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KINETICS O F BITUMINOUS COAL CHAR GASIFICATION

WITH GASES CONTAINING STEAM AND HYDROGEN

by
J. L. Johnson
I n s t i t u t e of G a s Technology
Chicago, Illinois 60616
I

INTRODUCTION I

C o r r e l a t i o n s t o quantitatively define the effects of pertinent intensive


v a r i a b l e s on the kinetics of c o a l o r c o a l c h a r gasification r e a c t i o n s a r e
. n e c e s s a r y f o r the rational d e s i g n of c o m m e r c i a l s y s t e m s t o c o n v e r t c o a l
to pipeline gas. T h e a v a i l a b l e information, which can b e applied to the
development of s u c h c o r r e l a t i o n s is r e l a t i v e l y limited, p a r t i c u l a r l y b e c a u s e
the data r e p o r t e d f r o m m a n y s t u d i e s conducted with i n t e g r a l contacting
s y s t e m s r e f l e c t , i n p a r t , undefined physical a n d c h e m i c a l behavior peculiar r

t o t h e specific e x p e r i m e n t a l s y s t e m s used. Although s o m e differential r a t e


data have been obtained with v a r i o u s carbonaceous m a t e r i a l s , they c o v e r
only n a r r o w r a n g e s of the conditions potentially applicable to c o m m e r c i a l
gasification s y s t e m s .

During t h e last s e v e r a l y e a r s , the Institute of Gas Technology (IGT) h a s


been conducting a continuing study t o obtain fundamental information o n the
gasification of c o a l s and c o a l c h a r s , which could b e used, along with s e l e c t e d
information in t h e l i t e r a t u r e , t o develop engineering c o r r e l a t i o n s which
quantitatively define t h e e f f e c t s of intensive v a r i a b l e s on gasification r a t e s
o v e r a wide range of conditions applicable to a v a r i e t y of conceivable gasifi-
cation p r o c e s s e s . The m o d e l s and c o r r e l a t i o n s developed a t the p r e s e n t
time a r e p r i m a r i l y applicable to bituminous c o a l c h a r s p r e p a r e d at m i l d o r
s e v e r e conditions i n e i t h e r i n e r t o r oxidizing a t m o s p h e r e s . Although we have
achieved s o m e s u c c e s s i n applying t h e s e c o r r e l a t i o n s to t h e gasification of
subbituminous and lignite c o a l s f o r limited r a n g e s of conditions, the gasifica-
tion k i n e t i c s of s u c h materials have shown wide deviations f r o m p r e d i c t i o n s
of t h e c o r r e l a t i o n s a t l o w e r t e m p e r a t u r e s and during i n i t i a l s t a g e s of
gasification.

228
-. ~ ._ .
i
i T h e objective of t h i s p a p e r is a ) to d i s c u s s the m o d e l s which have been
developed; b) to p r e s e n t the c o r r e l a t i o n s d e r i v e d f r o m t h e s e models; and
c ) to d e m o n s t r a t e t h e c o n s i s t e n c i e s between predictions of t h e s e c o r r e l a t i o n s
and v a r i o u s e x p e r i m e n t a l gasification data obtained p r i m a r i l y with bituminous
coal c h a r s . We obtained the e x p e r i m e n t a l information u s e d i n developing the
models f r o m two m a i n s o u r c e s . Initial development of the model f o r applica-
tion to the gasification of devolatilized c o a l c h a r in hydrogen and s t e a m -
hydrogen m i x t u r e s w a s b a s e d both on data obtained i n a n extensive study
conducted a t IGT with a h i g h - p r e s s u r e thermobalance a p p a r a t u s and on
differential r a t e data obtained by i n v e s t i g a t o r s at the Consolidation Coal
Company f o r the gasification of Disco c h a r i n a s m a l l - s c a l e fluid bed. 93,' ' l9

Then, the m o d e l w a s extended t o apply to the gasification of c h a r containing


volatile m a t t e r and to gasification with g a s e s containing c a r b o n monoxide,
carbon dioxide, and methane, a s well a s s t e a m and hydrogen, using data
obtained p r i m a r i l y i n the thermobalance study.

The t h e r m o b a l a n c e h a s b e e n a p a r t i c u l a r l y useful tool f o r obtaining funda-


m e n t a l gasification information, since with t h i s type of a p p a r a t u s , gasification
r a t e s can be m e a s u r e d at constant, well-defined, environmental conditions.
Since a m a j o r amount of the information u s e d i n the formulation of the kinetic
models developed, w a s based o n data obtained i n s e v e r a l hundred t e s t s con-
ducted with the t h e r m o b a l a n c e , a brief d e s c r i p t i o n of t h i s a p p a r a t u s i s given
below.

EXPERIMENTAL

The t h e r m o b a l a n c e is a n a p p a r a t u s capable of continuously weighing a coal


sample which i s undergoing r e a c t i o n in a gaseous environment of d e s i r e d
composition at a constant p r e s s u r e . The t e m p e r a t u r e c a n e i t h e r be kept
constant o r v a r i e d . (10 " F / m i n i s the m a x i m u m r a t e f o r the a p p a r a t u s used
a t IGT. ) T h e n a t u r e of gas-solid contacting with the a p p a r a t u s used i n this
study i s shown i n F i g u r e 1. T h e c o a l s a m p l e i s contained i n the annular s p a c e
of a w i r e - m e s h b a s k e t bounded on the inside by a hollow, s t a i n l e s s - s t e e l tube
and on the outside by a w i r e m e s h s c r e e n . To f a c i l i t a t e mass and h e a t
t r a n s f e r between the bed and its environment, the thickness of the bed is only
2 - 3 p a r t i c l e d i a m e t e r s when using -2Ot40 USS s i e v e - s i z e p a r t i c l e s . G a s flow
r a t e s used with t h i s s y s t e m a r e sufficiently l a r g e r e l a t i v e to gasification r a t e s ,
that g a s conversion i s limited t o l e s s than 1 %
' f o r devolatilized coal c h a r .

229

5
SlGt L TO
RECI DER

-WINDLASS

It
INERT
GAS

GOLD CHAIN

f
-
-
-
PRODUCT
GAS

-SAMPLE
iJ BASKET

'I
/

tREACTOR

1-112-1009
FEED REACTANT GAS

F i g u r e 1. DLAGRAM O F THERMOBALANCE REACTOR

The following i s a typical t e s t procedure: The w i r e m e s h basket i s


initially in an upper cooled portion of the r e a c t o r in which a downward, i n e r t
g a s flow is maintained. During t h i s time the d e s i r e d t e m p e r a t u r e and p r e s s u r e
conditions a r e established in a lower heated portion of the r e a c t o r i n the
p r e s e n c e of a flowing gas. A t e s t is initiated by lowering the basket into
the heated reaction zone, a p r o c e d u r e which t a k e s 5 - 6 seconds. Theoretical
computation indicates that about 2 minutes a r e required f o r the s a m p l e to
achieve r e a c t o r t e m p e r a t u r e , a s m e a s u r e d by s e v e r a l t h e r m o c o u p l e s
surrounding the basket i n the reaction zone. This computation i s reasonably
c o r r o b o r a t e d by various kinetic indications and by the behavior of the t h e r m o -
couples in reattaining t h e i r p r e s e t t e m p e r a t u r e s . The s a m p l e is kept in the
heated portion of the r e a c t o r f o r the specified time while its weight is con-
tinuously r e c o r d e d . The t e s t is terminated by raising the basket back to the
upper, cooled portion of the r e a c t o r .

230
During a test, the d r y feed gas flow r a t e s a r e m e a s u r e d by o r i f i c e m e t e r
and the d r y product g a s flow r a t e s by a wet-test m e t e r . Periodic samples
of product g a s a r e taken to d e t e r m i n e the d r y g a s ' composition by m a s s
spectrograph. Feed and product s t e a m flow r a t e s a r e m e a s u r e d by gravi-
m e t r i c means, and the solids r e s i d u e s a r e analyzed f o r t o t a l carbon and
hydrogen.

F i g u r e 2 shows some typical, smoothed, weight l o s s - v e r s u s - t i m e c h a r a c -


t e r i s t i c s obtained using a n a i r - p r e t r e a t e d hvAb Pittsburgh coal c h a r f r o m the
Ireland mine. T h e s e c u r v e s a r e d i s c u s s e d i n m o r e detail in a subsequent

0.7

0.E
(I

E
-
::
0
Q 0.5
\ Q
r
0
\
0

z- 0.4
?u
a
E O.?
lJl
v)

:
0

I
0.2

P TEMPERATURE = 1700'F
W

0.1

C I I I I I I
I 2 3 4 5 6 7

TIME, min

A-112-1011

F i g u r e 2 . TYPICAL WEIGHT-LOSS CURVES OBTAINED WITH THE


HIGH-PRESSURE THERMOBALANCE FOR GASIFICATION O F
AIR-PRETREATED IRELAND MINE COAL CHAR IN
HYDROGEN AND IN NITROGEN

section of t h i s paper. The composition of the c o a l c h a r , used extensively


in the experimental study, i s given in Table 1.

