSACTIONS

90

Table II. Constant Operating Parameters

Fe203,
Wt, g
800

Fluidized Bed
Bed
Cross
Height, era Sectmn, cm 2
33 to 38

18

Oxygen Flow Rate*

cc/Mm
cc/cm2-Min
1950+_50

t08 +_2.8

02 flow rote 108 _+2.8 cc/cmZ-min

Pressure Drop
Across Bed
mm/Hg

FeCI 3 feed rote g / c m Z - m i n

{3 1.0 9 . 4 0 Z~ .26 9 .21
Temperature, 5 0 0 ~ C

80

60 to 80

/0

70-

*By stoichiometry ttus amount of O~ reacts with 18.15 -+ 0.47 g/mm of FeCI3
(1.01 -+ 0.126 g/cm2-min).

O--r,

.10

o--

[]

S 60
O.

the g a s s t r e a m d e c r e a s e s the m i c r o a m p r e a d i n g b e c a u s e c h l o r i n e g a s i s a s t r o n g a b s o r b e r of light with

wave l e n g t h s between 280 and 390 m p . C a l i b r a t i n g and
m o n i t o r i n g t h i s g a s a n a l y s i s unit involved the u s e of a
s t a n d a r d O r s a t g a s a n a l y s i s a p p a r a t u s . The g a s a n a l y s i s m e t h o d involved m e a s u r i n g a v o l u m e of g a s b e f o r e
and a f t e r p a s s i n g through a solution of p o t a s s i u m
hydroxide.

"6
.

03

50

L9
LL

,,

S t a r t - u p of the fiuidized bed r e a c t o r w a s a c c o m p l i s h e d b y c h a r g i n g 800 g of Fe203 into the r e a c t o r ,

i n t r o d u c i n g O2 for f l u i d i z a t i o n , and then b r i n g i n g the
b e d up to the d e s i r e d o p e r a t i n g t e m p e r a t u r e which
r a n g e d f r o m 400 ~ to 650~
When the Fe203 b e d r e a c h e d
o p e r a t i n g t e m p e r a t u r e , a slow feed (0.25 g / c m 2 - m i n ) *
*

*(cc/cm2-mm) refers to cm 3 of 02 per cm 2 of reactor cross sectmn per minute.

p a s s e d through the b e d for 5 m i n . T h i s p r o c e d u r e

t e n d e d to r e m o v e f i n e s f r o m the b e d , p r o m o t e d p a r t i c l e
s i z e growth of Fe203 p a r t i c l e s , and s t a b i l i z e d the bed,
which p r o m o t e d s m o o t h o p e r a t i o n . A f t e r t h i s bed c o n ditioning s t e p , final t e m p e r a t u r e a d j u s t m e n t s w e r e
m a d e and FeC13 feeding w a s r e s u m e d . F e r r i c c h l o r i d e
feed r a t e s w e r e v a r i e d by use of a v a r i a b l e s p e e d
m o t o r which d r o v e the feed s c r e w . Bed weight, bed
height, 02 flow r a t e , and p r e s s u r e w e r e e s s e n t i a l l y
h e l d c o n s t a n t d u r i n g e x p e r i m e n t a l r u n s . The m a g n i t u d e
of t h e s e p a r a m e t e r s i s shown in Table II. The amount
of FeC13 c o n v e r t e d to Fe203 and Ctz w a s c a l c u l a t e d f r o m
the known oxygen flow r a t e and the p e r c e n t Clz in the
p r o d u c t g a s s t r e a m , R e a c t i o n [4]. Continuous a n a l y s i s
of the p e r c e n t C12 in the p r o d u c t g a s a l l o w e d d e t e r m i n a t i o n of s t e a d y - s t a t e o p e r a t i o n which w a s i n d i c a t e d by
c o n s t a n t C12 g a s c o m p o s i t i o n . The p e r c e n t c o n v e r s i o n
of FeCI3 to Fe203 w a s a l s o c a l c u l a t e d f r o m the FeC13
f e e d r a t e , and the amount of u n r e a c t e d FeC13 in the
s y s t e m c o n d e n s e r and dust c o l l e c t o r .
The p e r c e n t c h l o r i n e in the o f f - g a s a s a function of
t i m e at s e v e r a l d i f f e r e n t feed r a t e s i s shown in F i g . 2.
I n s p e c t i o n of F i g . 2 i n d i c a t e s that s t e a d y - s t a t e c o n d i t i o n s w e r e e s t a b l i s h e d in f r o m 5 to 10 rain. Wide f l u c t u a t i o n s in the p e r c e n t c h l o r i n e w e r e d e t e c t e d i m m e d i a t e l y and i n d i c a t e d d e v i a t i o n s f r o m s t e a d y - s t a t e
o p e r a t i o n . T h e s e d e v i a t i o n s w e r e c a u s e d by channeling,
b e d slugging, and plugs f o r m i n g e i t h e r at the inlet or at
s o m e point d o w n s t r e a m .
M a j o r o b j e c t i v e s of e x p e r i m e n t s w e r e to m a x i m i z e
the c o n v e r s i o n of FeC13 to Fe203 and C12, and to p r o duce an o f f - g a s containing a high (>90 pet) c h l o r i n e
content, which would be s u i t a b l e for r e c y c l e a s a c h l o r METALLURGICAL TRANSACTIONS

