I

RELATIONSHIP BETWEEN THE GASIFICATION REACTIVITIES O F COAL CHAR AND THE PHYSICAL AND CHEMICAL PROPERTIES O F COALANDCOALCHAR J a m e s L. Johnson Institute of G a s Technology 3424 S. State S t r e e t Chicago, Illinois 6061 6 INTRODUCTION A variety of experimental investigations have studied, a t elevated p r e s s u r e s , t h e gasification kinetics of coal c h a r s i n hydrogen a n d i n g a s e s containing steam and hydrogen. T h e bulk o t h e s e investigations, however, have been p r i m a r i l y f concerned with the characterization of gasification r a t e s a s a function of environm e n t a l conditions such a s t e m p e r a t u r e , p r e s s u r e , and g a s composition, and have provided little systematic information concerning relationships between gasification reactivities and t h e physical and chemical p r o p e r t i e s of coal o r coal char.

85

T h i s study w a s t h e r e f o r e initiated t o evaluate possible relationships between gasification reactivities and simple compositional p a r a m e t e r s f o r c o a l c h a r s derived f r o m a wide variety of coals and c o a l - m a c e r a l concentrates. T h e i n t e r n a l s t r u c t u r a l changes that occur during t h e c o u r s e of gasification of a few coal c h a r s of varying rank w e r e a l s o explored. The gasification reactivities of individual c o a l c h a r s w e r e determined i n hydrogen o r i n a 50:50 steam-hydrogen m i x t u r e at 35 a t m o s p h e r e s , using a high-pressure thermobalance. Most t e s t s w e r e conducted a t 1700"F, although, i n a special s e r i e s of t e s t s designed t o investigate the catalytic effects of exchangeable cations on lignite c h a r reactivities, t e m p e r a t u r e s w e r e v a r i e d f r o m 1400" t o 1700F. The following r e s u l t s a r e d i s c u s s e d i n t h i s p a p e r : The relationship between t h e initial carbon content and t h e gasification reactivities determined i n t h e hydrogen a t 1700"F, f o r coal c h a r s derived f r o m 36 c o a l s and m a c e r a l concentrates ranging i n rank f r o m a n t h r a c i t e to lignite. The effect of exchangeable cation concentrations ( s o d i u m and c a l c i u m ) on gasification reactivities of lignites i n hydrogen at 1 7 0 0 F and i n steam-hydrogen m i x t u r e s a t 1400" t o 1700F.
0

The surface area and p o r e volume variations that o c c u r during gasification in hydrogen and i n steam-hydrogen m i x t u r e s at 1 7 0 0 F of c o a l c h a r s derived f r o m anthracite, m e t a l l u r g i c a l coking coal, high-volatile A bituminous coal, subbituminous A coal, and lignite.

EXPERIMENTAL PROCEDURE
\

The high-pressure thermobalance used i n this work t o obtain gasification r e a c tivity f a c t o r s h a s been d e s c r i b e d previously ( 4 ) . The m a i n f e a t u r e of this a p p a r a t u s i s that t h e weight of a small fixed-bed sample of c o a l c h a r ( 1 / Z t o 1 g r a m ) contained i n a w i r e - m e s h b a s k e t c a n be continously m e a s u r e d a s it undergoes gasification i n a d e s i r e d gaseous environment at constant t e m p e r a t u r e and p r e s s u r e . In all t e s t s conducted, --20+40 U. S. sieve s i z e p a r t i c l e s w e r e used, and g a s flow r a t e s in t h e r e a c t o r w e r e maintained at sufficiently high values t o r e s u l t i n nenligible g a s conversion. Under t h e s e conditions, coal-char gasification could b e considered to o c c u r under constant known environmental conditions. Coal c h a r s w e r e produced by initially exposing the raw coals t o nitrogen a t 1 a t m o s p h e r e for

86

60 minutes, a t the s a m e t e m p e r a t u r e t o b e used during subsequent gasification i n hydrogen o r in steam-hydrogen m i x t u r e s . The weight loss 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 during gasification i n individual t e s t s w e r e then used a s a b a s i s f o r computing gasification reactivity f a c t o r s , using a p r o c e d u r e d e s c r i b e d below. C e r t a i n of the solid f e e d s and r e s i d u e s w e r e analyzed for internal s u r f a c e a r e a , p o r e volume, and t r u e density. S u r f a c e a r e a s w e r e computed f r o m adsorption i s o t h e r m s obtained with a Model 2100 O r r s u r f a c e a r e a - p o r e volume a n a l y z e r manufactured by t h e M i c r o m e r e t i c s Corp., which was a l s o used t o obtain t r u e d e n s i t i e s i n helium. Adsorption i s o t h e r m s obtained in nitrogen a t 77K w e r e i n t e r p r e t e d with t h e BET equation to compute s u r f a c e a r e a , and i s o t h e r m s obtained in c a r b o n dioxide at 298K w e r e i n t e r p r e t e d with t h e Dubinin-Polanyi equation a s modified by Kaganer ( 7 ) to compute s u r f a c e a r e a . In general, surface a r e a s computed f r o m nitrogen a n d c a r b o n dioxide adsorption i s o t h e r m s w e r e not i n a g r e e m e n t , and values obtained i n carbon dioxide w e r e considered t o b e m o s t reflective of equivalent i n t e r n a l s u r f a c e a r e a , which is consistent with t h e findings of o t h e r investigators ( 2 , 3 , 6, 7, 1 2 ) . Apparently, the penetration of nitrogen into the m i c r o p o r o u s s t r u c t u r e of c o a l s or carbonized coal c h a r s i s severely limited by slow, activated diffusion p r o c e s s e s a t 77"K, leading to v e r y low apparent s u r f a c e a r e a s : on t h e other hand, f o r p a r t i a l l y gasified coal c h a r s having m o r e open m i c r o p o r o u s structures, c a p i l l a r y condensation of nitrogen c a n lead t o unreasonably high a p p a r e n t surface a r e a s ( 1,8). Adsorption i s o t h e r m s obtained with carbon dioxide a t t h e higher t e m p e r a t u r e of 2 9 8 K facilitate activated diffusion into m i c r o p o r o u s s t r u c t u r e s , and c a p i l l a r y condensation is inhibited by t h e lower relative p r e s s u r e s employed ( 0 . 0 0 3 to 0 . 0 2 ) . Although t h e r e is some question concerning whether carbon dioxide a d s o r p t i o n i s o t h e r m s should b e i n t e r p r e t e d i n t e r m s of m i c r o p o r e volume (8,9, 10, 1 1 ) r a t h e r than m i c r o p o r e s u r f a c e area ( 2 , 3 , 6, 7 , 1 2 ) , the distinction i s not of i m p o r t a n c e i n e m p i r i c a l c o r r e l a t i o n s with gasification kinetic p a r a m e t e r s . This is b e c a u s e t h e calculation methods used t o compute n u m e r i c a l values of m i c r o p o r e volume a n d m i c r o p o r e s u r f a c e a r e a a r e virtually identical, differing only i n t h e n u m e r i c a l constants used. Thus, reported values of m i c r o p o r e volumes can b e converted to corresponding values of m i c r o p o r e s u r f a c e a r e a by a fixed constant. In this study w e have chosen t o compute surface a r e a values, favoring the argument that c a r b o n dioxide adsorption on a carbon s u r f a c e should be r e s t r i c t e d to a monolayer t h i c k n e s s , a s a r e s u l t of t h e quadruple interaction of the c a r b o n dioxide molecules with t h e v-bonds of t h e carbon s u r f a c e ( 2 , 7). An Aminco m e r c u r y i n t r u s i o n p o r o s i m e t e r capable of a hydrostatic p r e s s u r e of
15, 000 p s i w a s used to obtain p o r e volume distributions f o r p o r e s having d i a m e t e r s g r e a t e r than about 120 a n g s t r o m s . P o r e volume distributions for p o r e s between about 12 and 300 a n g s t r o m s w e r e obtained f r o m adsorption i s o t h e r m s obtained i n

nitrogen at 77K a t relative p r e s s u r e s up to about 0 . 9 3 . Good a g r e e m e n t w a s obtained with these two m e t h o d s i n t h e overlap region f r o m 180 to 300 a n g s t r o m s , similar t o r e s u l t s r e p o r t e d by Gan (3).

a .

DEFINITION O F RELATIVE REACTIVITY FACTOR, f, Weight loss 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 in individual thermobalance t e s t s w e r e interpreted to obtain relative reactivity f a c t o r s f o r the coal c h a r s used, b a s e d on a quantitative model developed previously at the Institute of G a s Technology t o d e s c r i b e the gasification k i n e t i c s of bituminous coal c h a r s a s 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, p r e t r e a t m e n t t e m p e r a t u r e , and c a r b o n conversion ( 4 ) . The e s s e n t i a l f e a t u r e s of this model a r e d e s c r i b e d below. C o a l - c h a r gasification i n g a s e s containing s t e a m and hydrogen a r e a s s u m e d t o o c c u r via t h r e e m a i n reactions:

a7 Reaction 1 Reaction 1 1 Reaction 111

2C

k l C +H,O f CO + H Z
C

+ 2Hz

k2 f CH, k 3 f CO

+ H, + H,O

+ CH4

where k,, k , and k, a r e rate constants f o r the t h r e e r e a c t i o n s shown and a r e , quantitatively defined i n the model a s a function of t e m p e r a t u r e , p r e s s u r e , and gas composition (accounting f o r CO, Hz, H,O, and CHI). The differential coal-char conversion r a t e is e x p r e s s e d by the relationship:

-=
where

:t

fLkT(l - X )

2/ 3

exp (4 Xz)

= base carbon conversion fraction

= time

X
9

fL

= relative reactivity factor f o r c o a l - c h a r gasification, which depends on

the p a r t i c u l a r coal c h a r and on the p r e t r e a t m e n t t e m p e r a t u r e u s e d i n preparing the coal c h a r = k,

kT
c1

+ k, + k3

= kinetic p a r a m e t e r defined as a function of p r e s s u r e and g a s composition.

B a s e carbon, r e f e r r e d t o i n t h e above definition of X, m e a n s t h e nonvolatile carbon in raw coal that r e m a i n s after standard devolatilization. B a s e c a r b o n conversion fractions can b e estimated f r o m weight loss-versus-time c u r v e s obtained i n thermobalance t e s t s , using t h e expression:

x = w/w, M -V M ) 1-V A
where

= weight l o s s fraction during initial devolatilization in nitrogen (approximately equal t o standard volatile m a t t e r a t elevated temperature) = a s h m a s s f r a c t i o n i n feed coal.

I
\

WIW, = total weight-loss fraction r e f e r r e d to original coal

VM

T h e relative reactivity factor, fL, depends on t h e p r e t r e a t m e n t t e m p e r a t u r e according t o t h e expression: fL = f o e x p ( 8 4 6 7 ) ( 1 / T -I/T) P

3)

where fo

88 reactivity f a c t o r dependent only on t h e inherent nature of t h e coal c h a r

T
T

= pretreatment temperature, " R = gasification t e m p e r a t u r e , "R.