231
T e h l s 1. COMPOSITION O F AIR-PRETREATED hvAb
PITTSBURGH NO. 8 COAL CHAR (Ireland Mine)

Ultimate Analysis, d r y wt %
Carbon 71. 1
Hydrogen 4.26
Oxygen 8. 85
Nitrogen 1.26
Sulfur 3.64
Ash 10.89
Total 100.00

P r o x i m a t e Analysis,

Fixed Carbon 60.7


Volatile 28. 4
Ash 10.9
Total 100.0

DESCRIPTION O F KINETIC MODELS

'When a c o a l o r coal c h a r containing volatile m a t t e r is initially subjected


t o an elevated t e m p e r a t u r e , a s e r i e s of complex physical and chemical changes
o c c u r i n the c o a l ' s s t r u c t u r e accompanied by t h e r m a l p y r o l y s i s reactions,
which r e s u l t in devolatilization of c e r t a i n coal components. The distribution
of the evolved products of t h e r e a c t i o n s , which initiate a t l e s s than 700 OF and
can be considered t o occur a l m o s t instantaneously at t e m p e r a t u r e s g r e a t e r
than 1300 "F. is generally a function of the t e m p e r a t u r e , p r e s s u r e , and g a s
composition existing during devolatilization and of the subsequent t h e r m a l and
environmental h i s t o r y of the g a s e o u s phase (including entrained liquids) p r i o r
to quenching.

When devolatilization o c c u r s i n t h e p r e s e n c e of a gas containing hydrogen


a t a n elevated p r e s s u r e , in addition t o t h e r m a l p y r o l y s i s reactions, coals o r
coal c h a r s containing volatile m a t t e r a l s o exhibit a high, although transient,
reactivity f o r the formation of methane. Although some i n v e s t i g a t o r s have
suggested that t h i s p r o c e s s o c c u r s c o n c u r r e n t with t h e r m a l pyrolysis reactions,

232
r e s u l t s of studies m a d e with a g r e a t e r time r e s o l u t i o n indicated that this
r a p i d - r a t e methane f o r m a t i o n o c c u r s at a r a t e which is at leas& a n o r d e r of
magnitude slower than devolatilization. 7r '' In t h i s s e n s e it o c c u r s consecu-
tively to devolatilization.

T h e amount of c a r b o n gasified to methane during t h e t r a n s i e n t period of


high reactivity i n c r e a s e s significantly with i n c r e a s e s i n hydrogen p a r t i a l
pressure. 79 138 l7 E x p e r i m e n t a l evidence i n d i c a t e s that, at sufficiently high
hydrogen p a r t i a l p r e s s u r e s , v i r t u a l l y all of the c a r b o n not evolved during
devolatilization c a n be g a s i f i e d t o methane during a v e r y s h o r t t i m e period
by t h i s p r o c e s s . l3 This is c o n t r a r y to s o m e proposed models, which a s s u m e
that only a limited amount of c a r b o n c a n be gasified i n this r e a c t i o n stage,
r e g a r d l e s s of the hydrogen p a r t i a l p r e s s u r e . 3 , l6

At t e m p e r a t u r e s g r e a t e r than 1700 "F, t h e t r a n s i e n t r e a c t i v i t y f o r r a p i d -


r a t e methane f o r m a t i o n e x i s t s f o r a v e r y s h o r t p e r i o d of t i m e . F o r coals,
o r coal c h a r s p r e p a r e d i n i n e r t a t m o s p h e r e s , t h i s period l a s t s only s e c o n d s
\ or less. l3 I G T ' s studies suggest that f o r a i r - p r e t r e a t e d c o a l c h a r s , t h i s
period i s m o r e extended, although the t o t a l a m o u n t s of c a r b o n which can b e
gasified by t h i s p r o c e s s at a given t e m p e r a t u r e and hydrogen p a r t i a l p r e s s u r e ,
a r e comparable f o r c o a l s and c o a l c h a r s p r e p a r e d at sufficiently low t e m p e r a -
t u r e s either in i n e r t g a s o r i n a i r .

After the devolatilization a n d r a p i d - r a t e methane f o r m a t i o n s t a g e s a r e


completed, c h a r gasification o c c u r s a t a r e l a t i v e l y slow r a t e , and v a r i o u s
m o d e l s to d e s c r i b e the gasification k i n e t i c s of t h i s m a t e r i a l f o r v a r i o u s
limited r a n g e s of conditions have been proposed. T h e differential r a t e s of
r e a c t i o n of devolatilized coal c h a r s a r e a function of t e m p e r a t u r e , p r e s s u r e ,
g a s composition, c a r b o n conversion, and "prior h i s t o r y . 'I

G e n e r a l Assumptions in t h e Development of Models

The models developed i n t h i s study f o r t h e quantitative d e s c r i p t i o n of c o a l


c h a r gasification k i n e t i c s assume that t h e o v e r a l l gasification p r o c e s s o c c u r s
i n t h r e e consecutive s t a g e s : 1 ) devolatilization, 2 ) r a p i d - r a t e methane f o r -
mation, and 3 ) l o w - r a t e gasification. The r e a c t i o n s i n t h e s e t h r e e s t a g e s a r e
independent. F u r t h e r , a feed coal c h a r contains two types of carbon, volatile
c a r b o n and b a s e carbon.

233
Volatile c a r b o n c a n be evolved s o l e l y by t h e r m a l pyrolysis, independent
of t h e g a s e o u s medium. T h e d i s t r i b u t i o n of evolved p r o d u c t s d e r i v e d f r o m
t h e volatile c a r b o n f r a c t i o n i s not defined i n t h e model. In any application
of the model t o a n integral contacting s y s t e m , the devolatilization products
a r e e s t i m a t e d by extrapolation o r interpolation of yields obtained in pilot-
s c a l e fluid o r moving-bed s y s t e m s . T h i s p r o c e d u r e c a n be applied f o r
n a r r o w r a n g e s of conditions and only f o r v e r y similar contacting s y s t e m s .

B a s e c a r b o n r e m a i n s in the c o a l c h a r a f t e r devolatilization is complete.


T h i s c a r b o n c a n b e subsequently g a s i f i e d e i t h e r in the r a p i d - r a t e methane
f o r m a t i o n s t a g e o r in the l o w - r a t e gasification stage.

A quantitative e s t i m a t i o n of t h e i n i t i a l amounts of volatile and b a s e c a r b o n


i s m a d e f r o m s t a n d a r d a n a l y s e s of the feed coal c h a r . T h e following defini-
tion h a s been m a d e :
0
Cv (volatile carbon), g / g of feed c o a l = C (total carbon), g / g of feed coal
t

- Cb0 ( b a s e c a r b o n ) , g / g of feed coal (1)

w h e r e Co r e p r e s e n t s the t o t a l c a r b o n in the feed coal c h a r obtained f r o m a n


t
u l t i m a t e a n a l y s i s and Co r e p r e s e n t s the c a r b o n i n the "fixed c a r b o n " f r a c t i o n
b
of the feed c o a l a s d e t e r m i n e d i n a p r o x i m a t e a n a l y s i s . It i s emphasized that
C i does not equal the fixed c a r b o n f r a c t i o n , s i n c e the fixed c a r b o n f r a c t i o n
includes, i n addition t o c a r b o n , o t h e r o r g a n i c c o a l components not evolved
during s t a n d a r d devolatilization.

E x p e r i m e n t a l r e s u l t s f r o m t h e r m o b a l a n c e o r f r e e - f a l l t e s t s conducted a t
IGT indicate that the a s s u m p t i o n of a constant volatile c a r b o n f r a c t i o n is valid
f o r c o a l heat-up r a t e s a s high a s 200 " F / s . However, other studies conducted
with e x t r e m e l y rapid heat-up r a t e s ( l o 4 to l o 7 " F / s ) have shown that quantities
of c a r b o n evolved during t h e r m a l p y r o l y s i s c a n exceed t h e volatile c a r b o n
f r a c t i o n defined i n t h i s model. b* An allowance f o r the i n c r e a s e i n evolved
c a r b o n would, t h e r e f o r e , have t o be m a d e i n s y s t e m s employing s u c h high
heating r a t e s .