a--a

A--a--A

'A

ix

,~. . . .

po--o

0--0

....

20
0---

I0

(g/cm 2 -ram) refers to grams of FeC13 per cm 2 of reactor cross secaon per minute.

of FeCI~ w a s i n t r o d u c e d into the r e a c t o r for 5 min,

a f t e r which O2 at a flow r a t e of 108 c c / c m 2 - m i n * w a s

9 ~

40

~50

Operating Procedure

_.,
0

i
I0

20
30
4O
TIME, minutes

t
5O

60

Fig. 2--Percent C12 in off-gas as a function of time.

inating agent. V a r i a b l e s s t u d i e d d u r i n g t h i s i n v e s t i g a tion included t e m p e r a t u r e , f e r r i c c h l o r i d e feed r a t e s ,
and the c a t a l y t i c effect of NaC1.
E f f e c t s of T e m p e r a t u r e
A s e r i e s of t e s t s w a s p e r f o r m e d at t e m p e r a t u r e s
r a n g i n g f r o m 400 ~ to 650~
T h e s e t e s t s w e r e conducted
in Fe203 b e d s which contained no NaC1. T e s t s w e r e
conducted at a FeC13 feed r a t e of 1.0 g / c m 2 - m i n and an
oxygen flow r a t e of 108 cm3/cm2-min. * I n s p e c t i o n of
*TheoreUcally an O~ flow of 108 cc/cm2-min should convert 1.0 g/cm2-min of
FeC13.

F i g . 3 shows that c o n v e r s i o n of FeC13 to Fe203 and C12

i s t e m p e r a t u r e dependent and i s v e r y low at t e m p e r a t u r e s below 500~
High c h l o r i n e c o n c e n t r a t i o n s (>90
pct) and high c o n v e r s i o n s (>90 pct) of FeC13 to FezO3
w e r e not e f f e c t e d at t e m p e r a t u r e s below 600~

E f f e c t s of V a r y i n g FeC13 F e e d R a t e s
A f t e r e s t a b l i s h i n g the n e c e s s i t y of conducting o p e r a t i o n s at or above 600~ a s e r i e s of t e s t s was conducted to d e t e r m i n e the effect of v a r y i n g FeC13 feed
r a t e on the p e r c e n t c o n v e r s i o n of FeC13 and the p e r cent c h l o r i n e in the o f f - g a s . T h e s e t e s t s w e r e c o n ducted at 600~ with an Oz flow of 108 c c / c m 2 - m i n and
without NaCI in the f l u i d i z e d Fe203 b e d . The r e s u l t s of
t h e s e t e s t s a r e shown in F i g . 4.
I n s p e c t i o n of F i g . 4 i n d i c a t e s that o p t i m u m r e s u l t s
f r o m the standpoint of both p e r c e n t c o n v e r s i o n and p e r V O L U M E 3, O C T O B E R 1 9 7 2 - 2 5 8 1