Equation 3 i s only applicable f o r T > T; f o r T d T, then f L = fo. P P At constant environmental conditions, Equation 1 can b e integrated t o yield M ( X ) = l e0 l - X Z s x- X d
= f L kT e

4)

Based o n Equation 4, a plot of M ( X ) v e r s u s 0 should yield a straight l i n e having a Values of M ( X ) can b e computed f r o m experimental slope equal to the t e r m f k thermobalance data, u s & Equation 2 to obtain values of X and using t h e defined value of a to evaluate t h e i n t e g r a l in Equation 4. Note that, f o r t e s t s conducted i n is 0.97; with this value, t h e t e r m ( 1 -X)2/3exp( 0.97 X ' ) p u r e hydrogen, t h e value of is approximately equal t o ( 1 - X ) , o v e r nearly a complete range of X. F o r this case, M ( X ) = -In( 1 X ) and v a l u e s of t h e specific gasification r a t e , (dX/d0) /( 1 - X ) , a r e constant and equal to f k L T'

F i g u r e 1 shows two types of behavior noted i n t h i s study i n experimental plots of M ( X ) v e r s u s 8 . Line A is typical of t h e c h a r a c t e r i s t i c s cbtained with t h e majority of coal c h a r s tested, with l i n e a r i t y exhibited o v e r t h e complete range of b a s e carbon conversion. The line shown does not extrapolate to t h e origin b e c a u s e c h a r samples initially exposed t o t h e gasifying environment in t h e thermobalance r e q u i r e 1 to 2 minutes t o heat up t o r e a c t o r t e m p e r a t u r e . A c h a r a c t e r i s t i c of the type shown f o r C a s e B w a s obtained with s o m e coal c h a r s , usually low-rank m a t e r i a l s , indicating a n initial period of t r a n s i e n t reactivity, which d e c r e a s e d during the first 5 to 10 m i n u t e s and remained constant t h e r e a f t e r . F o r coal c h a r s exhibiting t h i s type of behavior, only the l i n e a r portion of t h e c u r v e corresponding to constant reactivity w a s u s e d to evaluate e x p e r i m e n t a l values o f f Lk T ' Values of the reactivity f a c t o r , f w e r e then obtained by dividing t h e t e r m fLkT by t h e value of kT defined i n t h e mo&l ( 4 ) f o r the reaction conditions used. RESULTS C o r r e l a t i o n of Reactivity F a c t o r s With Carbon Content i n Raw Coals The reactivity f a c t o r s f o r coal c h a r s derived f r o m 36 coals and coal m a c e r a l concentrates were d e t e r m i n e d i n hydrogen a t 1 7 0 0 F and 35 a t m o s p h e r e s . T h e distribution of coals u s e d with r e s p e c t to rank and lithotype i s d e s c r i b e d i n Table 1 . In t h i a study a variety of c o r r e l a t i o n s w e r e evaluated i n attempting t o quantitatively r e l a t e t h e s e reactivity f a c t o r s with simple, compositional p a r a m e t e r s included in ultimate, proximate, and p e t r o g r a p h i c analyses of t h e r a w coals. The b e s t success, however, w a s achieved with one of the simplest c o r r e l a t i o n s considered - a relationship between reactivity f a c t o r s and initial carbon contents. T h i s c o r r e l a t i o n is i l l u s t r a t e d i n Figure 2, w h e r e t h e line drawn c o r r e s p o n d s to t h e expression: fL = 6 . 2 Y ( l - Y )

5)

where fL Y

89

= relative reactivity f a c t o r of coal c h a r = concentration of carbon in r a w coal ( d r y , a s h - f r e e ) , g / g coal.

Table 1. NUMBERS O F EACH COAL T Y P E USED IN CORRELATION Whole - Vitrain - Fusian 1
2

Coal Rank Lignite Subbituminous C Subbituminous B Subbituminous A High-Volatile C Bituminous High-Volatile B Bituminous High-Volatile A Bituminous Low-Volatile Bituminous Anthracite Total

Total

1 3 1 1
4

1 1 2 2 2 1 2

1 16

-9
36

11

F o r r e a s o n s discussed below, it should b e emphasized that, f o r lignite c o a l c h a r s , t h e correlation shown i n F i g u r e 2 is applicable only when the r a w lignite is initially t r e a t e d i n acid to r e m o v e exchangeable cations. T h e standard deviation of experimental reactivity f a c t o r s shown i n F i g u r e 2 and of reactivity f a c t o r s calculated f r o m Equation 5 is about 0 . 1, which i s equivalent to t h e reproducibility of experimentally determined reactivity f a c t o r s . Interestingly, t h e correlation proposed does not uniquely distinguish between m a c e r a l types. Effects of Exchangeable Cation Concentration on Lignite Char Reactivity If reactivity f a c t o r s determined f o r coal c h a r s derived f r o m untreated r a w lignites w e r e included i n F i g u r e 2, then a considerable amount of s c a t t e r would be apparent above the c o r r e l a t i o n line at low c a r b o n concentrations. One p h a s e of this study, however, showed that the reactivities of lignite c h a r s obtained f r o m lignites initially t r e a t e d i n HC1 o r HCI -HF acid w e r e generally significantly less than t h e corresponding reactivities exhibited by lignite c h a r s derived f r o m u n t r e a t e d lignites. T h i s was not observed with s e v e r a l bituminous and subbituminous c o a l c h a r s . T h i s behavior apparently resulted f r o m a catalytic effect of exchangeable cations inherently p r e s e n t i n raw lignites i n carboxyl functional groups, which c a n be removed i n acid by t h e following type of reaction: -COONa

+ H+

= -COOH t Na'

With t h i s explanation, one can reasonably expect that this catalytic effect would predominate in lignites and would d e c r e a s e rapidly with increasing c o a l rank, corresponding to a rapid d e c r e a s e i n t h e amount of coal oxygen combined i n carboxyl functional groups. A s e r i e s of t e s t s w e r e conducted to obtain a quantitative m e a s u r e of t h e effects of exchangeable cation concentration ( s o d i u m and c a l c i u m ) on c h a r reactivity f a c t o r s f o r gasification in hydrogen and in steam-hydrogen m i x t u r e s . T h e s e t e s t s w e r e conducted with lignite c h a r s derived f r o m r a w lignites, with t h e lignite c h a r s derived f r o m raw lignites initially demineralized i n hydrochloric a c i d t o r e m o v e exchangeable cations and with t h e lignite c h a r s derived f r o m raw lignites initially demineralized i n hydrochloric a c i d t o which various amounts of calcium o r sodium w e r e then added by cation exchange in sodium a c e t a t e o r c a l c i u m a c e t a t e solutions. R e s u l t s of one

90
1

s e r i e s of t e s t s corresponding t o gasification i n hydrogen at 1700F a r e shown in F i g u r e 3. The r e s u l t s in F i g u r e 3 w e r e c o r r e l a t e d with t h e expression: fL/fL = 1 where fL =

+ 54.7'

YNa

+ 14.0

YCa

= reactivity f a c t o r of lignite t o which sodium o r calcium was added reactivity f a c t o r of a c i d - t r e a t e d lignite (Y Na' YCa = O ) concentration of exchangeable sodium o r calcium i n lignite before devolatilization in nitrogen, g / g fixed carbon.

YNa, YCa

Although t h e correlation given i n Equation 6 w a s developed f r o m data obtained with p r e p a r e d lignites t h a t did not contain both calcium and sodium a t the s a m e time, it d o e s apply reasonably well to untreated lignites containing, i n some c a s e s , both calcium and sodium. T h i s i s d e m o n s t r a t e d in T a b l e 2. T a b l e 2. COMPARISON O F CALCULATED AND EXPERIMENTAL REACTIVITY RATIOS 'Ca Lignite Savage Mine, Montana ( w h o l e ) Savage Mine, Montana (vitrain) Glenharold Mine, N. Dakota (whole) Glenharold Mine, N. Dakota (vitrain) 'Na fL If., Calculated 2.1 1.5 1.9 1.3 Experimental 1.7 1.7 2.0
/

g / g fixed c a r b o n

0.043 0.019 0.031 0.019

0.000 0.004 0.009 0.002

1.2
I

A t e s t s e r i e s w a s a l s o conducted t o d e t e r m i n e effects of exchangeable calcium and sodium concentrations o n the reactivities on a Montana lignite c h a r i n s t e a m hydrogen m i x t u r e s at t e m p e r a t u r e s f r o m 1400F t o 1700F. Results obtained a r e i l l u s t r a t e d i n Figure 4, which plots values of t h e kinetic t e r m , f kT, a s a function of t e m p e r a t u r e and cation concentration. Although t h e s e resultsLhave not yet been quantitatively c o r r e l a t e d , t h e y apparently show that sodium and calcium significantly enhance gasification i n steam-hydrogen m i x t u r e s , even m o r e so than f o r gasification i n hydrogen alone. F i g u r e 4 shows that t h e effect of calcium concentration o n reactivities is substantially t h e s a m e a s t h e effect of sodium concentration a t corresponding conditions ( c o n t r a r y t o t h e behavior obtained i n p u r e hydrogen), and that relative catalytic effects tend t o d e c r e a s e with i n c r e a s i n g gasification temperature. A significant additional r e s u l t of t h e t e s t s e r i e s conducted with steam-hydrogen m i x t u r e s w a s that t h e reactivity of acid-treated Montana lignite (YCa, ' N a = O ) r e m a i n s constant f o r gasification in steam-hydrogen m i x t u r e s over a t e m p e r a t u r e r a n g e f r o m 1400" t o 1700F. T h i s is shown i n F i g u r e 5. which plots experimental values of f k v e r s u s values of k calculated f r o m c o r r e l a t i o n s developed to d e s L T c r i b e bituminous c o a l c h a r g a s i f i A t i o n kinetics ( 4 ) . The line drawn c o r r e s p o n d s to a constant value of f = 1 . 3 , which is about the s a m e value obtained f o r gasification i n p u r e hydrogen at k'O0"F.

1
1

91
Variations i n Internal Char Surface A r e a s During Gasification

I
I

The variations i n i n t e r n a l s u r f a c e a r e a s w e r e m e a s u r e d f o r s e v e r a l c h a r s at different stages of gasification i n hydrogen or steam-hydrogen m i x t u r e s . The compositions of t h e c o a l s f r o m which t h e s e c h a r s w e r e p r e p a r e d a r e given in Table 3 . F i g u r e 6 shows t h e variations i n s u r f a c e a r e a m e a s u r e d i n carbon dioxide with different b a s e carbon conversion fractions f o r a s e r i e s of t e s t s conducted with Montana lignite c h a r s . F i g u r e 6 shows that t h e internal s u r f a c e a r e a of the Montana lignite c h a r tends t o r e m a i n constant over a m a j o r range of b a s e carbon conversion fractions and is essentially independent of c h a r p r e t r e a t m e n t o r gasification conditions. T h e apparent surface areas of carbonized c h a r s ( X = 0 ) a r e lower than the nominal value of p a r t i a l l y gasified c h a r s . T h i s difference m a y reflect that, even with carbon dioxide, penetration into the m i c r o p o r e s t r u c t u r e i s somewhat inhibited before the s t r u c t u r e i s opened up by p a r t i a l gasification. F i g u r e 7 shows variations in apparent s u r f a c e a r e a m e a s u r e d in nitrogen f o r Montana lignite c h a r s . The c h a r a c t e r i s t i c s shown tend t o support the suggestion made previously that, at low levels of conversion, nitrogen penetration into the m i c r o p o r e s t r u c t u r e is s e v e r l y inhibited, but that, at higher c a r b o n conversions, unreasonably high apparent s u r f a c e a r e a s a r e obtained b e c a u s e of capillary condensation. In F i g u r e 8, variations in s u r f a c e a r e a m e a s u r e d in c a r b o n dioxide ( S ) obtained with some o t h e r coal c h a r s a r e compared with r e s u l t s obtained Montana lignite c h a r s . Although surface a r e a s m e a s u r e d f o r c h a r derived f r o m anthracite, high-volatile bituminous coal, and lignite remained essentially constant during t h e c o u r s e of conversion i n hydrogen and steam-hydrogen m i x t u r e s , surface a r e a s f o r the subbituminous coal c h a r generally d e c r e a s e d with increasing carbon conversions during gasification i n hydrogen. Interestingly, of the f o u r coal c h a r s tested, only the subbituminous coal c h a r exhibited decreasing specific gasification rates during gasification with hydrogen that paralleled the d e c r e a s e i n s u r f a c e a r e a . T h i s i s shown in F i g u r e 9. Although generalizations based on the kinetic behaviors exhibited by only four coal c h a r s a r e not justified, t h e s e r e s u l t s do suggest that a f o r m of kinetic correlation t o d e s c r i b e coal-char gasification r a t e s that is m o r e meaningful than that derived f r o m the Equation 1 m a y be the following:

si%

where

relative reactivity p e r unit of internal s u r f a c e a r e a internal s u r f a c e a r e a p e r m a s s of carbon p r e s e n t .

S =

With t h i s interpretation, the constancy of t h e values of f L and Sco of anthracite, high-volatile bituminous, and lignite coal c h a r during gasification t n hydrogen corresponds to a constant value of X f o r e a c h c h a r . F o r t h e subbituminous coal c h a r , X is a l s o constant, although Sc d e c r e a s e s with increasing carbon conversion, apparently because of t h e grow& of c r y s t a l l i t e s . F o r the gasification t e m p e r a t u r e s used, t h i s growth is probably unusual and not c h a r a c t e r i s t i c of m o s t coal c h a r s . T h i s i s particularly t r u e if t h e f i r s t - o r d e r kinetics observed i n a variety of previous studies of the gasification of a f a i r l y l a r g e number of coal c h a r s i n hydrogen a r e a s s u m e d to correspond to constant values of X and S f o r the individual coal c h a r COZ tested.