The b a s e c a r b o n conversion f r a c t i o n , X, is defined a s :

c; - Cb
= b a s e carbon gasified -
-
b a s e c a r b o n i n feed c o a l c h a r
c;:

234
\

where

C = b a s e c a r b o n i n coal c h a r a t a n i n t e r m e d i a t e l e v e l of
gasification, g / g feed coal c h a r

When making a kinetic a n a l y s i s of the t h e r m o b a l a n c e data, it w a s n e c e s -


s a r y to r e l a t e the m e a s u r e d values of weight-loss f r a c t i o n , AW/Wo, to the
b a s e c a r b o n conversion fraction, X. When devolatilixation is complete,
e s s e n t i a l l y all of the o r g a n i c oxygen h a s been gasified. T h e r e a f t e r , additional
weight loss, which p r i m a r i l y r e s u l t s f r o m gasification of the b a s e carbon, is
accompanied by t h e evolution of a constant f r a c t i o n of noncarbon components
i n the coal such a s nitrogen, hydrogen, and sulfur. E s t i m a t e s of a n a v e r a g e
value of the f r a c t i o n of noncarbon components gasified along with the b a s e
c a r b o n f o r e a c h type of coal c h a r t e s t e d , have been b a s e d on a n a l y s e s of c h a r
r e s i d u e s obtained i n t h e r m o b a l a n c e and pilot- s c a l e fluid-bed t e s t s . With
this simplifying a s sumption, the following r e l a t i o n s h i p s r e s u l t :

0
Cb = (1 - V - A ) ( l -y)
\
and

where

V = volatile m a t t e r i n feed c o a l c h a r (including m o i s t u r e ) ,


g / g feed c o a l c h a r

A = nongasifiable m a t t e r i n feed coal c h a r (including a s h and some


sulfur), g / g feed coal c h a r

y = noncarbon m a t t e r evolved along with b a s e carbon,


g / g b a s e c a r b o n evolved

Thus, f r o m Equations 2 , 3 , and 4 -


(AW/Wo) -V
X = (5)
1-V-A

T h e r e s u l t s shown in F i g u r e 2 c a n b e i n t e r p r e t e d by the t h r e e r e a c t i o n
s t a g e s defined above. C u r v e A c o r r e s p o n d s to a t e s t i n which a i r - p r e t r e a t e d
Ireland m i n e coal c h a r w a s exposed to a nitrogen a t m o s p h e r e a t a p r e s s u r e
of 500 psig. During the f i r s t minute when t h e s a m p l e i s heating up in the

235

i
thermobalance, the weight l o s s c o r r e s p o n d s to the evolution of volatile
matter. After t h i s period, no f u r t h e r significant weight l o s s o c c u r s . The
total weight l o s s of approximately 26 % c o r r e s p o n d s closely to the volatile
m a t t e r in t h e feed coal c h a r obtained by standard proximate analysis.
Within the context of the t h r e e reaction s t a g e s defined, weight l o s s i n this
t e s t o c c u r s e n t i r e l y i n the devolatilization stage, w h e r e a l l of the volatile
carbon h a s been gasified; a l l of the b a s e carbon r e m a i n s in the devolatilized
coal char. When t h e c h a r resulting f r o m this t e s t is then exposed to hydro-
gen at 500 psig (curve B), the reaction of the hydrogen with b a s e carbon to
f o r m m e t h a n e r e s u l t s in f u r t h e r weight l o s s . T h i s reaction, which t a k e s
place a t a m u c h lower rate than devolatilization, o c c u r s i n the low-rate
gasification stage. With t h i s p a r t i c u l a r sample, t h e r e w a s no reaction in
the r a p i d - r a t e m e t h a n e f o r m a t i o n stage because the reactivity of the coal
c h a r in t h i s stage w a s destroyed during prolonged exposure to nitrogen.

Weight l o s s a s a r e s u l t of t h e reaction i n the r a p i d - r a t e methane f o r m a -


tion stage is illustrated by c u r v e C, w h e r e a s a m p l e of the original coal c h a r
w a s exposed only to hydrogen at 500 psig with no initial exposure to nitrogen.
T h e r e is a weight l o s s during t h e f i r s t minute of this t e s t which is considerably
g r e a t e r than the corresponding weight l o s s obtained during this period when
the coal c h a r w a s exposed to nitrogen ( c u r v e A ) . The difference i n the amount
of weight loss between c u r v e s C and A during the f i r s t minute, o r so, i s
caused by gasification of b a s e c a r b o n i n the rapid-rate m e t h a n e formation
stage. Weight l o s s e s of the magnitude exhibited by c u r v e B during this
initial period a r e negligible. T h i s is consistent with the a s s u m p t i o n that b a s e
carbon gasification in the r a p i d - r a t e methane formation stage and in the low-
r a t e gasification stage o c c u r consecutively.

C u r v e D is qualitatively similar t o c u r v e C, except that t h e r e is a g r e a t e r


weight l o s s f r o m r a p i d - r a t e m e t h a n e formation resulting f r o m the higher
hydrogen p r e s s u r e .

236
C o r r e l a t i o n s f o r Rapid-Rate Methane F o r m a t i o n Stage

The amount of b a s e c a r b o n gasified during the r a p i d - r a t e methane f o r m a -


tion s t a g e c a n be e s t i m a t e d by t h e b a s e c a r b o n conversion level, XR, ob-
tained f r o m weight l o s s - v e r s u s - t i m e c h a r a c t e r i s t i c s 2 m i n u t e s a f t e r a
s a m p l e i s lowered into the r e a c t o r . As indicated previously, t h i s c o r r e s p o n d s
to the t i m e r e q u i r e d f o r c o a l heat-up. During t h i s p e r i o d negligible conversion
o c c u r s in t h e l o w - r a t e gasification stage, although devolatilization and r a p i d -
r a t e methane formation r e a c t i o n s should be complete at t e m p e r a t u r e s above
approximately 1500 " F . Values of XR have b e e n c o r r e l a t e d with hydrogen
partial pressure, P according to the following e x p r e s s i o n f o r data obtained
H,'
i n t e s t s conducted at a v a r i e t y of conditions:

where
\
= hydrogen p a r t i a l p r e s s u r e , a t m
PH2
= r e l a t i v e reactivity f a c t o r f o r r a p i d - r a t e methane formation
fR
dependent on the p a r t i c u l a r c a r b o n a c e o u s solid. (Defined a s
unity f o r a i r - p r e t r e a t e d I r e l a n d m i n e c o a l c h a r . )

o! = kinetic p a r a m e t e r dependent on g a s composition and p r e s s u r e

The value of Q i n the above e x p r e s s i o n is approximately 0. 97 f o r t e s t s con-


ducted in p u r e hydrogen o r in hydrogen-methane m i x t u r e s , and i s approxi-
m a t e l y equal to 1 . 7 f o r a wide v a r i e t y of g a s compositions containing s t e a m
and hydrogen. T h i s p a r a m e t e r w i l l be d i s c u s s e d i n g r e a t e r d e t a i l i n a l a t e r
section on the l o w - r a t e gasification s t a g e . It i s of i n t e r e s t h e r e , however,
that f o r the c a s e w h e r e cy = 0.97, then M(X ) E
R - - ln(1 - XR )'
In F i g u r e 3 , a plot of the function, M(XR), v e r s u s hydrogen p a r t i a l p r e s s u r e ,
P f o r a number of t e s t s conducted on the t h e r m o b a l a n c e with a i r - p r e t r e a t e d
H2 '
Ireland m i n e coal c h a r , shows t h e good a g r e e m e n t between t h e s e data and t h e
c o r r e l a t i o n f o r m given i n Equation 6. Equation 6 a l s o a p p e a r s to be r e a s o n -
ably applicable to the gasification of s o m e coals, a s w e l l a s to coal c h a r s .

237
07
TEMPERATURE RANGEF: GAS
0 1550- 1600
06 A 1700

-a 0 1750
v 1600
X
0 1600- 1650
? 05
z
0
I-
V
3
(L
04

z
0
4
I-
03

00
' > IO 20 30
HYDROGEN PARTIAL PRESSURE,atm
40 50 60 70

A-112- 1006

F i g u r e 3 . CORRELATION O F BASE CARBON CONVERSION FOR


GASIFICATION O F AIR-PRETREATED IRELAND MLTE
COAL CHAR I N T H E RAPID-RATE METHANE FORMATION STAGE

Data obtained by Birch, &, f o r the hydrogenation vf Brown coal i n a


fluid bed and by Hiteshue, e t a l . , lo f o r t h e hydrogenation of a hvAL FittsburgkA
c o a l i n a fixed bed a r e given in F i g u r e s 4 and 5 . Details of the p r o c e d u r e s
used in treating the data f r o m t h e s e t w o investigations have beer, previoczly
described." It i s of practical i n t e r e s t that r e i a t i v e l y s m a l l variations in
values of f R & r e exhibited by the different m a t e r i a l s considered. Simiizr
s m a l l d e g r e e s of variation have ale0 been noted f o r s e v e r a l other bituminous
c o a l c h a r s tested a t IGT using t h e thermobalance.