I00

O0

ix

90

90

80

80

"5

7O

'~
> 60

70
O(M

60
O

(9 5 0
i
I.L
0
Z

cent c h l o r i n e in the off-gas was obtained at a feed r a t e

of 0.83 g FeC13/cm2-min. T h i s feed r a t e gave an offgas c o n t a i n i n g 87 pct C12 and an 87 pct c o n v e r s i o n of
FeC13. Fig. 4 a l s o shows that high c o n v e r s i o n s of
FeCla a r e r e a d i l y effected but only at the e x p e n s e of
having a low c o n c e n t r a t i o n of C12 in the o f f - g a s . It
should a l s o be o b s e r v e d that C12 c o n c e n t r a t i o n and
FeC13 c o n v e r s i o n s above 90 pct w e r e obtained at high
FeC13 feed r a t e s or at t e m p e r a t u r e s above 600~ a s
shown in F i g s . 3 and 4. An a d v e r s e factor a s s o c i a t e d
with o p e r a t i n g at t e m p e r a t u r e s of 600~ or above is
due to the c o r r o s i v e n a t u r e of both FeC13 and C12 at
elevated temperature. Accordingly, studies were initiated to d e t e r m i n e if the p r e s e n c e of NaC1 in the Fe203

5O
rr
ILl
>

FeCI 3 feed rate 1.0

g/cm2-min

40

40

5O

9 FeCI 3 converted to
Fe203, pct

- 30

o 9o
<[
(.9

z~ CI 2 in o f f gas, vol pct

20

o.

(.9
rO

02 flow rate t08__28

cc/r rn2- m in

o4

-~ I00 9

Temperature,

d_ 80
U_
0

- 20

500 ~ C

FeCl 3 f e e d rote

1.0 g / c m 2 - m i n

02 flow rate 108+_2.8 c c / c m Z - m i n

A
-

ol

I
450

4O0

I
I
I
500
550
600
TEMPERATURE,
"C

I
650

_z 7 0 ~ -

I0

NoCl

Fig. 3---Co nversion of F e C ] 3 a n d p e r c e n t C12 in o f f - g a s a s a

f u n c t i o n of t e m p e r a t u r e .

tO0

& ~ t

&

90 -

'x/z~
"'9149

~ ~ , . 9s .

I
I

0
70~

I
2
IN

I
.3

I
4

FLUIDIZED

I
5

BED,

wt

pct

F i g. 5 - - P e r c e n t C12 in o f f - g a s a s a f u n c t i o n of p e r c e n t NaC1
in Fe203 bed.

I00

I00

- 90

9o

,0tO/~ ''-

t.t,
80 -

80

"5

8O

CL

O(M

d
h

6o

6o

50

r~
Ud

50

o~

Temperature, 600 ~ C
02 flow rate 108_+ 2 8
cc/cmZ-min

40

20

70

9 FeCI3 converted to
Fe20~,, pct

Zx CI2 in off-gas,

>
Z
0
c)

40
~D
U-

<>

-6

:.

Or)

30

60

~_ 5 o
0

~40

30

vol pct

20

30

# NaCl in bed

0.2
04
FeCl 3 FEED

I
0.6
RATE,

0.8
1.0
g/cm2-min

tO
.2

Fig. 4 - - C o n v e r s i o n of FeC13 a n d p e r c e n t CI 2 in o f f - g a s a s a
f u n c t i o n of FeC13 f e e d r a t e .

2 5 8 2 - V O L U M E 3, OCTOBER 1972

500*

02 flow rote 108__.2.8

20

JO

Temperature,

0.2

C
cc/cm2-min

2.5 wt pct

0 No NaCI in bed
I
I
0.4
0.6
0.8

I
1.0

1.2

FeCI 3 FEED RATE, g/cm2-min

Fig. 6 - - P e r c e n t C12 in o f f - g a s a s a f u n c t i o n of FeC13 f e e d r a t e
and bed composition.

METALLURGICAL TRANSACTIONS

,oo

'0<>

9o-

' *~$-$l..