92

I -

I-

i ,

93
Interestingly, i n t h e kinetic model previously r e f e r r e d to, the value of (Y i n Equation 1 i s approximately 1.7 f o r a variety of g a s compositions containing s t e a m and hydrogen a t elevated p r e s s u r e s . Empirically, this value c o r r e s p o n d s to decreasing values of X with increasing carbon conversions when i n t e r p r e t e d i n terms of Equation 7. T h i s o c c u r s even when t h e t o t a l internal s u r f a c e a r e a s rem a i n constant during conversion i n steam-hydrogen m i x t u r e s , as w a s shown in F i g u r e 6 f o r Montana lignite char. Some additional evidence was obtained i n this study that can b e i n t e r p r e t e d i n t e r m s of the formulation given in Equation 7. F i g u r e 10 shows values of Sco obtained during gasification of a coal c h a r derived f r o m B r a z i l i a n m e t a l l u r g i d l coal. at various t e m p e r a t u r e s , with hydrogen and steam-hydrogen m i x t u r e s . With this m a t e r i a l , the c h a r s u r f a c e a r e a , Sco , is not a function of c a r b o n conversion level and is the s a m e i n hydrogen and in s k a m - h y d r o g e n m i x t u r e s , but d e c r e a s e s with increasing gasification t e m p e r a t u r e . The reactivity factor, which is c h a r a c t e r i s t i c of r e s u l t s obtained at a specific t e m p e r a t u r e , a l s o % c r e a s e s with increasing t e m p e r a t u r e and i s proportional t o i n t e r n a l c h a r s u r f a c e a r e a , a s shown i n Figure 11. T h i s p a r t i c u l a r c h a r then c a n b e considered t o have a constant value of A, independent of t e m p e r a t u r e , conversion, o r gasification medium, but does exhibi: a decreasing internal s u r f a c e a r e a with increasing t e m p e r a t u r e , a f e a t u r e that probably r e f l e c t s i t s u s e a s a m e t a l l u r g i c a l coking coal. Variations in Char P o r e Volumes During Gasification F i g u r e 1 2 i l l u s t r a t e s typical pore-volume distributions of p a r t i a l l y gasified coal c h a r s . With the exception of untreated Montana lignite ( C u r v e F ) , the f e a t u r e s exhibited i n F i g u r e 12 a p p e a r to b e generally s i m i l a r to the distributions obtained by Stacy and Walker ( 9 ) with some c o a l c h a r s resulting f r o m a fluid-bed hydrogasification. Whereas Curves A through E tend to show a plateau a t a p o r e d i a m e t e r of about 55 a n g s t r o m s , possibly indicative of the lack of development of significant transitional p o r e s , Curve F shows a significant variation i n p o r e volume through t h i s r a n g e of p o r e diameters. It m a y b e pertinent, therefore, that t h e gasification r a t e s of unt r e a t e d Montana lignite c h a r i n a steam-hydrogen m i x t u r e w e r e about 7 t i m e s f a s t e r than the largest of the gasification r a t e s obtained with c h a r s corresponding to C u r v e s A through E. It is thus possible that, with sufficiently l a r g e gasification r a t e s , dynamic modifications that tend to occur within coal s t r u c t u r e s a s carbon i s removed a r e inhibited. The plateau in pore-volume variations a t a p o r e d i a m e t e r of 55 a n g s t r o m s exhibited by m o s t coals t e s t e d h a s suggested the following simplified representation of pore-volume c h a r a c t e r i s t i c s : Total p o r e volume a c c e s s i b l e v i a p o r e s l e s s than 55 a n g s t r o m s is defined a s "micropore" volume, and p o r e volume a c c e s s i b l e via p o r e openings having d i a m e t e r s between 55 and 20,000 a n g s t r o m s i s defined a s "macropore" volume. Micropore and m a c r o p o r e volumes obtained with different coal c h a r s a r e shown in F i g u r e s 13 and 1 4 a s a function of t h e b a s e c a r b o n conv e r s i o n fraction. Note that i n t h e s e figures, volumes a r e r e p r e s e n t e d p e r m a s s of initial b a s e carbon r a t h e r than p e r m a s s of remaining carbon and, therefore, are proportional to volumes on a p e r p a r t i c l e b a s i s . F i g u r e 13 shows s u r p r i s i n g l y little variation in m a c r o p o r e volume with increasing conversion f o r C u r v e s A through E. In viewing t h e s e r e s u l t s , r e m e m b e r that t h e t r u e density of b a s e c a r b o n i n these coal c h a r s i s about 2 g r a m s / c u cm, corresponding to a total volume of 0. 5 cu c m / g r a m of initial b a s e carbon. Thus, if the space initially occupied by gasified b a s e c a r b o n w e r e added to t h e m a c r o p o r e volume, m a c r o p o r e volumes would i n c r e a s e significantly with increasing carbon conversion. T h e r e s u l t s shown i n F i g u r e 13, however, indicate that t h i s is not generally the case, with the exception of Curve F , which does show a s h a r p i n c r e a s e i n m a c r o p o r e volume up t o conversions of about 0.8.

I
t\

94

F i g u r e 1 4 shows t h a t m i c r o p o r e volumes tend to initially i n c r e a s e with increasing c a r b o n conversion, r e a c h a maximum, and then d e c r e a s e with increasing conversion, approaching z e r o a t complete conversion. Interestingly, the m i c r o p o r e volume c h a r a c t e r i s t i c s corresponding to untreated Montana lignite c h a r gasified i n a steam-hydrogen mixture a r e essentially identical to the c h a r a c t e r i s t i c s f o r the o t h e r Montana lignite c h a r s , a s opposed to the behavior noted i n F i g u r e s 1 2 and 13. Thus, the rapid gasification r a t e s that evidently affect s t r u c t u r a l transitions a t a "macro" level apparently do not affect s t r u c t u r a l t r a n s i t i o n s on a "micro" level., T h i s is consistent with the r e s u l t s d i s c u s s e d previously, which showed a n insensitivity i n l i g n i t e - c h a r - s u r f a c e a r e a s to initial a c i d t r e a t m e n t or t o gasification conditions. T h e variations i n total p a r t i c l e volume with b a s e carbon conversion m e a s u r e d with the m e r c u r y p o r o s i m e t e r a r e shown in F i g u r e 15. T h e volumes r e p r e s e n t t h e s u m of solid volume plus p o r e volumes a c c e s s i b l e via p o r e openings having d i a m e t e r s of l e s s than 120 m i c r o n s . A s indicated i n F i g u r e 15, total p a r t i c l e volumes tend to d e c r e a s e with i n c r e a s i n g b a s e carbon conversion fraction, p a r t i cularly at conversions g r e a t e r than about 0. 5. Because t h e s e r e s u l t s w e r e somewhat unexpected when initially observed, s o m e additional t e s t s w e r e conducted to obtain photographic evidence of quantitative changes t h a t o c c u r r e d i n individual e x t e r n a l coal-char p a r t i c l e dimensions b e f o r e and a f t e r gasification in hydrogen a t 1700F. In t h i s s e r i e s of tests, a few p a r t i c l e s each of anthracite, high-volatile A bituminous coal, and Montana lignite w e r e initially photographed in s e v e r a l orientations under optically c a l i b r a t e d conditions; w e r e gasified i n the thermobalance to relatively high levels of c a r b o n conversion; and w e r e then photographed again. Detailed examination of t h e photographs obtained did show a significant reduction i n p a r t i c l e volumes, consistent with t h e r e s u l t s shown in F i g u r e 15. The fraction of volume reduction of e a c h t y p e of c h a r was independent of initial p a r t i c l e diameter i n the r a n g e f r o m about 200 to 800 m i c r o n s . T h i s f a c t and the f a c t that external topological c h a r a c t e r i s t i c s r e m a i n e d unchanged except f o r a diminishment i n size inidicated that t h e o b s e r v e d shrinkage o c c u r r e d throughout individual p a r t i c l e s and w a s not t h e r e s u l t of a "shrinking c o r e " phenomenon. SUMMARY AND CONCLUSIONS The overall evidence obtained in t h i s study suggests t h e tentative conclusion that gasification of c o a l c h a r s with hydrogen and steam-hydrogen m i x t u r e s o c c u r s p r i m a r i l y at c h a r s u r f a c e s located within m i c r o p o r e s . T h i s conclusion is supported by the relationships indicated between specific gasification r a t e s and internal c h a r s u r f a c e a r e a s , p a r t i c u l a r l y for gasification i n hydrogen. With the m a j o r i t y of coal c h a r s , internal s u r f a c e a r e a r e m a i n s constant during gasification a n d is independent of gasification conditions, possibly indicating a n invariance i n a v e r a g e crystallite dimensions during t h e gasification p r o c e s s . With s o m e c o a l c h a r s , however, surface a r e a s t e n d t o d e c r e a s e with i n c r e a s i n g conversion o r increasing gasification tempera t u r e , which would b e indicative of a growth i n c r y s t a l l i t e dimensions. P a r t i c l e shrinkage o c c u r s during coal-char gasification.due a l m o s t solely to contraction of t h e m i c r o p o r o u s p h a s e ( s o l i d s plus p o r e s a c c e s s i b l e via openings with d i a m e t e r s l e s s than 55 a n g s t r o m s ) , possibly b e c a u s e of the continuous r e orientation of individual c a r b o n c r y s t a l l i t e s . Macropore cavities a l s o shrink a t higher l e v e l s of conversion, b u t in a m a n n e r analogous to cavities i n a m e t a l l i c solid undergoing t h e r m a l contraction. Although a c c e s s i b l e m a c r o p o r e volumes may i n c r e a s e somewhat during t h e initial s t a g e s of conversion, this i n c r e a s e m a y c o r r e s pond t o a n increasing a c c e s s i b i l i t y of t h e m a c r o p o r e cavities p r e s e n t initially. Although t h e r e a r e s o m e significant d i f f e r e n c e s in the variations in s u r f a c e a r e a s a n d p o r e volumes for v a r i o u s coal c h a r s during gasification, the different coal chars t e s t e d exhibit a s u r p r i s i n g s i m i l a r i t y i n variations i n a v e r a g e m i c r o p o r e d i a m e t e r with increasing b a s e carbon conversion. T h i s is shown i n F i g u r e 16, which plots

,
1

95
values of the a v e r a g e m i c r o p o r e d i a m e t e r , D, v e r s u s t h e b a s e c a r b o n conversion fraction, X. The a v e r a g e m i c r o p o r e d i a m e t e r w a s computed f r o m t h e expression

-=D
where

4v

V = m i c r o p o r e volume ( a c c e s s i b l e pore-opening d i a m e t e r <55A). c a n b e considered to be Although the r e l a t i v e gasification reactivity factor, f "char surface a r e a " and "re&tivity p e r unit of char t h e product of two t e r m s surface a r e a " - t h i s study h a s not produced enough data t o evaluate c o r r e l a t i o n s between these s e p a r a t e p a r a m e t e r s and o t h e r coal p r o p e r t i e s . The study h a s shown, however, that f itself c o r r e l a t e s well with the initial carbon content of raw c o a l s f o r m o s t of t k e coal c h a r s t e s t e d . Lignites r e p r e s e n t a special case, b e c a u s e of the catalytic effects of exchangeable cations, particularly sodium and calcium, which predominate i n lignites b e c a u s e carboxyl functional groups a r e present. T h i s catalytic effect is g r e a t e r f o r gasification i n steam-hydrogen m i x t u r e s than i n hydrogen alone and tends to d e c r e a s e with i n c r e a s i n g gasification temperature. ACKNOWLEDGMENT This work w a s conducted a t the Institute of G a s Technology with p r i m a r y support f r o m the A m e r i c a n G a s Association. REFERENCES

1. Dubinin, M. M., " c h e m i s t r y and P h y s i c s of Carbon,

2. Everett, D. H., P r o c . Chem. SOC. 3, (1957).

" Vol. 11. ( E d . P. L. Walker, J r . ) . Marcel.Dekker, Inc., New York, 1966, p. 51.

3. Gan, H., Nandi, S. P. and Walker, P. L., "Porosity i n A m e r i c a n Coals, " Stock No. 2414-00059, U. S. Government Printing Office, Washington, D. C. 1972.

4. Johnson, J. L . , in Advances i n Chemistry S e r i e s No. 1974. 5. Kaganer, M. E., Zh. F i z . Khim. 6. Marsh, H. and Siemieniewska,
7. Marsh, H.