T h e gasification of b a s e c a r b o n in the r a p i d - r a t e methane formation stage


is apparently only dependent on hydrogen p a r t i a l p r e s s u r e and i s not d e -
pendent on t h e p a r t i a l p r e s s u r e s of other gaseous s p e c i e s normally p r e s e n t
in gasifying a t m o s p h e r e s . This is partly indicated in F i g u r e 3 f o r t e s t s

238
0 10 20 30 40
HYDROGEN PRESSURE, atm
A-112-1005

F i g u r e 4. CORRELATION O F BASE CARBON CONVERSION FOR


GASIFICATION O F BROWN COAL IN A FLUID BED I.N T H E
\
RAPID-RATE METHANE FORMATION STAGE'

a
X

/
Y

2 0.8

2-
0
I-
U 0.6
Z
3
LL I A A S L O P E = 0.0105 atm-'

0 1470
A 2190

0 20 40 60 80 100
HYDROGEN PRESSURE, otm-l
1-112-1008

F i g u r e 5. CORRELATION O F BASE CARBON CONVERSION FOR


GASIFICATION O F hvAb PITTSBURGH COAL IN A FIXED BED
IN THE RAPID-RATE METHANE FORMATION STAGE'O
239
conducted with hydrogen-methane and hydrogen-steam m i x t u r e s , and h a s
a l s o been o b s e r v e d with s y n t h e s i s - g a s m i x t u r e s . In a s y s t e m containing
no hydrogen, n o evAution of b a s e c a r b o n o c c u r s except through gasification
i n the l o w - r a t e gasification stage. In F i g u r e 6, t h i s effect is i l l u s t r a t e d f o r
t e s t s conducted with p u r e s t e a m . After the first few m i n u t e s , t h e r e is no
difference in the weight-loss t r a c e s f o r a s a m p l e of a i r - p r e t r e a t e d coal c h a r
initially l o w e r e d into a s t e a m a t m o s p h e r e , and one which w a s devolatilized
i n nitrogen p r i o r t o being exposed to the s t e a m a t m o s p h e r e . T h i s behavior
c a n b e c o m p a r e d t o r e s u l t s shown i n F i g u r e 2 f o r similar t e s t s conducted i n
hydrogen.

0.8I

::
- 0.7
.- -
In
0

0
al 0.6 -
L
al

m
\
m 0.5 -
NITROGEN-PRE-
z TREATED COAL
0
,=
V
0.4 - CHAR, H20 AT

U
U
LL

cn COAL CHAR, N, AT 500 psig


cn
sc
I TEMPERATURE = 1700OF
c3
W
3 0.1 -

0 I 2 3
TIME,
4
min
5 6 7 8
i
A-112-IOZ2

F i g u r e 6. WEIGHT-LOSS CURVES OBTAINED IN HIGH-PRESSURE


THERMOBALANCE FOR GASIFICATION O F AIR-PRETREATED
IRELAND MINE COAL CHAR IN STEAM AND IN NITROGEN

240
Although the effects of p r e t r e a t m e n t t e m p e r a t u r e on reactivity in the
r a p i d - r a t e methane formation stage have not been systematically studied i n
this investigation, s o m e indication is apparent f r o m the r e s u l t s given i n
F i g u r e 7. It shows total weight l o s s e s f o r m a t e r i a l s subjected to different
p r e t r e a t m e n t s i n nitrogen obtained a f t e r gasification of air - p r e t r e a t e d coal
char in hydrogen f o r 1 hour. Below 1000"F, no effect of the nitrogen p r e -
t r e a t m e n t is apparent on subsequent weight l o s s i n hydrogen. Above t h i s
t e m p e r a t u r e , however, the total weight l o s s f o r m a t e r i a l s initially exposed
to nitrogen tends to d e c r e a s e with increasing t e m p e r a t u r e , and above
approximately 1500 "F, no r a p i d - r a t e methane formation o c c u r s with these
materials.

The c o r r e l a t i o n d e s c r i b e d by Equation 6 w a s developed based on data ob-


tained f r o m thermobalance t e s t s conducted above 1500 "F, w h e r e coal c h a r
samples w e r e submitted to r a t h e r specific heat-up rates c h a r a c t e r i s t i c of
the experimental a p p a r a t u s (approximately 30 O F / s). The fact that t h i s
c o r r e l a t i o n a p p e a r s to apply f o r data obtained i n o t h e r experimental s y s t e m s
w h e r e heat-up r a t e s a s high a s 200 "F/s w e r e employed, suggests that,
within a limited range of heat-up r a t e s , b a s e carbon conversion in the rapid-
r a t e methane formation stage is independent of heat-up r a t e f o r f i n a l t e m p e r a -
t u r e s g r e a t e r than 1500 O F . This conclusion only a p p l i e s f o r the case w h e r e
reaction i n the r a p i d - r a t e methane formation stage goes to completion. At
sufficiently low t e m p e r a t u r e s , the amount of b a s e carbon conversion which
can be attributed to r a p i d - r a t e methane formation, is l e s s than that which
would be predicted by Equation 6, even f o r exposure to hydrogen for p e r i o d s
a s long a s 1 hour. T h i s is apparent f r o m the r e s u l t s shown f o r curve A
in F i g u r e 7.

Data obtained in a s e r i e s of experiments conducted a t lower t e m p e r a t u r e s ,


such a s those i l l u s t r a t e d in Figure 7 , have been c o r r e l a t e d using a m o r e
I
detailed m o d e l to d e s c r i b e the r a p i d - r a t e methane f o r m a t i o n p r o c e s s p r i o r
to the completion of this reaction. This m o d e l is d e s c r i b e d in a previous
publication. It is of i n t e r e s t here, however, t o point' out c e r t a i n c h a r a c -
t e r i s t i c s of t h i s m o d e l which rationalize the independence of total b a s e
Y

i
24 1
E
c
0

q m

242
\

c a r b o n conversion i n the r a p i d - r a t e methane f o r m a t i o n stage f r o m heating


r a t e and final t e m p e r a t u r e f o r t e s t s conducted above 1500 "F. T h e following
c r i t i c a l s t e p s a s s u m e d i n the model r e l a t e to t h i s r a n g e of conditions:

A. -+ A*

A* -4 B
A*
b a s e c a r b o n t hydrogen- methane (9)
T h i s model, which i s qualitatively similar to one p r o p o s e d by Mosely and
Patterson, l3 a s s u m e s that the coal c h a r initially f o r m s a n active i n t e r m e d i a t e ,
A,, (Equation 7 ) which c a t a l y z e s the r e a c t i o n between b a s e c a r b o n and
g a s e o u s hydrogen t o f o r m methane (Equation 9). T h i s reaction, however,
c o m p e t e s with a r e a c t i o n i n which A , deactivates to f o r m the inactive s p e c i e s ,
B (Equation 8).

The following e x p r e s s i o n is a s s u m e d t o d e s c r i b e t h e r a t e of r e a c t i o n in
Equation 9:

where

k,(T) = rate constant dependent on t e m p e r a t u r e , T

= concentration of s p e c i e s , A, m o l / m o l of b a s e carbon
NA*
t = time

The r a t e s of r e a c t i o n s i n Equations 7 and 8 a r e a s s u m e d to be f i r s t o r d e r ,


leading to t h e e x p r e s s i o n -
I d(NA t N )/dt = - k2(T) *
* NA*
where,

k2(T) = r a t e constant, dependent on t e m p e r a t u r e

r NAO
= concentration of s p e c i e s , Ao, m o l / m o l base carbon

24 3
Combining Equations 10 and 11 l e a d s to the expression -
= - fR +$+ pH:l - X)2h exp(-aX2) (12)

If, then, it i s a s s u m e d that the r a t i o k,(T)/k,(T) i s independent of t e m p e r a t u r e


and is equal to then Equation 12 can be integrated to yield the following
expression f o r the condition a t which a l l of the species A
. h a s b e e n converted
to B.
X-
M(XR) =/, ' = fRB * NA
0 P
0 HZ

Comparing this e x p r e s s i o n with Equation 6 indicates that BNo = 0.0092


AO.
atm-'. Since no definition of the t e m p e r a t u r e history w a s r e q u i r e d i n the
development of Equation 1 3 , the suggested m o d e l indicates that the amount of
b a s e carbon conversion to m e t h a n e during the r a p i d - r a t e methane formation
step i s independent of heat-up r a t e or t e m p e r a t u r e level when the intermediate,
A, h a s been completely deactivated.

C o r r e l a t i o n s f o r Low-Rate Gasification Stage

F o r p r a c t i c a l purposes, coal c h a r s undergo low-rate gasification only


a f t e r the devolatilization and r a p i d - r a t e methane formation reactions a r e ,
completed. R e s u l t s obtained with the thermobalance indicate that, a t t e m -
p e r a t u r e s g r e a t e r than 1500"F, c h a r reactivity over a m a j o r r a n g e of carbon
conversion in the low-rate stage is substantially the s a m e whether devola-
tilization o c c u r s in nitrogen, o r i n a gasifying a t m o s p h e r e a t the s a m e
conditions. Therefore, t h i s study t r e a t s low-rate char gasification a s a
p r o c e s s essentially independent of devolatilization conditions, with one
important exception: The t e m p e r a t u r e of devolatilization, since it h a s been
shown in this study a s w e l l a s by Blackwood' that the reactivity of a c h a r a t
a given t e m p e r a t u r e , T, d e c r e a s e s with i n c r e a s i n g p r e t r e a t m e n t t e m p e r a t u r e ,
To, when T
0
=.T. This effect i s quantitatively r e p r e s e n t e d i n the c o r r e l a t i o n s
p r e s e n t e d below. However, t h e m o d e l adopted does not account f o r p r e t r e a t -
m e n t effects on gasification during initial s t a g e s of c h a r gasification, which

a
244
o c c u r p a r t i c u l a r l y a t gasification t e m p e r a t u r e s l e s s than 1600 OF. At t h e s e
lower t e m p e r a t u r e s , specific p r e t r e a t m e n t conditions such a s g a s a t m o s -
p h e r e and time of p r e t r e a t m e n t produce somewhat complex effects during
subsequent gasification f o r b a s e c a r b o n c o n v e r s i o n s of l e s s than 10 %.
T h e s e limitations have no p r a c t i c a l significance in using the simplified
model developed to d e s c r i b e coal c h a r gasification kinetics at higher t e m -
p e r a t u r e s , o r f o r b a s e carbon c o n v e r s i o n l e v e l s sufficiently g r e a t e r than
10 %.