\0

801h

o 7o-

<~

c~
L~
rr 6 0 l.iJ
>
z
0
o 50Temperature, 500* C

CONCLUSIONS

0 z flow rote 108_+ 2.8 cc/cmZ-min

40-

30
0

NaCI in bed 2.5 wt pct

No NaCI in bed

1
1
0.2
0.4
Feel:5 FEED

I
0,6
RATE,

I
I
0.8
1.0
g/cm2-min

1.2

Fig. 7--Percent conversion of FeC13 as a function of FeCI a

feed rate and bed composition.
would p e r m i t o p e r a t i o n at l o w e r t e m p e r a t u r e s . A l o w e r
t e m p e r a t u r e would be d e s i r a b l e b e c a u s e it would r e duce c o r r o s i o n and p o s s i b l y p e r m i t the u s e of n i c k e l or
Inconel a s m a t e r i a l s of c o n s t r u c t i o n .
E f f e c t s of NaC1 A d d it io n s
During an e a r l i e r study i n v o l v i n g NaC1-FeC13 s a l t
m i x t u r e s , 8 it w a s o b s e r v e d that the v a p o r p r e s s u r e of
Fee13 is s i g n i f i c a n t l y r e d u c e d by the p r e s e n c e of even
s m a l l a m o u n t s of NaC1 and that oxidation of FeCI3 is
c a t a l y z e d by NaC1. A c c o r d i n g l y , a s e r i e s of t e s t s w as
m a d e in which NaC1 additions w e r e m a d e to the Fe~O~
bed in a m o u n t s r a n g i n g f r o m 0 to 5 pet of the bed
w e ig h t . T h e s e t e s t s w e r e a l l conducted at 500~ a feed
r a t e of 1.0 g F e C 1 3 / c m 2 - m i n , and a gas flow of 108
c c / c m 2 - m i n . T h e p e r c e n t C12 in the o f f - g a s is p l o t t ed
v s the wt pet NaC1 in F i g . 5. I n s p e c t i o n of F i g . 5 shows
that C12 c o n c e n t r a t i o n s r a n g e d f r o m 89 to 95 pct and

METALLURGICALTRANSACTIONS

that as l i t t l e as 0.2 wt pet NaC1 e f f e c t i v e l y c a t a l y z e d

the r e a c t i o n b e t w e e n F e e l 3 and O2.
An a d d i t i o n a l s e r i e s of t e s t s w a s conducted under the
s a m e conditions but with the wt p et NaC1 in the bed h e l d
co n st an t . The r e s u l t s of t h e s e t e s t s a r e shown in F i g .
6 along with data f r o m a s e r i e s of t e s t s conducted at
500~ but without NaC1 in the bed. The e f f e c t i v e n e s s of
NaC1 a s a c a t a l y s t can be r e a d i l y s e e n by i n s p e c t i o n of
F i g . 6. The p e r c e n t Fee13 c o n v e r s i o n is shown in F i g .
7. R e s u l t s obtained in s i m i l a r t e s t s but without NaC1
a r e shown for c o m p a r i s o n . T h e s e r e s u l t s show that
Fee13 c o n v e r s i o n s above 95 p ct and an o f f - g a s c o n t a i n ing o v e r 90 pct C12 a r e obtainable at 500~ when NaCI
i s u s e d to c a t a l y z e the d e c h l o r i n a t i o n of Fee13 by Oz.
R e f e r e n c e to F i g . 3 shows that c o m p a r a b l e r e s u l t s
r e q u i r e d a t e m p e r a t u r e of 650~ in the a b s e n c e of NaC1.

This study has shown that FeCI3 can be fed into a

fluidized bed of Fe203 and can be dechlorinated by reaction with 02 to produce an off-gas containing over 90
pct C12 and with conversions of FeCI3 above 95 pct.
These results can be achieved at 500~ when NaCI is
added to the bed as a catalyst. In the absence of NaCl,
a temperature of 650~ is required to achieve comparable results. The work also showed that as little
as 0.2 wt pct NaC1 in the bed effectively catalyzed reaction between FeCI3 and 02.
ACKNOWLEDGMENT
The a u t h o r s w i s h to a c k n o w l e d g e the w o r k of David
E. Lan g e on the low t e m p e r a t u r e oxidation of Fee13 in
a closed system. Mr. Lange is presently a Graduate
Student at A r i z o n a State U n i v e r s i t y .
REFERENCES
1. J. J. Hennand J. A. Barclay U. S. Bur. Mineslnf Circ., 8450, 1970.
2. W. E. Dunn, Jr., etaL: U. S. Patent 3,376,ll2, 1965.
3. E. W. Nelson,etal.: U. S. Patent 3,092,456, 1959.
4. R. H. Sawyer:U. S. Patent 2,642,339, 1948.
5. W. H. Hughesand K. Arkless: BritishPatent 992,317, 1965.
6. Z. I. Latin and A. A. Furman: Zh. PriM. Khim., 1970,vol.43, no. 4,
pp. 830-34.
7. C. E. Wicksand F. E. Block: U. S. Bur. MinesBull. 605, 1963.
8. H. F. Johnstone, H. C. Weinganther, and W.E. Winsche:J. Amer.
Chem. Soc., 1942, vol. 64, pp. 241-44.

VOLUME 3, OCTOBER 1972-2583