131,"Coal

Gasification,

"

2, 2202 (1959). Fuel (London) 4 3

355 ( 1 9 6 5 ) .

and Wynne-Jones. W . F . K . ,

Carbon 1, 281 (1964).

8. Spencer, D.H. T. and Bond, R. L., in Advances i n C h e m i s t r y S e r i e s No. 55, "Coal Science, " 724, 1966. 9. Stacy, W. 0. and Walker, P. L., "Structure and P r o p e r t i e s of Various Coal Chars, 'I Stock No. 2414-00058, U.S. Government Printing Office, Washington, D.C., 1972.
!

96
10. Toda, Y . , Study on P o r e Structure of Coals and Fluid Carbonized Products, Report No. 5 of the National Institute for Pollution and Resources. Japan, 1973. 1 1 . Toda. Y . , Hatauci, M . , Toyoda, S., Yoshida, Y. 187 ( 1 9 7 1 ) . and Honda, H . , Fuel 50 ( 2 ) ,

12. Walker, P. L. a n d P a t e l , R. L . , Fuel 49 ( l ) , 91 ( 1 9 7 0 ) .

COAL RANK

AA

o
VV
t

ANTHRACITE, Ivb hvAb, hvBb, hvcb SUB A, SUB 8, SUB C LIGNITE (ACID-TREATEO

I.o

0.8

06 .

OPEN POINTS: WHOLE COALS AND VlTRAlNS CLOSED POINTS: FUSAINS

70
TIME, 8. min
.u, m.

80

90

\.\
10 0
A7SCUI4?

CARBON CONTENT OF RAW COAL, % (dry, ash-free)

F i g u r e 1. TYPES O F CORRELATION CHARACTERISTICS

F i g u r e 2. CORRELATION O F REACTIVITY FACTORS

MONTANA L I G N I T E ( V I T R A I N )

SODIUM

OR

CALCIUM

FEED CONCENTRATION ( Y N o O R g / g fixed carbon

A
~

Yea)
75051143

Figure 3.

E F F E C T OF CATION CONCENTRATION ON REACTIVITY

.OFLIGNITE CHAR IN HYDROGEN AT 1 7 0 0 F AND 3 5 ATMOSPHERES

98

000 .01
1400

I I111111

0.m1

001 .0

I IIIllll 0.01

I I IlU

0.10
.,MI,,.,

1500

1600

1700
. a

TEMPERATURE. .F

k, ,min" (Calculated)

F i g u r e 4. E F F E C T O F CATION CONCENTRATION ON REACTIVITY O F MONTANA LIGNITE CHAR IN STEAM-HYDROGEN MIXTURES AT 1400' TO 1700'F AND 3 5 ATMOSPHERES

F i g u r e 5. REACTIVITY O F ACID-TREATED M~NTANA LIGNITE CHAR IN STEAMHYDROGEN MIXTURES AT 1400' T O 1700'F AND 3 5 ATMOSPHERES

'---I

;?
W

PRETREATMENT*

TEMP,*
1400

52oc v)
E

DM-CA DM-CA OM-CA ' DM-CA l RAW

DM DM DM DM

t+-HzO

t+-eo
Hz-HzO

t+-&O Hz-HzO
&H2O

1500 1600 1700 1400

10 70 I700 1700 10 70

+H20
t+-H20 HZ

? V

DM

RAW

HZ

'OM. DEMINERALIZED IN HCL 0Y-W DEMINERALIZED IN HCL WITH SUBSEWENT CATION EXCHAffil RAW. UNTREATED
I I I I I I I I I

BASE CARBON CONVERSION FRACTION, X

.,~,.,

F i g u r e 6 . VARIATIONS IN SURFACE AREA MEASURED I N CARBON DIOXIDE (Sco,) WITH BASE CARBON CONVERSION FRACTION FOR MONTANA LIGNITE CHARS GASIFIED AT VARIOUS CONDITIONS

1500

99

TEMP,"F

500 F f R Y r E N T A

DM
OM

K
0 0
0.1

GAS HZ- H20 H,

- H,O H, - H , O
H,
H7

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6

1500 1400 1600

1700 1700

DM DM

0.2 0.3 0.4 0 . 5 0.6 0.7 0.8 0.9 BASE CARBON CONVERSION F R A C T I O N , X
A 15051142

Figure 7. VARIATIONS IN APPARENT SURFACE AREA MEASURED IN NITROGEN WITH BASE CARBON CONVERSION FRACTION FOR MONTANA LIGNITE CHARS GASIFIED AT VARIOUS CONDITIONS
10 00

,
I

002,

v .

A
'a %

' a. .
0

00

ANTHRACITE hrAb SUBlllTUylNoUs A

A 6
0
Q

LIGNITE IUWTREATEDI
LlWlTE [ACID-TREATED1

HYmOGEN GASIFICATION CLOSED POINTS STEAM-MIOROOEN GASIFlCAlION

W E N POINTS

L
i

Figure 8. VARIATIONS IN Scoz WITH BASE Figure 9. RELATIONSHIP BETWEEN SPECIFIC CARBON GASIFICATION RATE AND FOR CARBON CONVERSION FRACTION FOR DIFFERENT C O A L CHARS GASIFLED IN GASIFICATION OF ROSEBUD SUBBITUMINOUS HYDROGEN AND STEAM-HYDROGEN A COAL CHAR IN HYDROGEN AT 1700F AND MIXTURES AT 1700F AND 35 ATMOSPHERES 35 ATMOSPHERES

Sc.

100

GASIFICATION

0.

OPEN POINTS:
00

1800 HYDROGEN GASIFICATION CLOSED POINTS: STEAM-HYDROGEN GASIFICATION

' '

0.2

04

' ' ' '

06

I
08
/

BASE CARBON CONVERSION FRAnION, X

F i g u r e 10. E F F E C T O F GASIFICATION TEMPERATURE ON INTERNAL SURFACE AREA OF CARVAO METALLURGICAL COAL CHAR

o k '

100 200 I 300 400 CHAR SURFACE A R E A , Scofsq m/g char (ash-free)
1-15051144

'

'

'

F i g u r e 11. RELATIONSHIP BETWEEN REACTIVITY FACTOR, fL, and S FOR CARVAO METALLURGICAL COAL CHAR

c0 2

9 LIGNITE.ACI0-TREATED
LIGNITE. LWTREATED

n ,
8

0 2

1
4

- H ~I O
2

1 0

I" 0

I1
IO

I
I0 '

I
IO'

I
1 0 '
.I*OIIO*

I 1
1' 0

0.5 EASE CARBON COMERSON FRACTION, X

.,y_ ,~,

PORE OPENING D I A M E T E R . D . o ~ ~ ~ ~ o ~ s

F i g u r e 12. TYPICAL PORE VOLUME DISTRIBUTIONS FOR DIFFERENT COAL CHARS GASIFIED IN HYDROGEN AND STEAM-HYDROGEN MIXTURES AT 1700F and 35 ATMOSPHERES

F i g u r e 1 3 , RELATIONSHIP BETWEEN MACROPORE VOLUME AND BASE CARBON CONVERSION FRACTION FOR DIFFERENT COAL CHARS

10 1

COAL

GASIFICATION M D l U h

0 ANTHRACITE 4 hvAb D SUBBITUMINOUS A 0 LIGNITE.UNTREATED 0 LIGNIT6.ACID-TREATED I LIGNITE.UNTREATED

HiHP
n 2 - v

HI
HI

HI

BASE CARBON CONVERSION F R A C T I O N , X

..1,0,1141

o h
05 BASE CARBON CONVERSION FRACTI0N.X
,r00,,1,.

F i g u r e 14. RELATIONSHIP BETWEEN MICROPORE VOLUME AND BASE CARBON CONVERSION FRACTION FOR DIFFERENT COAL CHARS

F i g u r e 15. RELATIONSHIP BETWEEN TOTAL PARTICLE VOLUME AND BASE CARBON CONVERSION FRACTION FOR D I F F E R E N T COAL CHARS

4
i n f

40t
0 SUBBITUMINOUS A 0 LIGNITE

GASIFICATION MEDIUM
HI-HpO Hp HzO

Hp

1 0

a
w

0 LIGNITE,

UNTR~ATED

HZ

ACID-TREATED V LIGNITE, UNTREATED

Hr

H ,

- - H.0 I I
0
AT5051140

O
0

0.2 0.4 0.6 0.8 BASE CARBON CONVERSION FRACTION, X

Figure 16. RELATIONSHIP BETWEEN AVERAGE MICROPORE DIAMETER AND BASE CARBON CONVERSION FRACTION FOR DIFFERENT COAL CHARS

102

RAPID DEVOLATILIZATION AND HYDROGASIFICATION OF BITUMIKXE COAL. D.B. Anthony, H.C. H o t t e l , J . B . Howard, and H.P. Meissner, Department of Chemical
Engineering, Massachusetts I n s t i t u t e of Technology, Cambridge, Massachusetts 02139 Rapid d e v o l a t i l i z a t i o n and h y d r o g a s i f i c a t i o n of a P i t t s b u r g h Seam bituminous c o a l were s t u d i e d and an epproximate c o a l conversion (weight l o s s ) model w a s developed t h a t accounts f o r secondary char-forming r e a c t i o n s among v o l a t i l e s . Approximately monol a y e r samples ef s m ~ l ccs1 p a r t i c l e s supported on wire mesh h e a r i n g elements were l e l e c t r i c a l l y heated i n hydrogen and hydrogen/helium mixtures. Coal weight l o s s was measured as a f u n c t i o n of r e s i d e n c e time (0.05-20 s e c . ) , temperature (400-11OO0C), heating rate ( l o 2 - l o 4 'C/sec.), t o t a l p r e s s u r e (0.001 - 100 atm), hydrogen p a r t i a l . 100 a t n ) , and p a r t i c l e s i z e 50 1000pm). Rate of weight l o s s under these p r e s s u r e (0 c o n d i t i o n s appears to be c o n t r o l l e d by thermal decomposition r e a c t i o n s t h a t form volat i l e s and i n i t i a t e a sequence of secondary r e a c t i o n s l e a d i n g t o c h a r . Thermal decompos i t i o n i s modelled a s a l a r g e number of p a r a l l e l f i r s t - o r d e r r e a c t i o n s having a s t a t i s t i c a l d i s t r i b u t i o n of a c t i v a t i o n e n e r g i e s (20-89 kcal/mole). The c o n t r i b u t i o n of secondary r e a c t i o n s t o weight l o s s i s d e s c r i b e d by a s e l e c t i v i t y expression derived from t h e assumption t h a t c h a r formation by t h e s e r e a c t i o n s competes with hydrogenation r e a c t i o n s and d i f f u s i o n a l escape of v o l a t i l e s from t h e p a r t i c l e .

Hydrogasification Kinetics of Biturdnous Coal and Coal Char

J. A. Gray, P. 3. D o n a t e l l i , P. M. Yavorsky

103

U.S.