T h e gasification data of Zielke and Gorin”. I9 and Goring, et.,obtained


f o r fluid-bed gasification of Disco c h a r , a s w e l l a s the bulk of data obtained
in IGT’s s t u d i e s with the h i g h - p r e s s u r e t h e r m o b a l a n c e and pilot-scale fluid
beds, w e r e used t o evaluate p a r a m e t e r s in a quantitative model developed
to d e s c r i b e c o a l c h a r gasification k i n e t i c s over a wide range of conditions
i n the l o w - r a t e gasification s t a g e . T h r e e b a s i c r e a c t i o n s w e r e a s s u m e d to
o c c u r i n g a s e s containing s t e a m and hydrogen:

Reaction I: H20 t C ;r C O t €3,

Reaction LI: 2H2 t C ;r CH,


Reaction ILI: H, t HzO t 2 C e C O t CH,

Reaction I i s the conventional s t e a m - c a r b o n reaction, which is the only one


that o c c u r s i n p u r e s t e a m at elevated p r e s s u r e s * o r with g a s e s containing
s t e a m a t low p r e s s u r e . Although, at e l e v a t e d t e m p e r a t u r e s t h i s reaction is
affected by thermodynamic r e v e r s i b i l i t y only f o r r e l a t i v e l y high s t e a m con-
v e r s i o n s , t h e r e a c t i o n i s s e v e r e l y inhibited by the poisoning effects of
hydrogen and c a r b o n monoxide at s t e a m c o n v e r s i o n s f a r r e m o v e d f r o m
equilibrium f o r t h i s reaction. Some i n v e s t i g a t o r s have a l s o noted inhibition
by methane.

Reaction 11, the only r e a c t i o n that could o c c u r i n p u r e hydrogen o r i n


hydrogen-methane m i x t u r e s , g r e a t l y depends on the hydrogen p a r t i a l p r e s s u r e .
Many i n v e s t i g a t o r s have found that, at e l e v a t e d p r e s s u r e s , the r a t e of t h i s
r e a c t i o n i s d i r e c t l y p r o p o r t i o n a l to t h e hydrogen p a r t i a l p r e s s u r e .

* Although s o m e methane h a s been d e t e c t e d in gaseous r e a c t i o n products


when gasification i s conducted with p u r e s t e a m , it i s u n c e r t a i n whether
t h i s methane r e s u l t s f r o m the d i r e c t r e a c t i o n of s t e a m with c a r b o n o r
f r o m the s e c o n d a r y r e a c t i o n of hydrogen, produced f r o m the s t e a m -
carbon r e a c t i o n , with the c a r b o n in t h e c h a r .
245
T h e stoichiometry of Reaction III limits i t s o c c u r r e n c e to s y s t e m s in
which both s t e a m and hydrogen a r e present. Although this r e a c t i o n is the
stoichiometric s u m of Reactions I and 11, this m o d e l c o n s i d e r s it to be a
t h i r d independent gasification reaction. This reaction, a r b i t r a r i l y a s s u m e d
to o c c u r i n the development of t h i s m o d e l t o facilitate correlation of ex-
p e r i m e n t a l data, h a s been suggested by Blackwood and McGrory4 a s being
n e c e s s a r y i n such a system. C u r r a n and Gorin5 a l s o a s s u m e d this reaction
t o c o r r e l a t e kinetic data f o r gasification of lignite at 1500 "F i n steam-
hydrogen- containing g a s e s .

The c o r r e l a t i o n s developed in t h i s study to d e s c r i b e kinetics i n the low-


rate gasification stage a r e s u m m a r i z e d a s follows:

dX/dt = f L kT (1 - X)2'3 exp(-QXZ) (14)


where,
k = k t k t k '
T I I I L U

H e r e , kI, krr, and km a r e r a t e constants f o r t h e individual r e a c t i o n s con-


sidered. It is a s s u m e d t h a t each of the t h r e e r e a c t i o n s occur independently,
but that the r a t e of e a c h is proportional to the same s u r f a c e a r e a and surface
reactivity terms. The term (1 - X)" is proportional to the effective surface
are? undergoing gasification, and the t e r m exp(--crX2) r e p r e s e n t s the relative
reactivity of the effective s u r f a c e a r e a , which d e c r e a s e s with increasing
conversion l e v e l f o r positive values of CY.

Individual p a r a m e t e r s in Equations 14 and 1 5 a r e defined a s functions of


t e m p e r a t u r e and p r e s s u r e according to the following e x p r e s s i o n s :

f L = fo exp (8467/To)

k1 -
- (17 1
t-16.35

246
-
kLI =
1t P
exp(2.67;i

H2
- 33,076/T) (1

exp -10.4520 t 19,97d/T)


)

I
I ' \
kIII =

ff = '
-
~
$2

H2
P
H2O
exp(12.4463 - 44,544/T)

i 1 t e x p ( 4 . 6 6 9 6 t 15,198/T) P

52.7 PH
/-:

0. 521
H 7.
PH
7.
PCH4PC0
E l
PH,PH,OKIII -/
pCH4
t 0.85PC, t 18.62 p__
. _
\'

1 + 54.3 P' 10.707P t 0. 50 P'/2 P


H2 HZO H2 H2O
where,
E E E
KI , KII, KIU = equilibrium constants f o r r e a c t i o n s I, II, and III,
considering carbon a s graphite

T = reaction t e m p e r a t u r e , "R

= maximum t e m p e r a t u r e t o which c h a r h a s b e e n exposed


TO
p r i o r to gasification, "R (if To < T , then a value of
T = T is u s e d in Equation 16)
0

'H,' 'H20'

P = p a r t i a l p r e s s u r e s of H2, H 2 0 , CO, and CH,, a h


'CO' CH,

fO
= r e l a t i v e reactivity f a c t o r f o r low-rate gasification
dependent on the p a r t i c u l a r carbonaceous s o l i d

Values of fo obtained in this study w e r e based on t h e definition f o = 1 . 0


f o r a specific batch of a i r - p r e t r e a t e d Ireland mine c o a l c h a r . Samples of
I
this coal c h a r obtained f r o m different a i r - p r e t r e a t m e n t t e s t s exhibited some

I v a r i a t i o n s i n reactivity a s determined by thermobalance t e s t s conducted a t


standard conditions. The values of f so determined, ranged f r o m approxi-
0
m a t e l y 0.88 to 1. 05. Results of t e s t s made with the thermobalance using a
v a r i e t y of c o a l s and coal c h a r s have indicated that the r e l a t i v e reactivity
f a c t o r , fo, generally tends to i n c r e a s e with d e c r e a s i n g r a n k , although

247
individual exceptions t o t h i s t r e n d exist.

M(X) =/,

=/, xR

The t e r m i A R
ex +cwXz dX =CR
tfLkTt
---- Values have been obtained
which r a n g e f r o m 0. 3 f o r a low-volatile bituminous c o a l c h a r to about 10 f o r
a North Dakota lignite. T h e r e a c t i v i t y of the Disco c h a r u s e d i n gasification
studies conducted by t h e Consolidation C o a l Company9*

+Jx
XR
‘9 is fo = 0.488.

An i n t e g r a t e d f o r m of Equation 14 w a s used to evaluate c e r t a i n p a r a m e t e r s


i n the above c o r r e l a t i o n s , b a s e d o n data obtained with the thermobalance.

w a s evaluated f r o m Equation 6 for t e s t s in

which no nitrogen p r e t r e a t m e n t w a s used. For t e s t s i n which the feed c o a l


c h a r w a s initially devolatilized in n i t r o g e n at t h e s a m e t e m p e r a t u r e and
p r e s s u r e to be subsequently used f o r gasification i n a gasifying a t m o s p h e r e ,
r e a c t i v i t y f o r r a p i d - r a t e m e t h a n e f o r m a t i o n w a s d e s t r o y e d above 1500 “F
and XR = 0. F o r this condition-

M(X) =lo X
= fLkT t

Typical plots of M(X) v e r s u s t a r e given in F i g u r e s 8, 9, and 10 f o r data


obtained with a i r - p r e t r e a t e d I r e l a n d m i n e coal c h a r . The slopes of the l i n e s
d r a w n c o r r e s p o n d to v a l u e s of fLkT c h a r a c t e r i s t i c of e a c h t e s t . R e s u l t s of
I
t e s t s conducted with p u r e s t e a m ( F i g u r e 8) w e r e c o r r e l a t e d using ~1 =0
c o n s i s t e n t with Equation 20 which c o r r e s p o n d s to the qituation i n which
s p e c i f i c gasification r a t e s , d x /at , i n c r e a s e with a n i n c r e a s i n g c a r b o n
c o n v e r s i o n level. F o r g a s i f i c a t i o n i n hydrogen o r steam-hydrogen m i x t u r e s
( F i g u r e s 9 and l o ) , however, s p e c i f i c gasification r a t e s g e n e r a l l y d e c r e a s e
with increasing conversion level.

248
2.0

3 95

\ 09

1. 1.5

T
- X
X
-
- z
2
&
m
-
I1
X
08 :
I-

LL
I z
z 0
fn
2 a
L 1.0 07 9z
z
3 0
LL V
z z
2 0
m
t
-I
06 a
a
w V
a W
a fn
8 35 2
0.5
/ PRESSURE =35.0otm
34

0 1700
53
A 1800
0 1900
32

31

0 3
0 2 4 6 8 IO 12 14

TIME,min

A-112-1007

F i g u r e 8. E F F E C T O F TEMPERATURE ON LOW-RATE GASIFICATION


O F AIR-PRETREATED IRELAND MINE COAL CHAR IN STEAM

249
0.9 x
..
z
0 I
2 2.0 6a
z- e
LL
i
0 3.8
I-
U
z 1.6 0
v)
3
LL
e
W
>
z z
0 1.2 0.7
GJ z
W 0
E
c
o.8
PRESSURE = 35.0 otm
3.6 m

3.5
LL
a
TEMPERATURE, OF W
v)
0 1700 1.4 a
0.4 m
A 1800 1.3
0 1900 1.2
1.I
0 1
0 20 40 60 80 too I20
TIME, min
8-112-1003

Figure 9 . E F F E C T O F TEMPERATURE ON LOWTRATE GASIFICATION


O F AIR-PRETREATED IRELAND MINE COAL CHAR IN HYDROGEN

250
I'
4.c

INITIAL BASE CARBON CONVERSION FRACTION = 0.43

\, 1.9

\
3s X

i
X 0
Y
I-
z O
a
CK
z- LL
0 z
I-
O
z 0
3 1.8
2.( W
>
z z
Q 8
G-I z
W 0
CT m
CT CK
a
8 O
w
v,
a
).6

0 46.5 16.2 1700 ).4


A 48.4 16.6 I800
0 47.0 20.0 1900
1.2

TIME, min
A-112-1002

F i g u r e 10. E F F E C T O F TEMPERATURE ON LOW-RATE


GASIFICATION O F AIR-PRETREATED IRELAND MINE
COAL CHAR IN STEAM-HYDROGEN MIXTURES

25 1

I
Carbon gasification r a t e s w e r e d i r e c t l y m e a s u r e d i n the fluid-bed t e s t s
conducted with Disco c h a r , 9 * and values of f k and O! can be obtained
I9
L T
dX/dt
graphically by plotting v a l u e s of I n v e r s u s Xz. Such a plot i s
x 13 dX/dt
illustrated in Figure I1,where the value of #(- a t X = 0 is equal
to fLkT and the slope of a given line is equal to 01. Generally, the c o r r e l a -
tions p r e s e n t e d a r e consistent with v a l u e s of fLkT and IY obtained f o r the
gasification of Disco c h a r at t e m p e r a t u r e s of 1600 and 1700 " F and p r e s s u r e s
of 1, 6, and 30 a t m o s p h e r e s f o r gasification with pure hydrogen and with
v a r i o u s steam-hydrogen m i x t u r e s . The c o r r e l a t i o n s a r e a l s o consistent
with individual r a t e s of methane and c a r b o n oxide formation r e p o r t e d in the
investigations conducted with Disco c h a r f o r initial l e v e l s of c a r b o n conver -
sion. Although the relative r a t e s of methane to carbon oxide f o r m a t i o n
w e r e r e p o r t e d to i n c r e a s e somewhat with i n c r e a s i n g conversion level,
a t r e n d not accounted f o r in the m o d e l developed in t h i s study, i n v e s t i g a t o r s
a t t h e Consolidation Coal Company have suggested that t h i s effect w a s
caused by a catalytic reaction d o w n s t r e a m of the fluid-bed r e a c t o r em-
ployed, in which some of the c a r b o n monoxide produced in the r e a c t o r was
converted t o methane.

The consistency between the calculated and experimental values of fLkT


f o r t e s t s conducted a t a v a r i e t y of conditions with the thermobalance using
a i r - p r e t r e a t e d Ireland m i n e coal c h a r i s demonstrated in Tables 2, 3 , and
4 and in F i g u r e s 12, 13, and 14. The c o r r e l a t i o n s developed have a l s o b e e n
used to p r e d i c t behavior in p i l o t - s c a l e moving- and fluid-bed t e s t s conducted
a t IGT and elsewhere. The a s s u m p t i o n s made in c h a r a c t e r i z i n g the nature
of g a s - s o l i d s contacting in t h e s e i n t e g r a l s y s t e m s have been previously
described. l4 The most important a s s u m p t i o n s made f o r fluid-bed s y s t e m s
a r e a ) the g a s in t h e fluid bed is p e r f e c t l y mixed and b ) when continuous
solids flow i s employed, the s o l i d s a r e in plug flow. F o r moving-bed
s y s t e m s , we assumed t h a t both g a s and solids w e r e i n plug flow. With
t h e s e simplifying assumptions, the conditions of p r i m a r y importance i n

252
U
a
U m Nmm o d m m m + e m 9 NN-Ilnoa -e* 0
d a -4- m a e a r - e e m e omr?m-lm m - 4 N
-i 0 --e 0 " N W " NNNN o-lmmma fua* m
L-
A.
2
U
-i
0
0
. . . 0
0 0 0
0 0 0
. 0. 0. 0. 0. . . . . 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 O d O d O 0
0 0 0 0 0 0 0
. . .
0 0 0
.
0
0
c d
c1 L)
Y
c
rd
-
I
Y c
z
.A

0
E
U
0
Y
rd
W
a
0
e-r-
- 4 - 0 ' .
-4-0
a e a N m d*eN
o a e m e a e m e
.-ANN- NNNN
l n o o o o N-a
r-lnmoo N V -
-4mNme N a v
-
. . . .
0
Q\
0: 0

0
. . . . . . . . . . . .
0 0 0
0 0 0
0 0 0 0 0
0 0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0 0 0
d0OdO
0 0 0
0 0 0
0
0

_-
c
0

*
4
-IN*
*G-m
o\*ooo m m o
a m e m m \ o a -
0

m m a O-4m-N
W

0
. . . 0. 0. 0. 0.0. 0 0 0 d o d d ~ d d0 0 0
0 0 0
NNO\ 03

0
I I l l I 1 . 1 I I I l l 1 I I I I I I l l I
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

m
m
u
L w e e
In
. . . . . . .
* * + N
m m a m
\c) aaa
-lm mm mmmm

J'

0 0 0 0 0 0 0 0 0
* 0 0 0 0
0 m m m 0 0 0 0 0 lnmmln
a a a er-eer- 4
e e e e
2 3 4 3 - 4 4
- 4 - d -

253
I

I
. . . . . . . . . . . 0. 0. 0. 0.
00000000 0 0 0

r - C O 9 m.O* PN0 *-\om 9 m F r c m 4 9 0 mmm m o o I


* m O a m * m a m N m * N N 4 \ O 4 O * O P m-l* m t - 0 0
mmI-mmmmN4NCO** ma\Omco**a m 4 9 ICmoCO
4000000000000
ddddddddooooo
. . . . . 0. 0. 0. 0. 4. 0. 0. 0. . . . . . . .
00000000 000 0000
N4-4 * a * 9

0ddodododdddd
. . . . . . . .
00000000
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
o o o o o o o o o o m m m
*** 00000000
*. *. *.
ddd 000

I
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N O N
. . .
I C O N It-t-m
* m 4 * m

z
o)

rd
F
0000000000000
* ** 000 0000
***
0000000000000 000 0000
r-I-Fbr-r-Fr-t-I-bFt- COCOm mmmm
4 4 4 3 4 H 4 4 4 4 - 4 4 4 4-44 3 4 4 r l

254
\DU'\DdmclWN \OW- O N m r l a 4 a m * N F mmC0r.m
m o o o * m o m o m m m o ~ ~ a m r n 4 c o a ~ 0r \ -4 c4 o 4 +
0 0 0 0 0 0 0 0 0 O N 0 * 4 4 4 O V N N 4 N M 4 O m m N 4
0
0
. . . . . . . . . . . .
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0
000
0 0 0
000000040000 0 0 0 0 0
ddddddoooooo
. . . . . . . . . . . 0 0 0 0 0

0
N N m a m a m ocoao N V 4 O O
* N0 0+ 0
In
0
a N a H N * a * m
0 0 0 N * O N O
04000
Nmm
O N 0
p
N
~ * a ~ 4 a * o r n m m
- I 4 4 4 m N O N 4 , 4 4
4 0 r - m ~ -
O W F N 4

d d d d d d o. o. o. o.o.o. . . . . .
o oooooo+oooo 00000
0
0
. 0. 0. 0. 0. 0. 0. 0.0. . . .
0 0 0 0 0 0 0 0 0 0 0
0 0 0 00000

+ ommm3acoa m m a
+ m*mNr-omF N O N

0
. . . . . . . . . N. +. * . d d d d d d d d o. o. o.o. . . . . .
N 4 - 3 N m - I N 3
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
I I I I I I I I I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 l l I I
o o o o o o o m m m m m ooooo
0 0 0 0 0 0 0 0 0 0 0 0
*. *. *. *. *.
0 0 0 0 0

N comco+mcooa a m m
m N m m 4 m m r - *
dddddd\dAd o o m
...
NNN

. . . . . . . . . . . .
0 0 0 0 0 0 C O P N O O N

*_ . .*,. *.,. *.,. *.,.