Energy Research and Development Administration P i t t s b u r g h Energy Research Center 4800 Forbes Avenue P i t t s b u r g h , Pennsylvania 15213 INTRODUCTION

Of t h e many processes c u r r e n t l y under development which w i l l convert c o a l t o environmentally acceptable s o l i d , l i q u i d , and gaseous f u e l s u t i l i z i n p p y r o l y s i s , s y n t h e s i s gas, s o l v e n t e x t r a c t i o n , or hydrogenation techniques, t h e d i r e c t hydrogenation of c o a l t o a raw gas t h a t i s e a s i l y upgraded t o p i p e l i n e q u a l i t y Is a promising approach. Such a process i s under development by t h e E.R.D.A., Pittsburgh .( 2 . ) Energy Research Center and is known as WDRANE,I B r i e f l y , t h e HYDRANE flow s h e e t is a s follows. Pulverized r a w c o a l is f e d t o t h e t o p zone of t h e h y d r o g a s i f i e r , operated a t 70 atm and 750-900" C, where i t f a l l s f r e e l y as a d i l u t e cloud of p a r t i c l e s through a hydrogen-rich g a s c o n t a i n i n g some methane from t h e lower zone. About 2 0 p c t of t h e carbon in t h e r a w c o a l i s converted t o methane, causing t h e coal p a r t i c l e s t o l o s e t h e i r v o l a t i l e matter and agglomerating c h a r a c t e r i s t i c s and t o form very porous, reactive c h a r p a r t i c l e s . This char f a l l s i n t o t h e lower zone, operated a t 70 atm and 900-980" C, where hydrogen feed gas maintains t h e p a r t i c l e s i n a f l u i d i z e d s t a t e and reacts with a n a d d i t i o n a l 25 p c t of t h e carbon t o make methane. The product g a s e x i s t s from t h e bottom of t h e dilute-phase zone and i s cleaned of entrained s o l i d s , t a r s and o i l s , and some unwanted gases. A f t e r cleanup, c a t a l y t i c methanation of t h e s m a l l amount o f r e s i d u a l carbon monoxide g i v e s a p i p e l i n e q u a l i t y , high-Btu, s u b s t i t u t e n a t u r a l gas. Char from t h e lower zone of t h e h y d r o g a s i f i e r is r e a c t e d w i t h steam and oxygen t o make t h e needed hydrogen. This process has t h e following advantages:

1. External hydrogen consumption p e r u n i t of methane produced i s low because t h e hydrogen already i n t h e c o a l is e f f i c i e n t l y utilized,
2. Process c o s t s a s s o c i a t e d with c o a l pretreatment, i n h e r e n t i n o t h e r c o a l conversion processes based on caking bituminous c o a l feedstocks, a r e eliminated, 95 percent of t h e product methane is produced d i r e c t l y i n t h e h y d r o g a s i f i e r thus r e q u i r i n g very l i t t l e c a t a l y t i c methanation, Simple r e a c t o r design, Produces law-sulfur c h a r byproduct f o r hydrogen peneration and lows u l f u r t a r s , and U t i l i z e s s e n s i b l e h e a t of the r e s i d u a l char from t h e h y d r o g a s i f i e r i n t h e hydrogen generation p l a n t .

3. 4.
\

5.

6.

Because of these advantages, c o a l and oxygen ( t h e c o s t l i e s t items i n g a s i f i c a t i o n ) requirements a r e minimized f o r t h e process, and thermal e f f i c i e n c y and carbon u t i l i z a t i o n 4). a r e high a t 78 p c t and 44 p c t , r e s p e c t i v e l y (2,

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Much of t h e h y d r o g a s i f i c a t i o n k i n e t i c d a t a on t h e l a b o r a t o r y s c a l e , f r e e - f a l l , dilute-phase r e a c t o r h a s a l r e a d y been published (5, 5) as w e l l as d a t a from a semiflow bench-scale r e a c t o r (1).I n t h i s paper w e review previous and some r e c e n t k i n e t i c d a t a w i t h regard t o t h e type of r e a c t o r used t o o b t a i n t h e d a t a , and t h e e f f e c t of t h e type of r e a c t o r on t h e conversion data. The conversion of t h e nonmineral elements i n t h e coal during h y d r o g a s i f i c a t i o n and t h e c h a r y i e l d are shown t o be r e l a t e d t o t h e carbon conversion r e g a r d l e s s of t h e r e a c t o r geometry used, so t h a t t h e c o n s t i t u e n t conversions can be c a l c u l a t e d once t h e carbon conversion i s known. This s i m p l i f i e s t h e r e a c t o r design i n t h a t only t h e carbon conversion need be k i n e t i c a l l y defined f o r a p a r t i c u l a r r e a c t o r geometry. EXPERIMENTAL REACTORS "Hot-Rod" Reactors (HR)

I n 1955 E l Paso N a t u r a l Gas Company entered i n t o a cooperative agreement w i t h t h e then U.S. Bureau of Mines S y n t h e t i c Fuels Research Branch t o i n v e s t i g a t e t h e hydrogenation of a subbituminous New Mexico c o a l t o produce high-Btu g a s and lowb o i l i n g aromatics. P a r t of t h e agreement c a l l e d f o r tests i n a r e a c t o r i n which dry c o a l could b e r a p i d l y brought t o t h e d e s i r e d o p e r a t i n g temperature and pressure. A normal autoclave r e q u i r e d over an hour t o reach temperature. Consequently, t h e e f f e c t of t h e h e a t i n g and cooling c y c l e s on t h e r e a c t i o n could n o t b e discerned. I n l a t e 1955, Hiteshue conceived t h e apparatus known as t h e "hot-rod" r e a c t o r and completed t h e E l Paso p r o j e c t using it. The apparatus along w i t h conversion d a t a were f i r s t reported by Hiteshue, Anderson, and S c h l e s i n g e r i n 1957 (i) and a g a i n d u r i n g 1960-1964 ( 2 , g ) . The "hot-rod" r e a c t o r , shown i n F i g u r e 1, was a 70-inch long s t a i n l e s s steel tube (type 304) having a 5/16-inch i n s i d e diameter and a 5/8-inch o u t s i d e diameter. A c o a l o r c h a r sample weighing 8 grams and screened t o 30 x 60 U.S. s i e v e s i z e was i n s e r t e d i n t o t h e t u b e between two porous s t a i n l e s s s t e e l d i s k s such t h a t a 32-inch l e n g t h w a s a v a i l a b l e t o f l u i d i z e t h e sample. The tube w a s heated w i t h e l e c t r i c a l c u r r e n t by connecting i t t o a transformer t h a t wae capable o f supplying 700 amperes a t 9 v o l t s . W i t h t h i s method o f h e a t i n g , t h e r e a c t o r , sample, and f e e d gas w e r e heated from room temperature t o 800' C i n about 2 minutes and t o 1200' C i n about 4 minutes, A t the end of t h e experiments, t h e r e a c t o r and sample were cooled t o room temperature in about 10 seconds by spraying with c o l d water. The flowsheet of t h e e n t i r e apparatus is shown i n Figure 2 and has been discussed i n d e t a i l i n t h e previously c i t e d r e f e r e n c e s , Free-Fall D i l u t e Phase Reactor (FDP) The agglomeration of bituminous c o a l s i n hydrogen i s a major problem i n designing a r e a c t o r f o r t h e i r continuous hydrogenation t o produce a high-Btu gas. It has been shown t h a t bituminous c o a l s , both caking and noncaking, w i l l agglomerate when r a p i d l y heated i n hydrogen a t 500 psig and 500" C o r a t 6,000 p s i g and 500 t o 800 C ( o l , 14). Texas lignite agglomerated a t 6,000 p s i g and 800' C b u t d i d 13, n o t agglomerate a t 500 p s i g and 500' C. Chars produced from carbonizing bituminous c o a l s , cokes, g r a p h i t e and a n t h r a c i t e , and a h i g h l y oxidized hvAb c o a l did n o t agglomerate. Feldmenn observed t h a t e t l e a s t 1 0 p c t of t h e v o l a t i l e matter i n P i t t s b u r g h s a hvAb c o a l , o r i g i n a l l y containing 36 p c t v o l a t i l e matter, had em t o b e removed t o o b t a i n a char t h a t would n o t agglomerate a t 1,000 p s i g and 800 C i n hydrogen i n subsequent "hot-rod" r e a c t o r t e s t s .

(i)

Lewis and Hiteshue ( 5 designed an e n t r a i n e d flow r e a c t o r f o r continuously 1) hydrogenating both caking (hvAb) and noncaking (hvCb) coals. They b e l i e v e d t h a t i f t h e suspension of c o a l i n t h e feed gas w a s d i l u t e enough ( d i l u t e phase), p a r t i c l e -

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p a r t i c l e c o l l i s i o n and subsequent agglomeration could be avoided. The r e a c t o r was a l / & i n c h i n s i d e diameter, 60-foot long h e l i c a l tube, and was operated a t 600 pSig and 8 0 C. The c o a l was e n t r a i n e d a t a rate of 60 g r s / h r i n hydrogen where t h e 0' hydrogen v e l o c i t y was 2 fps. Experiments w i t h t h e h e l i c a l r e a c t o r were unsuccessful because of s o l i d s p l w g i n g a t about t h e 500 t o 550' C zone i n t h e h e l i c a l tube. Changing t o a s t r a i g h t , h o r i z o n t a l tube r e a c t o r having an i n t e r n a l d i a n e t e r of 5/16 inches and a length of 20 f e e t d i d n o t a l l e v i a t e t h e plugging problem.
A 4-inch diameter v e r t i c a l r e a c t o r where t h e c o a l p a r t i c l e s would n o t c o n t a c t t h e r e a c t o r wall during d e v o l a t i l i z a t i o n w a s found t o o p e r a t e very s u c c e s s f u l l y . It was f u r t h e r shown t h a t reducing t h e diameter t o l e s s than 3 inches caused plugging, again due t o c o a l p a r t i c l e s contacting t h e r e a c t o r wall. Figure 3 shows t h e l a b o r a t o r y dilute-phase r e a c t o r t h a t evolved fro= t h e s e s t u d i e s .
A l a r g e a m u n t of k t n e t i c d a t a has been reported f o r t h i s r e a c t o r using l6, l. D e t a i l s of t h e J ) P i t t s b u r g h seam hvAb and I l l i n o i s 1/6 hvCb c o a l s (5, l a b o r a t o r y r e a c t o r and method of operation are discussed i n t h e previous references.

a,

The present FDP r e a c t o r i s a 3.26-inch i n s i d e diameter pipe t h a t is heated through t h e wall and contained i n a 10-inch diameter p r e s s u r e s h e l l . Coal i s i n j e c t e d i n t o t h e top of t h e r e a c t o r through a 5/16-inch i n s i d e diameter, water-cooled nozzle using a r o t a r y feeder and p a r t of t h e feed gas. The c o a l f r e e - f a l l s through a 5-foot long r e a c t o r concurrently w i t h t h e feed gas a t a p a r t i c l e r e s i d e n c e t i m e of less than a second. Agglomeration i s avoided because t h e r a p i d h e a t i n g d e v o l a t i l i z e s t h e p a r t i c l e s before many p a r t i c l e c o l l i s i o n s with t h e wall o r o t h e r p a r t i c l e s can occur. The char product i s recovered from a cooled hopper a f t e r each experiment and is analyzed. Gas flows and compositions a r e measured over steady state p e r i o d s of t h e experiment so t h a t mass balances can be c a l c u l a t e d . Two-Stage Integrated Reactor I n o r d e r t o r e a c t f r e s h d i l u t e phase c h a r with hydrogen a s i n t h e i n t e g r a t e d r e a c t o r system described previously, and t o measure r e a c t i v i t y and methane y i e l d at carbon converaion l e v e l s expected i n a commercial r e a c t o r , a two-stage l a b o r a t o r y h y d r o g a s i f i e r w a s b u i l t c o n s i s t i n g of a dilute-phase r e a c t o r i n t e g r a t e d w i t h a second s t a g e r e a c t o r t h a t could b e operated a s e i t h e r a moving-bed o r fluid-bed r e a c t o r . Figure 4 i l l u s t r a t e s t h e v e r s i o n using a fluid-bed second s t a g e . Because t h e diameter of t h e c o a l p a r t i c l e s increased s u b s t a n t i a l l y due t o s w e l l i n g and some agglomeration during d e v o l a t i l i z a t i o n , a char crusher was used t o reduce t h e p a r t i c l e s i z e t o a level acceptable f o r f l u i d i z a t i o n . I n t h e moving-bed v e r s i o n , no crusher was used as shown i n Figure 5. The t r u e composition of product gas from t h e i n d i v i d u a l s t a g e s could n o t b e determined d i r e c t l y because a l a r g e amount of mixing occurred between gas n e a r t h e bottom of t h e d i l u t e phase r e a c t o r and gas near t h e top of t h e second s t a g e r e a c t o r . The o v e r a l l methane y i e l d f o r t h e two-stage u n i t was determined i n some c a s e s , and these y i e l d s were compared t o y i e l d s from previous d i l u t e phase r e a c t o r experiments. The mixing problem was n o t unexpected s i n c e t h e r e w a s no gas seal l e g used between t h e two r e a c t o r s because of t h e small s c a l e of t h e equipment. The mixing was caused from convection c u r r e n t s c r e a t e d from t h e f a l l i n g c h a r p a r t i c l e s and t h e h o t r e a c t o r w a l l s . The operation of t h e twc-stage h y d r o g a s i f i e r is described i n much g r e a t e r d e t a i l elsewhere (Is). KINETIC MODEL Within about t h e f i r s t few inches of f r e e - f a l l i n t h e FPD r e a c t o r , t h e c o a l p a r t i c l e s a r e r a p i d l y heated and d e v o l a t i l i z e d y i e l d i n g a "popcorn" c h a r It i s g e n e r a l l y accepted t h a t during t h e p e r i o d of d e v o l a t i l i z a t i o n , chemical bonds