0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
moooooooo mmm 0 0 0 0 0 0 0 0 0 0 0 0 m m m m m
m a a a a a a a a a a a r+r-+Fr-+Fr-+r-F +++r-+
, 4 4 4 + 4 4 4 4 4 4 4 4 d 4 4 4 4 4 4 + 4 4 4 4 4 4 - 4 4

255
............
000000000000 ddddddoooooooo
........... 4 0 4

............
000000000000 ddodddddddddd; Ad;

. . . . . . . . . . . . 0. 0.0.0.0.0.0.0.~ .0 4
000000000000
. 0. -. 4. -.0-40
4
...
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 l l I 1 1 1
mmmmmmmmmmmm mmmmmmmmmmmmmm mmm
. . * * *. *. *.*.*.*.*.*.*.* .* .* .*0.0
*****e******
..........
000000000000
*.*.
0
d 0 O O O O O O O O O O O O

............
mNmm***NNm4-
00-4000000000

*0*0 *0 *0*0*0*0*0*0*0*0*0 *0*0 *0 *0 *0 *0 *0 *0 *0 *0 *0*0 *0 *0 *0*0*0


000000000000 00000000000000 000
wCOCOwWaJwcowwww m m m m u . m m m m m m u . P m 000
-l-l4.-4d4-4'-4#-l44-4 & 4 M r - l - - I d 4 ~ 4 # - l 4 - 4 4N
~ NN

256
500
TEMPERATURE=1700°F
4 00

IO
II I I
61

I I
0 0.2 0.4 0.6 0.8 I13
X2
a - 1 1 2 - 1004

F i g u r e 11. E F F E C T S O F PRESSURE AND GAS COMPOSITION ON


LOW -RATE GASIFICATION O F DISCO CHAR IN
STEAM-HYDROGEN MIXTURES9' l 9

- 1 0 NO PRIOR EXPOSURE TO NITROGEN


OR STEAM-HYDROGEN MIXTURE / I
'c 0.10 - A COAL CHAR INITIALLY DEVOLATILIZED
._
E IN NITROGEN, OR PARTIALLY GAS
F E D WITH STEAM AND HYDROGE
I-- IN A FLUID BE0
z
z
z
0.08

s
W 0.06
2l
K
D
W
5 0.04
1
3
J
V
a
0.02 TEMPERATURE RANGE 1600'-1900'F
PRESSURE RANGE 1-70 otm

0. 1 4
0 ' 0.02 0.04 0.06 0.08 0.10 0.12
EXPERIMENTAL RATE CONSTANT, rnin-l
I
~-IIZ-IOIO

F i g u r e 12. COMPARISON O F EXPERIMENTAL AND CALCULATED


RATE CONSTANTS FOR LOW-RATE GASIFICATION O F
AIR-PRETREATED IRELAND MINE COAL CHAR IN HYDROGEN
257
0 NO PRIOR EXPOSURE TO NITROGEN OR
STEAMIHYDROGEN MIXTURE
-,

/
A COAL CHAR INITIALLY DEVOLATILIZED
O.Io - IN NITROGEN, OR PARTIALLY GASIFIED
WITH STEAM AND HYDROGEN
IN A FLUID BED
I-
2 0 0 / 0 A
CQ
v,
0.08
z
8
IX
0
5W 0.04.
J
3
Ya
u 0.02. RANGE : 1700.- 1800.F
RANGE : 3 5 - 7 0 aim

Ol/ I I I 1 I

0 0.02 0.04 0.06 0.08 0.10 0 2


EXPERIMENTAL RATE CONSTANT, rnin-1
A-112-IO15

(a)

STEAM AND HYDROGEN


IN A FLUID BED

W
5
0.4 -
n
W
G1
2 0.2- TEMPERATURE RANGE:
Y
a
1700'- I90O0F
PRESSURE RANGE:
V
35-70 aim

0 0.2 0.4 0.6 0.8 I.o


EXPERIMENTAL RATE CONSTANT, rnin-l

A-112-1016

(b)

F i g u r e 13. COMPARISON O F EXPERIMENTAL AND CALCULATED


RATE CONSTANTS FOR LOW-RATE GASIFICATION O F
AIR-PRETREATED IRELAND MINE C O A L CHAR
I N STEAM-HYDROGEN MIXTURES
258
-'-I 0 NO PRIOR EXPOSURE TO NITROGEN
OR STEAM-HYDROGEN MIXTURE
A COAL CHAR INITIALLY DEVOLATILIZED
IN NITROGEN OR PARTIALLY
E

p
GASIFIED WITH STEAM AND
HYDROGEN IN A FLUID BED

a
004

TEMPERATURE RANGE
1550*-1900'F
a 002
V PRESSURE RANGE
3 5 - 7 0 atrn

0
0 002 004 006 008 010 012
EXPERIMENTAL RATE CONSTANT, rnin-'
A , I 2 101)

(4
16

/
COAL CHAR INITIALLY DEVOLATILIZED
IN NITROGEN OR PARTIALLY GASIFIED
- 14 WITH STEAM AND HYDROGEN IN A
I
FLUID BED
5
E

/
12 TEMPERATURE RANGE :
I-- 170Oe-200O0F
z
a
IO
z
s 08
W
t
(r
0.6
0
W
l-
a
J 04
3
Ya
02

0
0 0 2 04 06 08 IO I2 14 I6
EXPERIMENTAL RATE CONSTANT, min-'
.-112-1018
F
( b)
F i g u r e 14. COMPARISON O F EXPERIMENTAL AND CALCULATED
RATE CONSTANTS FOR LOW -RATE GASIFICATION O F
AIR-PRETREATED IRELAND MINE COAL CHAR LN SYNTHESIS GASES

239
i
(1

c h a r a c t e r i z i n g i n t e g r a l gasification behavior in individual t e s t s include c o a l I


c h a r f e e d r a t e and composition, p a r t i c l e residence t i m e s in the r e a c t o r , i
r e a c t o r t e m p e r a t u r e , p r e s s u r e , feed g a s composition, and flow r a t e . For
c a s e s w h e r e coal c h a r containing volatile m a t t e r w a s used a s a feed material,
r a p i d - r a t e methane formation and devolatilization w e r e a s s u m e d to o c c u r
i n a f r e e - f a l l s p a c e above the r e a c t i o n beds employed in t h e s y s t e m s . When
devolatilized c o a l c h a r w a s the feed m a t e r i a l , no r a p i d - r a t e methane f o r m a -
tion w a s considered to occur. P r e d i c t e d and experimental i n t e g r a l r a t e s of
carbon oxides and methane f o r m a t i o n a r e compared in F i g u r e s 15-19, which
show good a g r e e m e n t f o r a wide r a n g e of experimental conditions.

Frequently, the PCH4/PL2r a t i o i n product g a s e s f r o m integral fluid-bed


s y s t e m s f o r the gasification of c o a l o r coal c h a r with steam-hydrogen con-
taining g a s e s is g r e a t e r than t h e equilibrium constant f o r the g r a p h i t e -
hydrogen-methane system. T h i s h a s often been i n t e r p r e t e d a s corresponding
t o a situation i n which the c o a l o r c o a l c h a r has a thermodynamic activity
g r e a t e r than unity with r e s p e c t t o graphite. The m o d e l s proposed in this
paper offer two other explanations f o r this phenomenon: Rapid-rate methane
f o r m a t i o n o c c u r s when c o a l o r c o a l c h a r containing volatile m a t t e r is used
a s a feed m a t e r i a l . The m e t h a n e yield resulting f r o m t h i s step i s kinetically
determined, independent of m e t h a n e ' s p a r t i a l p r e s s u r e . Under c e r t a i n con-
ditions then, values of the ratio, P /PL2. g r e a t e r than that corresponding
c H4
t o the equilibrium for the graphite-hydrogen-methane s y s t e m c a n r e s u l t .
Values of the PCH4/@H2 r a t i o g r e a t e r than that corresponding to the equilibrium
considered can a l s o o c c u r f o r l o w - r a t e gasification of c o a l c h a r according t o
the model a s s u m e d in t h i s study. T h i s i s i l l u s t r a t e d i n F i g u r e 20, w h e r e the
r e s u l t s shown w e r e based on computations of gas yields i n a hypothetical
fluid-bed f o r c h a r gasification with a p u r e s t e a m feed g a s , using the c o r r e l a -
tions d e s c r i b e d above. The r e a s o n f o r the behavior i l l u s t r a t e d is that, a t
i n t e r m e d i a t e v a l u e s of hydrogen p a r t i a l p r e s s u r e , the r a t e of Reaction LU,
which produces methane, i s g r e a t e r than the r e v e r s e r a t e of Reaction 11 in
which methane i s consumed when a potential f o r carbon deposition by this