() E.

such a s methylene bridges, oxygen bonds, and s i d e c h a i n s are e a s i l y broken r e s u l t i n g i n e v o l u t i o n o f hydrogen r i c h v o l a t i l e matter and a l a r g e number of f r e e r a d i c a l 20, 21, 22). These f r e e r a d i c a l s can r e a c t w i t h hydrogen forming s t r u c t u r e s (2, hydrocarbon gases and s o l i d species t h a t are a c t i v e f o r f u r t h e r hydrogenation t o v o l a t i l e m a t e r i a l or combine by polymerization t o form a highly aromatic, u n r e a c t i v e char s t r u c t u r e . During f r e e - f a l l , b u t a f t e r rapid d e v o l a t i l i z a t i o n has occurred ( a f t e r about 6 inches), t h e s o l i d carbon is very r e a c t i v e i n behavior as though n o t enough t i m e has elapsed f o r s i g n i f i c a n t polymerization t o proceed (2). However, when t h e char i s f u r t h e r r e a c t e d with hydrogen i n a second-stage r e a c t o r such a s a fluidized-bed or moving-bed, t h e h y d r o g a s i f i c a t i o n rate i s about two o r d e r s of magnitude slower ( , 1 g). Thus, t h e c o a l s t r u c t u r e and r e a c t i v i t y change c o n s t a n t l y during r e a c t i o n . Feldmann (2) has proposed t h a t f o r k i n e t i c modeling purposes t h e carbon i n t h e raw c o a l can b e divided i n t o t h r e e t y p e s during hydrogasification. Type 1 carbon i s t h e highly r e a c t i v e s p e c i e s which is f l a s h e d o f f almost instantaneously during r a p i d heat-up and d e v o l a t i l i z a t i o n , Type 2 i s t h e s o l i d carbon which r e a d i l y h y d r o g a s i f i e s during most o f t h e p a r t i c l e f r e e - f a l l , and Type 3 i s t h e low-reactivity carbon contained i n t h e remaining, polymerized char s t r u c t u r e . Johnson (23) h a s proposed a very s i m i l a r model.

In developing a r e a c t i o n r a t e expression f o r t h e h y d r o g a s i f i c a t i o n of c o a l i n t t h e FDP r e a c t o r (2).h e Type 1 carbon i s assumed t o d e v o l a t i l i z e instantaneously and t h e remainder of h y d r o g a s i f i c a t i o n occurs w i t h Type 2 carbon. The r e a c t i o n can be w r i t t e n as
Char

+ +

AH2

+ +

CH4
2

1)

f o r t h e d a t a a t high hydrogen p a r t i a l p r e s s u r e s (PH 50-60 atm) Char

AH2

(A),

and a s ,

CHI,

Oil

Light Hydrocarbons

2)

f o r d a t a a t lower hydrogen p a r t i a l p r e s s u r e s (5). An e m p i r i c a l c o r r e l a t i o n of A , t h e s t o i c h i o m e t r i c c o e f f i c i e n t , has been developed from t h e h i g h p r e s s u r e d a t a and is

where x i s t : t o t a l

'ac t i o n a l carbon conversion.

1.0 f o r x ax-2.6 for 1.8 f o r x

<
>

0.45

0.45 0.55

5 0.55

3)

The o i l y i e l d h a s been as h i g h a s 5X f o r P i t t s b u r g h s e a r hvAb c o a l and 6% f o r I l l i n o i s /I6 hvCb coal. A small amount of carbon oxides a r e produced ( u s u a l l y l e s s than 4% of t h e product pas) and are i n equilibrium according t o the water-gas s h i f t r e a c t i o n a s shown i n F i p r e 6 . The h y d r o g a s i f i c a t i o n of Type 2 carbon follows t h e r a t e equation

e dt

k PH 2 (a-x)
H2

4)

where x i s t h e f r a c t i o n a l carbon conversion, P

t h e hydrogen p a r t i a l pressure, a t h e
i

107

f r a c t i o n of t h e carbon which is a v a i l a b l e f o r r e a c t i o n i n the r e p i n e being considered and k t h e r e a c t i o n rate constant. Another way of w r i t i n g Equation 4 where t h e d e v o l a t i l i z e d carbon i s not included i n t h e f r a c t i o n a l carbon conversion i s

where 2 = (x-E)/(l-E) and B = (a-E)/(l-F). E corresponds t o t h e f r a c t i o n of carbon t h a t was d e v o l a t i l i z e d . A s s d n g the coal p a r t i c l e s being fed t o t h e d i l u t e phase r e a c t o r a t t a i n t e r m i n a l v e l o c i t y and t h e same temperature a s t h e r e a c t o r w a l l almost i w e d i a t e l y , Equation 4 may be a p p l i e d t o t h e FDP r e a c t o r a s

where UT i s t h e p a r t i c l e terminal velocity. length y i e l d i n g

X

Equation 6 i s i n t e g r a t e d over t h e r e a c t o r

dx
'HZ E

7)

I n t h e i n t e g r a t i o n , P B ~ s assumed constant and equal t o t h e hydrogen p a r t i a l p r e s s u r e i i n t h e product pas because extensive backmixing occurs due t o t h e h o t r e a c t o r w a l l s and t h e downward flow of char. The f r a c t i o n of Type 1 carbon i s accounted f o r a s E i n t h e i n t e g r a t i o n . Within t h e c o n s t r a i n t t h a t 0 < a I 1. t h e b e s t f i t of carbon conversion d a t a from t h e FDP r e a c t o r is obtained when a = 1 - ( 2 ) . T h i s means t h a t e s s e n t i a l l y a l l of t h e carbon i s a v a i l a b l e f o r hydrogasification.
~

The h y d r o g a s i f i c a t i o n of char i n a "hot-rod", moving-bed, o r fluid-bed r e a c t o r follows t h e 8am.e rate expression given by Equation 4 , however, t h e r e a c t i o n i s much slower because most of t h e carbon t h a t i s r e a c t i n g i s of t h e Type 3 v a r i e t y . Application of Equation 4 t o fluid-bed and moving-bed r e a c t o r s h a s been discussed elsewhere (E). The rate expression does n o t take i n t o account t r a n s i t i o n s between t h e various r e a c t i v e types of carbon i n t h e c o a l nor mass t r a n s f e r r e s i s t a n c e . In f a c t t h e hydrogasification of char i s so complex because of t h e change i n carbon s t r u c t u r e during r e a c t i o n , t h a t t h e above simple c l a s s i f i c a t i o n of carbon may n o t apply i n a l l casea. Johnson's model (23)takes i n t o account t h e continuous d e a c t i v a t i o n of t h e char b u t a160 adds another constant i n t o t h e w d e l w h i c h mst b e e v a l u a t e d using experimental data. Generally t h e more constants t h e r e are i n a m.odel, t h e b e t t e r t h e model w i l l f i t r e g a r d l e s s of t h e accuracy of t h e proposed r e a c t i o n mechanism, and t h e pore experimental d a t a is needed t o e v a l u a t e t h e constants. F o r t h i s reason, Equation 4 was kept simple so t h a t d a t a from various r e a c t o r s could b e e a s i l y cor,pared. With t h i s perspective, t h e d a t a from each of t h e r e a c t o r systems will now be discussed.
1

\'

EWERIMENMI, RESULTS FLIP Reactor Using Equation 7 and a terminal v e l o c i t y of 9 f p s , Feldmann (2) determined E and k values f o r carbon conversion data a t 900' C and 725' C. These values are l i s t e d in Table 1. I n a l a t e r p u b l i c a t i o n , Feldmann (2) reanalyzed t h e 725" C data a s a function of hydrogen p a r t i a l p r e s s u r e and presented r e c e n t 850"-900 C ( t o t a l

108

TABLE 1.- FDP Reactor k i n e t i c d a t a

~ ~~

(2)
k atrn-lhr-l 6 21

Reactor Wall Temp., O C 725 900

T o t a l Reactor Press., a t m 103,205 205

E, %

22

14

TABLE 2 . - U l t i m a t e and proximate a n a l y s e s of f e e d s Coals IIR-2 Pgh hvAb 74.1 5.1 1.5 1.5 7.6 10.2 100 1.4 35.3 53.1 Chars HR-2C
Ill. C6 hvCb
~~~~

Run S e r i e s
Wt.%
C

HR-1

FDP Pgh hvAb 78.1 5.3 1.6 1.1 8.2 5.7 100 1.2 36.4 56.7
I l l . (16 hvCb

HR-1c
~

Pgh hvAb

Pgh hvAb 78.8 1.9 1.6 1.1 1.9 14.7 100 0

H N S
0 Ash

Moisture

VM

FC

74.2 5.1 1.5 1.9 8.8 8.5 100 1.9 33.9 56.5

74.4 5.2 1.7 1.3 11.5 5.9 100 1.4 36.8 55.9

83.9 2.8

-------

10.2 0.9 26.0

-----

-----

TABLE 3.Reactor Wall, Temp., C 725 725 850-900 850-900

FDP Reactor k i n e t i c d a t a T o t a l Reactor Press., a t m 103,205 103,205 69-108 69-108

Lc

E, %

atm-lhr-' 5.3* 14.7 24. 7* 33.0

23.1 9.4 21.5 12.2

*Total carbon conversion.

p r e s s u r e 69-108 atm) d a t a (k). The ultimate and proximate analyses of t h e feed c o a l s a r e shown in Table 2 f o r t h e FDP and "hot-rod" r e a c t o r s . Figures 7 and 8 show t h e carbon conversion d a t a as t o t a l carbon conversion and a s carbon conversion t o equivalent methane (carbon in methane and ethane). The d i f f e r e n c e between t o t a l carbon conversion and carbon conversion t o methane

measured (2). These e r r o r s becove obvious when t h e carbon and ash recoveries a r e much lower than 100 p c t . Figure 9 i n d i c a t e s t h a t t h e hydrogen p a r t i a l p r e s s u r e as w e l l as r e a c t o r temperature g r e a t l y influences t h e anount of o i l produced, e s p e c i a l l y below a p a r t i a l p r e s s u r e of 30 a t m . The i n c r e a s e in oil y i e l d w i t h decreasing hydrogen p a r t i a l pressure agrees w i t h t h e divergence of the two carbon conversion curves i n Figures 7 and 8. Apparently t h e higher hydrogen p a r t i a l p r e s s u r e s enhance t h e hydrocracking of t h e o i l products. Residence time of t h e hydrocarbon vapors in t h e r e a c t o r a l s o a f f e c t s t h e o i l y i e l d causinp lower amounts of o i l a t i n c r e a s i n g residence time as shown in Figure 10. A s i n d i c a t e d in F i g u r e 5 , t h e o i l y i e l d was determined by recovery from t h e gas sample and main t a i l gas streams. However, some of t h e o i l w a s l o s t by condensation on t h e char r e c e i v e r w a l l and t o some e x t e n t on t h e char in t h e r e c e i v e r . Therefore t h e oil y i e l d d a t a are now beinp reexamined where t h e y i e l d in t h e gas sample stream is m u l t i p l i e d by t h e r a t i o of t h e t o t a l product gas flowrate t o t h e sample gas f l o w r a t e i n o r d e r t o e s t i m a t e t o t a l o i l y i e l d . These values w i l l probably be higher than t h e r e p o r t e d values. The values of t h e k i n e t i c parameters in Equation 7 f o r t h e d a t a in Figures 7 and 8 are l i s t e d i n Table 3. These parameters were evaluated both f o r t o t a l conversion and f o r carbon conversion t o equivalent methane. The v a l u e of a 1 gave t h e b e s t f i t of t h e t o t a l carbon conversion d a t a and w a s subsequently used t o f i t t h e carbon conversion t o methane data. The terminal v e l o c i t y of a s i n g l e char p a r t i c l e was c a l c u l a t e d using the equation

is due mainly t o t h e production of carbon oxides and o i l . Some experimental e r r o r i s a l s o introduced in measuring t h e flowrate and composition of t h e feed and product gases, and in recovery and a n a l y s i s of t h e s o l i d and l i q u i d products. @ f t e n t h e run times were n o t long enough t o c o l l e c t enough oil so t h e y i e l d could be a c c u r a t e l y

f o r 500

<

d p U ReD = peT U,
' 5

-[

3.1g(Ps-P
pgg

)ZP

1/2
8)

200,000

( ) correcting t h i s value for the effect zand,

of t h e cloud oi p a r t i c l e s (25). Table 4 lists t h e parameters used f o r c a l c u l a t i n g t h e terminal v e l o c i t i e s . A terminal v e l o c i t y of 16.5 f p s w a s used f o r t h e 805' 9 0 C d a t a and 10.7 f p s (average of 9.9 and 11.5) f o r t h e 725" C d a t a . 0' The t o t a l r e a c t o r p r e s s u r e has a l a r g e i n f l u e n c e on t h e terminal p a r t i c l e v e l o c i t y because t h e p r e s s u r e determines f o r t h e most p a r t t h e s i z e of t h e c h a r p a r t i c l e s produced and hence t h e bulk a n d p a r t i c l e d e n s i t i e s . This i s i l l u s t r a t e d in Figure 1 where t h e char bulk d e n s i t y is p l o t t e d versus t o t a l r e a c t o r pressure. 1 A s t h e p r e s s u r e i n c r e a s e s , t h e bulk d e n s i t y increases. The bulk d e n s i t y is higher when t h e feed gas contains about 50 p c t methane i n s t e a d of pure hydrogen. Apparently, increasing t h e r e a c t o r p r e s s u r e dampens t h e explosive e n i s s i o n o f gases during t h e r a p i d d e v o l a t i l i z a t i o n r e a c t i o n . A high concentration of hydrogen i n t h e r e a c t o r causes more of t h e carbon t o be reacted out of t h e p a r t i c l e s t r u c t u r e r e s u l t i n g in a lower bulk d e n s i t y char (and lower p a r t i c l e d e n s i t y ) than is obtained when t h e r e a c t o r feed gas contains about 50 p c t Eethane. Some char p a r t i c l e s i z e d a t a is l i s t e d in Table 5 showing how i n c r e a s e s i n r e a c t o r temperature and p r e s s u r e cause decreases in t h e mean char p a r t i c l e diameter.

TABLE 4.~~ ~~ ~~~

Parameters used t o c a l c u l a t e terminal v e l o c i t y

~ ~~

Temperature, Pressure, a t m - lb/hr f t 2 W, dp, i n . Pb, l b / f t 3 ps*, l b / f t 3

725 205 165 0.0521 13.33 36.8 1.408 0.05745 3.3 1264 3.0 9.9

725 103 128 0.0667 8.0 22.1 0.7074 0.05745 4.1 1010 2.8 11.5

900 205 145 0.0345 12.29 33.9 1.199 0.06409 2.8 542 3.0 8.4
~~ ~ ~~

900 69 207 0.0660 5.8 16.0 0.4035 0.06409 4.6 573 3.6 16.5

Estimated by t h e ratio of b u l k d e n s i t i e s and p a r t i c l e d e n s i t y of 16.0 l b / f t 3 (26) f o r c h a r produced a t 85O0-9OO0 C and 69 atm, e.g., 16 36.8.
I

**Ratio of t e r m i n a l v e l o c i t y t o s i n g l e p a r t i c l e terminal v e l o c i t y a t a s p e c i f i c mass feed r a t e p e r u n i t area (25).

TABLE 5.-

E f f e c t of r e a c t o r temperature and p r e s s u r e on average char p a r t i c l e s i z e Averape Char P a r t i c l e Diameter*. i n .

Press.,

atm/Temp., 69 83 103 205

-0.0667
0.0521

750

800
0.0735

850
0.0628 0.0566

900
0.0537 0.0501 0.0485 0.0345

--

I -

--

0.0492

0.0529

, Pittsburgh
mesh feed.

seam hvAb c o a l , 50 x 100

111
The e f f e c t of f e e d r a t e p e r u n i t r e a c t o r c r o s s s e c t i o n on t h e average c h a r p a r t i c l e diameter i s s h a m i n F i g u r e 12. A s t h e feed r a t e i s i n c r e a s e d f o r a f i x e d r e a c t o r diameter, t h e number of p a r t i c l e c o l l i s i o n s i n c r e a s e and hence t h e mean char p a r t i c l e s i z e i n c r e a s e s due t o agglomeration. At a mass f e e d rate of 2 2 1 W h r f t 2 , P i t t s b u r g h seam c o a l y i e l d e d an average c h a r p a r t i c l e diameter o f 1.70 mm (0.0669 inches) compared t o 0.487 mm (0.0192 inches) f o r char produced fron: I l l i n o i s #6 hvCb c o a l under i d e n t i c a l r e a c t o r conditions. The maximum c a p a c i t y i n t h e dilute-phase s e c t i o n of t h e two-stage i n t e g r a t e d r e a c t o r i s l i m i t e d by t h e s i z e o f t h e c h a r produced i n t h e d i l u t e phase s e c t i o n t h a t may be f l u i d i z e d adequately i n t h e seconds t a g e fluid-bed s e c t i o n . Therefore, t h e dilute-phase r e a c t o r c a p a c i t y w i l l b e much higher f o r I l l i n o i s c o a l than f o r P i t t s b u r g h c o a l because of t h e smaller s i z e char Particles produced. The feed rates p e r u n i t a r e a i n Figure 1 2 a r e probably low because t h e c o a l i s not completely d i s t r i b u t e d a c r o s s t h e dilute-phase r e a c t o r c r o s s s e c t i o n before rapid heat-up and d e v o l a t i l i z a t i o n , when t h e c o a l i s s u s c e p t i b l e t o cakinp. A s mentioned e a r l i e r , t h e c o a l is f e d by a 5/16 inch diameter tube i n t o a 3.26 i n c h diameter r e a c t o r . The p a r t i c l e s h i t t h e w a l l of t h e r e a c t o r about 12 inches down from t h e end of t h e feed nozzle. I f d e v o l a t i l i z a t i o n i s completed w i t h i n 6 inches from t h e end o f t h e nozzle, a feed r a t e c a l c u l a t e d t o b e 300 l b s / h r f t 2 of r e a c t o r CKOSS s e c t i o n a c t u a l l y corresponds t o a r a t e of 1000 l b s / h r f t 2 o f cross-sectional a r e a occupied by t h e p a r t i c l e s . Data from a f r e e - f a l l carbonizer 1 2 inches i n diameter, a t t h e Morgantown Energy Research Center, show t h a t P i t t s b u r g h c o a l w a s processed a t 1000 l b s / h r f t 2 and yielded char w i t h a mean diameter of about 0.508 m (0.02 i n c h e s ) . The f e e d c o a l w a s 70 p c t through 200 mesh.

(c),

The r e a c t i o n rate c o n s t a n t s f o r t h e FDP r e a c t o r are shown on a n Arrhenius p l o t i n Figure 13. The r e l a t i v e l y low a c t i v a t i o n energy of 15.1 kcal/mole of carbon r e a c t e d appears t o i n d i c a t e t h a t t h e r e a c t i o n may b e c o n t r o l l e d by mass t r a n s f e r of hydrogen t o t h e r e a c t i o n sites and not by t h e r a t e of h y d r o g a s i f i c a t i o n . Feldmann (2) has suggested t h a t i n t h e higher temperature range t h e r a t e may b e b e t t e r described as p r o p o r t i o n a l t o kgPH2, where k i s a mass t r a n s f e r c o e f f i c i e n t f o r hydrogen through t h e gas f i l m surrounding t8e p a r t i c l e . This seems reasonable s i n c e a s t r a i g h t l i n e could have j u s t as e a s i l y f i t t h e t o t a l carbon conversion d a t a i n Figures 7 and 8. The a c t i v a t i o n energy f o r carbon h y d r o g a s i f i c a t i o n i n an e n t r a i n e d flow r e a c t o r was determined by Zahradnik and Glenn (2)o be 15 kcal/mole, i n t agreement with t h e v a l u e obtained i n t h i s work. They suggest t h a t t h i s a c t i v a t i o n energy r e p r e s e n t s t h e d i f f e r e n c e i n a c t i v a t i o n energy between t h e h y d r o g a s i f i c a t i o n and polymerization r e a c t i o n s . An Arrhenius p l o t of Feldmann's i n which he c a l c u l a t e s k by i n t e g r a t i n g Equation 7 from zero t o x i n s t e a d of from E t o x , shows some low temperature FDP data. The a c t i v a t i o n energy i s 29.8 kcal/mole f o r tempera t u r e s below 580' C , and decreases t o 6.4 kcal/mole f o r temperatures above 580' C . The k values were c a l c u l a t e d t h i s way because E could not be determined f r o g t h e ~ a v a i l a b l e data and because P H w a s approximately constant. This change i n a c t i v a t i o n energy supports Feldmann's suggestion t h a t t h e r e a c t i o n i s mass t r a n s f e r controlled. More comments w i l l b e made on t h e s e r e s u l t s a f t e r reviewing some low-temperature "hot-rod" r e a c t o r data.

(L)

The.data presented f o r t h e FDP r e a c t o r a r e based mainly on P i t t s b u r g h seam hvAb coal. This c o a l was s t u d i e d e x t e n s i v e l y because of i t s extreme s w e l l i n g and agglomera t i n g p r o p e r t i e s . If t h e r e a c t o r could process badly caking coal t h a n s u r e l y i t could e a s i l y handle mildly caking coals. I l l i n o i s 16 hvCb c o a l i s m i l d l y caking and FDP r e s u l t s on t h i s c o a l are shown i n Figure 14. The conversion of I l l i n o i s c o a l has n o t been s t u d i e d over a wide range of hydrogen p a r t i a l p r e s s u r e as h a s t h e P i t t s b u r g h coal, but does appear t o be more r e a c t i v e based on comparison of t h e two coals i n Figure 1 4 a t t h e same r e a c t o r conditions.

"Ho t-Rod" Reactors

112