260
0.572
lo=
fR: 0.694

w.
aE
L
r
1

0.10 -
PRESSURE i 140 otrn

X I

AV G

0 1252 0.0029
A 1291-1317 0 0029
0 1347-1376 0.0029
V 1440 0.0029
0 1485 0.0095

0 0.05 0.10 0.15


EXPERIMENTAL METHANE
FORMATION RATE, Ib-mol./hr
1-112-1020

F i g u r e 15. -COMPARISON O F EXPERIMENTAL AND CALCULATED


INTEGRAL RATES O F METHANE FORMATION FOR HYDROGENATION
O F MONTOUR BITUMINOUS COAL CHAR (17 % Volatile M a t t e r ) IN A
MOVING-BED REACTOR (IGT Study)

V TEMPERATURE RANGE. I590'-l88OoF


PRESSURE RANGE:' 15-103 atm

Z 04-
E

0
V 0.3 - FEED SOLIDS
COAL CHAR
WITHOUT
COAL CHAR VOLATILE
WITH MATTER
I VOLATILE (PARTIALLY
FEED GAS MATTER GASIFIED)

0
SYNTHESIS GAS . .A , . v .

0 0.1 0.2 0.3 0.4 05 06 0.7


EXPERIMENTAL (CO + COz). mol/mol feed C
e-112-1021

F i g u r e 16. COMPARISON O F EXPERIMENTAL AND CALCULATED


INTEGRAL RATES O F CARBON OXIDES FORMATION FOR GASIFICATION
O F AIR-PRETREATED IRELAND MINE COAL CHAR IN 2 - , 4-, AND
6-INCH-INSIDE-DIAMETER FLUID-BED REACTORS (IGT Studies)
26 1
d
!

Y
TEMPERATURE RANGE : 1590" 1880' F
PRESSURE RANGE : 15- IO3 atm

fo' 1.0
- f,= 1.0

FEED SOLIDS

qO& CHAR
WITHOUT
COAL CHAR VOLATILE
WITH MATTER
VOLATILE (PARTIALLY
FEED GAS MATTER GASIFIED:

H 2 0 OR H2/H20 0 0
SYNTHESIS GAS b v

0 0.1 0.2 0.3


EXPERIMENTAL CH4, mol/mol feed c
A- II2-1014

Figure 17. COMPARISON O F EXPERIh4ENTAL AND CALCULATED


INTEGRAL RATES O F METHANE FORMATION FOR GASIFICATION
O F A q - P R E T R E A T E D IRELAND MINE COAL CHAR IN 2 - , 4-, AND
6 -INCH-INSIDE -DIAME TER FLUID-BED REACTORS (IGT Studie 8 )
0.6

L
/
r
0.5 - TEMPERATURE RANGE : 1602'- 1816' F
- PRESSURE RANGE: 4.1 - 9.5 otrn

\
E
-0 to ~ 0 . 4 8 8
E 0.4 -
N
0
V
+ 0.3 -

D
W
5 0.2 -
3
FEED GAS

V
J
a
V
0.1 -

0 0.1 0.2 0.3 0.4 0.5 C 6


EXPERIMENTAL (CO+COz), mol/rnol C-hr A-112-1013

\ F i g u r e 18. COMPARISON O F EXPERLMENTAL AND CALCULATED


INTEGRAL RATES O F CARBON OXIDES FORMATION FOR
GASIFICATION O F DISCO CHAR IN A FLUID-BED REACTOR"

.
' t
2
V
0.06
TEMPERATURE RANGE
PRESSURE RANGE. 4.1-9.5otm
: 1602'-1816'F

,"
I o.031
1
0
w
t+ 0.02
I y o
V
1 FEED GAS
9 0.01 0 HzO. H20/N2

0
, p
A H20/H2
HzO~H2
,
0 001
0.01 002
0.02 003
0.03 0 .00 4
0 4 005
0.05 C 16
L EXPERIMENTAL CH4, mol/rnol C-hr
*-1,2-1012

F i g u r e 19. COMPARISON O F EXPERLMENTAL AND CALCULATED


INTEGRAL RATES O F METHANE FORMATION FOR
GASIFICATION O F DISCO CHAR IN A FLUID-BED REACTORlZ

263
TOTAL PRESSURE,

GRAPHITE

0.3mol C IN GAS
BASIS:
mol F E E D H z 0

0.001

RECIPROCAL TEMPERATURE, OR-' X IO4 A-112-1019

F i g u r e 20. CALCULATED VARIATIONS O F THE METHANE


l'EQUILIBRIUM'' RATIO ( P
CH4
/eH,)
FOR GASIFICATION
O F CARBON WITH STEAM IN 4 BACKMIXED REACTOR

reaction exists. The p a r t i a l p r e s s u r e dependencies defined in t h e c o r r e l a -


t i o n s developed a r e such, however, that, a t sufficiently high hydrogen I

p a r t i a l p r e s s u r e s , Reaction II d o m i n a t e s and equilibrium f o r t h i s r e a c t i o n


i s approached.
'
T h e qualitative t r e n d s exhibited in F i g u r e 20 and even t h e m a g n i t u d e s
of t h e s e t r e n d s b e a r a s t r i k i n g r e s e m b l a n c e t o a s i m i l a r plot given by
Squires's to c o r r e l a t e the a c t i v i t i e s of c o a l s and c h a r s f o r e q u i l i b r i u m i n
the char-hydrogen-methane s y s t e m with t e m p e r a t u r e and p r e s s u r e .

264
SUMMARY OF NOTATION

A nongasifiable m a t t e r i n feed c o a l c h a r (including a s h and


s o m e sulfur), g / g feed c o a l c h a r

b a s e c a r b o n in c o a l c h a r a t a n i n t e r m e d i a t e gasification
level, g / g feed c o a l c h a r

c a r b o n in the fixed carbon f r a c t i o n of t h e feed coal c h a r


a s d e t e r m i n e d by a proximate analysis,$ g/g feed c o a l
char

total carbon in the feed coal char a s d e t e r m i n e d by a n


ultimate analysis, g / g feed coal c h a r

cV
volatile c a r b o n in feed coal, g / g feed coal c h a r

fO
relative reactivity factor f o r l o w - r a t e gasification
dependent on the p a r t i c u l a r carbonaceous solid

fL r e l a t i v e reactivity f a c t o r f o r l o w - r a t e gasification
dependent on the p a r t i c u l a r carbonaceous solid and
pretreatment temperature

fR r e l a t i v e reactivity factor for r a p i d - r a t e methane


formation, dependent on the p a r t i c u l a r carbonaceous
solid

kT o v e r a l l r a t e constant f o r l o w - r a t e gasification, min-’

k r a t e constants, m i n - ’
*(T)’ k3(T)
r a t e constants f o r Reactions I, 11, and ILL, min-’
kI’ kII’ kIII
E E E
equilibrium constants f o r Reactions I, 11, and I11
K, ’ KII’ KIII considering c a r b o n a s graphite

concentration of species A a t any time, mol/mol


base carbon

initial concentration of s p e c i e s A mol/mol base carbon


0’

concentration of s p e c i e s A, a t a n y t i m e , m o l / m o l b a s e
carbon

PH,,PHz0, Pco, Pco,,PCH4= ~ ; ~ i a : ~ ~ e s s u r eofs H,, H,O, CO, CO2 and

265
t = time, m i n
T = r e a c t i o n t e m p e r a t u r e , OR

= p r e t r e a t m e n t t e m p e r a t u r e , "R
TO

V = volatile m a t t e r in feed coal c h a r (including m o i s t u r e ) ,


g / g feed coal char

wO
= weight of f e e d c o a l c h a r , g

AW = weight l o s s of c o a l c h a r during gasification, g

X = total b a s e c a r b o n conversion f r a c t i o n
= b a s e c a r b o n conversion f r a c t i o n a f t e r r e a c t i o n in
xR r a p i d - r a t e m e t h a n e f o r m a t i o n s t a g e is completed

G r e e k Symbols

CL = kinetic p a r a m e t e r , dependent on g a s composition and c


pressure J

B = k,(T)/k,(T) r a t i o

Y = noncarbon m a t t e r evolved along with b a s e carbon,


g / g b a s e c a r b o n evolved

ACKNOWLEDGMENT
.f

T h e w o r k conducted i n t h i s study w a s s p o n s o r e d by t h e A m e r i c a n G a s
Association, the U . S. D e p a r t m e n t of t h e I n t e r i o r , Office of Coal R e s e a r c h ,
and t h e F u e l Gas A s s o c i a t e s . T h e author w i s h e s to e x p r e s s his appreciation
f o r the p e r m i s s i o n of t h e s e g r o u p s to publish this paper.

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268