The results from t h e "hot-rod" r e a c t o r tests of Hiteshue, Friedman, and Madden b e r e f e r r e d t o a s HR-1 series when c o a l is used a s t h e s t a r t i n g r e a c t a n t and HR-1C when char is used. Unpublished d a t a of Feldmann and Williams w i l l be r e f e r r e d t o as HR-2 and HR-2C series. The weight l o s s and carbon conversion data a r e shown i n Figures 1 5 and 16, respectively. f o r t h e HR-2 series e x p e r i r e n t s . I n most of t h e HR-2 tests t h e r e a c t o r temperature was maintained low enough t h a t Type 2 carbon conversion appeared t o occur over a period of about 6 minutes. Once t h e temperature exceeded about 600" C, Type 3 carbon w a s r a p i d l y formed. The conversions a t which t h e curves i n Figure 1 5 o r 16 appear t o l e v e l off correspond t o t h e t r a n s i t i o n p o i n t s a t which t h e hydrogasification occurs predominately with Type 3 carbon. For t h e tests a t 800 C, t h e d e v o l a t i l i z a t i o n and Type 2 carbon conversion both occur i n less than a minute. This is mre c l e a r l y v i s i b l e when t h e r a t e constants a r e p l o t t e d on t h e same Arrhenius graph with t h e FDP d a t a i n Figure 13. For t h e d a t a up t o 600" C , Equation 4 w a s i n t e g r a t e d s t a r t i n g from zero carbon conversion, and t h e v a l u e s of k and a were determined from a least-squares f i t of t h e d a t a (E w a s found t o be very c l o s e t o z e r o i n t h e r e g r e s s i o n a n a l y s i s f o r temperatures below 520' C). For t h e 800" C d a t a , t h e i n t e g r a t i o n was s t a r t e d from E with a = 1, and a g a i n k and E were determined from a least-squares a n a l y s i s of the data. The v a l u e s of t h e s e parameters are l i s t e d i n Table 6. The model was a l s o f i t t o t h e t o t a l weight l o s s d a t a in F i g u r e 15. As i s obvious in Figure 16, t h e carbon conversions c a l c u l a t e d from t h e carbon analyses were n o t c o n s i s t e n t a t 425" C and 69 atm w i t h e i t h e r t h e t o t a l conversion data i n F i g u r e 15 o r d a t a a t 35 a t m . Therefore, t h e carbon g a s i f i c a t i o n r a t e constant a t 425' C w a s c a l c u l a t e d by e x t r a p o l a t i n g t h e l i n e obtained when k i s p l o t t e d versus $ ( r a t e c o n s t a n t f o r t o t a l conversion). The k v a l u e a t 425' C can a l s o be estimated by assuming t h e curve must pass through 0.0588 (average of two d a t a p o i n t s ) a t 6 minutes. This method gives a k value of 0.255 atm-l hr-' compared to 0.365 arm-? 'nr-lby e x t r a p o l a t i o n ,

(L) w i l l

I n t h e Arrhenius p l o t of F i g u r e 13, t h e low temperature "hot-rod" r e a c t o r d a t a appears t o b e c o n s i s t e n t with t h e dilute-phase r e a c t o r data. Unfortunately, low temperature FDP d a t a is very d i f f i c u l t t o obtain i n o r d e r t o v e r i f y t h e low tempera t u r e "hot-rod'' r e a c t o r d a t a because of agglomeration and plugging. The high temperature "hot-rod" r e a c t o r d a t a cannot v e r i f y t h e FDP d a t a because t h e heat-up r a t e and residence t i m e s a r e such t h a t they o p e r a t e in d i f f e r e n t carbon conversion regimes. The key d i f f e r e n c e between t h e FDP r e a c t o r and t h e "hot-rod" r e a c t o r is t h e c o a l heat-up r a t e . I n t h e FDP r e a c t o r t h i s rate is on t h e o r d e r of 1000 C/sec whereas i n t h e "hot-rod" r e a c t o r t h e rate is about 7 C/sec. By achieving r e a c t i o n ' temperature quickly enough, t h e k i n e t i c s of Type 2 carbon h y d r o g a s i f i c a t i o n can be observed

The carbon conversion d a t a f o r the HR-1 series e x p e r b e n t s a r e shown i n Figure 17. In t h e s e tests t h e d e v o l a t i l i z a t i o n and Type 2 carbon conversion occurred i n less than a minute because o f t h e high temperatures. Therefore t h e curves f o r t h e most p a r t r e p r e s e n t Type 3 carbon conversion. Johnson (23) h a s observed i n thermobalance experiments t h a t d e v o l a t i l i z a t i o n and Type 2 carbon conversion a r e e s s e n t i a l l y complete w i t h i n 2 minutes a t temperatures above about 800" C. The heat-up r a t e i n t h e thermobalance t e s t s was about t h e same as in t h e "hot-rod" r e a c t o r tests. The HR-1 s e r i e s d a t a were f i t using Equation 4 with a = 1 and i n t e g r a t i o n s t a r t i n g from E. The k i n e t i c parameters a r e l i s t e d i n Table 7. Choosing a = 1 simply means t h a t e s s e n t i a l l y a l l t h e carbon beyond t h e f r a c t i o n E is Type 3. Here E r e p r e s e n t s t h e sum of Types 1 and 2 carbon. F i g u r e 18 i l l u s t r a t e s t h e e f f e c t of t h e r e a c t o r temperature on t h e amount of carbon t h a t can be hydrogasified as Types 1 and 2. High temperatures and hydrogen

113
TAELC 6.K i n e t i c p a r a a e t e r s f o r UR-2 series data
1 ;

Temp., * C

PI! , a t n
69 69 69 69 69 69 69 69

E 0 0 0 0 0 .175 0 .243

atv-lhr-l

UT** -

%**
a t r - l hr-

425 470 490 520 600 600 800 800

.071* .189 .199 .179 .232 1.0 .315

1.0

0.383* 0.447 0.625 1.47 0.976 0.00751 1.22 0.0123

.099 .261 .278 .264 .272 .344

---

0.510 0.504 0.838 2.07 1.08

---

---

1.66

Extrapolated usinp t o t a l conversion kT values. is 0.255 atn-lhr-

Ey another method, t h e k value

**

Subscript T i n d i c a t e s t o t a l conversion p a r a p e t e r s ( t o t a l weipht loss).

TABLE 7.-

K i n e t i c p a r a u e t e r s f o r ER-1 s e r i e s d a t a

Tenp.,

PH

, atr
18.0 35.0 69.0
4.1

a 1.0 1.0
1.0 1.0

1 . atv-lhr-l

800 800 800 1200 1200 1200

.252 .355 .A50

.298

18.0 35.0

l.@
1.0

.377 .514

0.0282 0.0154 0.0160 0.363 0.137 0.350

TABLE 8.- E f f e c t of hydropen p a r t i a l p r e s s u r e on c a r t o n conversion in t h e hot rod r e a c t o r Carbon Conversion, p e t 1 pin. 2 pin. 5-6 c i n . 30.7.25.7 39.4,40.4 52.0,55.5,52.6,54.6 9.10 12.1 10.4 14.5 17.6 18.4 17.5 17.9 21.0 23.7 24.3 31.2 25.6 25.8 33.9

Test -

Tenp..

Fp,,

ata

BR-1 HR-1 HR-1 m-2

m-2
ER-2 IIR-2 HR-2 HR-2 HR-2

800 800 800 500 490 600 600 700 800 800

18 35 69 35 69 35 69 35 35 69

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-----

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---

-----------

p a r t i a l pressures result i n a l a r g e amount of carbon being hydrogasified i n t h e Types 1 and 2 regime.. I n f a c t Moseley and Paterson (22) have shown t h a t a t a hydrogen p a r t i a l p r e s s u r e of 500 a m and 900' C, t h e carbon is r a p i d l y g a s i f i e d t o completion. There is a l a r g e d i f f e r e n c e i n t h e l e v e l of Types 1 and 2 carbon conversion 0' between t h e HR-1 d a t a a t 8 0 C and t h e corresponding HR-2 tests. This discrepancy is s h a m i n Table 8 and is e s p e c i a l l y n o t i c e a b l e at 800" C and 69 atm. Under t h e s e c o n d i t i o n s t h e conversions from t h e HR-1 t e s t s range from 52 t o 54.6 p c t a t a residence t i m e of 5 minutes whereas t h e corresponding conversions f o r t h e HR-2 tests ranged from 31.2 t o 33.9 p c t a t a residence time of 6 minutes. The l a c k of response o f conversion t o changes i n hydrogen p a r t i a l p r e s s u r e i n t h e HR-2 tests suggests t h a t the r e a c t i o n r a t e was s t r o n g l y mass t r a n s f e r c o n t r o l l e d . This can be v e r i f i e d by comparing t h e gas v e l o c i t i e s i n t h e HR-1 and HR-2 experiments i n Table 9. I n t h e HR-1 t e s t s t h e s u p e r f i c i a l hydrogen feed g a s v e l o c i t y was 36 cm/sec compared t o a v e l o c i t y o f 1 t o 2 cm/sec i n t h e HR-2 tests. Apparently t h e pas v e l o c i t y w a s low enough i n t h e HR-2 tests t h a t a t the higher temperatures t h e mass t r a n s f e r r e s i s t a n c e through t h e p a r t i c l e gas f i l m was s i g n i f i c a n t . In a d d i t i o n , t h e slower p a r t i c l e heat-up r a t e may have c o n t r i b u t e d t o t h e d i f f e r e n c e i n conversions. has Anthony (2) demonstrated, however, t h a t varying t h e h e a t i n g r a t e from 180 t o 10,000" C/sec has no e f f e c t on t h e c o a l conversion. H e found smaller p a r t i c l e sizes and more highly dispersed samples t o be extremely important because t h e f l u x of v o l a t i l e s emerging from t h e c o a l p a r t i c l e may l i m i t t h e counter d i f f u s i o n of hydrogen i n t o t h e p a r t i c l e . This r e s t r i c t i o n makes i t d i f f i c u l t f o r t h e h y d r o g a s i f i c a t i o n r e a c t i o n t o compete with polymerization r e a c t i o n s t h a t produce a r e l a t i v e l y i n a c t i v e char. I n Table 1 0 t h e Types 1 and 2 carbon conversion f o r FDP and "hot-rod" r e a c t o r The HR-2 tests were d e f i n i t e l y mass t r a n s f e r c o n t r o l l e d whereas t e e t e ere coxqare:. i t is d i f f i c u l t t o conclude t h i s i n t h e FDP tests compared t o t h e HR-1 tests because of t h e l a r g e d i f f e r e n c e i n r e s i d e n c e t i m e . I n t h e FDP r e a c t o r t h e residence t i m e w a s less than 1 second and i n t h e "hot-rod" r e a c t o r i t was two orders of magnitude g r e a t e r . Anthony (2) s h a m t h a t Types 1 and 2 carbon conversions are complete has 0' a f t e r about 3 seconds at 69 arm, 9 0 C, and a heating r a t e of 750' C/sec. His s t a r t i n g c o a l p a r t i c l e s i z e was 70 microns compared t o about 220 microns i n t h e FDP experiments. Therefore Types l a n d 2 carbon conversion i n t h e FDP tests probably d i d n o t reach completion. Photographs of some of t h e c h a r s under a scanning e l e c t r o n microscope r e v e a l t h e porous s t r u c t u r e produced i n t h e FDP and "hot-rod" r e a c t o r s under various conditions. F i g u r e 19 compares c h a r s produced i n t h e FDP r e a c t o r a t 725' C , 205 a t m ( t o p - l e f t ) , and a t 850 C, 69 a t m (bottom-left). The c h a r produced a t 69 a t m appears t o b e much more porous and less dense than t h e char made a t 205 atm. As discussed previously, this e f f e c t shows up a s a l a r g e d i f f e r e n c e i n bulk density.

0' F i g u r e 20 compares c h a r s produced i n t h e "hot-rod" r e a c t o r a t 6 0 C, 69 a t m (bottom) and a t 800 C, 69 a t m ( t o p ) a t d i f f e r e n t residence times. The low temperature c h a r h a s nuch l a r g e r pores w h i l e t h e high temperature c h a r h a s a l a r g e r number of very small pores. This d i f f e r e n c e i n t h e pore size is probably r e l a t e d t o t h e higher emission r a t e o f v o l a t i l e matter from t h e p a r t i c l e s r e a c t e d a t 8 0 C. I n a d d i t i o n , t h e super0' f i c i a l hydrogen v e l o c i t y i n t h e 600 C test was 0.9 cm/sec versus 1.1 cm/sec i n t h e 800' C t e s t . Both t h e s e c o n d i t i o n s (high v o l a t i l e s emission, low gas v e l o c i t y ) l i m i t c o u n t e r d i f f u s i o n of hydrogen i n t o t h e c h a r s t r u c t u r e r e s u l t i n g i n l e s s Competition f o r t h e polymerization r e a c t i o n . Comparison o f t h e FDP and "hot-rod" char Samples i n d i c a t e s t h a t t h e pore s t r u c t u r e of t h e FDP char is more h i g h l y developed with pores having t h i n walls. The samples i n Figure 20 were crushed t o 100 pct t h r u 60 mesh 8 0 t h a t t h e g r o s s pore s t r u c t u r e is n o t a s clear as p o s s i b l e .

115

TABLE 9 - Effect of hydrogen velocity on carbon conversion . in the hot rod reactor at 8 0 C 0'
I

pH

Series HR-1 HR-2HR-1 HR-2 HR-lC HR-2C Pgh. Pgh. Pgh. Pgh. Pgh. Ill.

, atm
2

132

Sample

velocity cmfsec 36.6 2.19 36.6 1.11 36.6 1.11

Average Carbon Residence Conv.. % Time, min. 39.9 31.2 53.7 33.9 31.4 31.2

hvAb Coal hvAb Coal hvAb Coal hvAb Coal hvAb Char 16 hvCb Char

35 35 69 69 69 69

5 6 5 6 15 15

TABLE 10.- Comparison of types 1 and 2 carbon conversion

in the FDP and "Hot-Rod" Reactors Tests FDP* pDP*

HR-1**

PH

, atm

Carbon Conv., % 27.2 32.2 33.2, 32.8 38.5, 40.3 23.7 25.6

HR-1** HR-2** HR-2** *From Figure 8, 850'-900" **800 C.

35.0 69.0 35.0 69 .n 35.0 69.0 C.

TABU 11.- Kinetic parameters for HR-1C series data

Temp,,

PH
7

, atm
18.0 35.0 69.0 69.0

a 1.0
10 . 10 .

E
.009 .027 .144 .136

800 800 800 800

*HR-SC data.

1.0

k amlr' t-h' .0234 .0178 .0110 .0137*

116
F i g u r e 2 1 shows t h e c h a r samples from FDP tests a t 850 C and 69 a t m using a l i g n i t e c o a l f e e d , The p o r e s t r u c t u r e appears very undeveloped compared t o t h e s t r u c t u r e obtained w i t h bituminous coal. Because of t h e l a c k of p a r t i c l e s w e l l i n g w i t h l i g n i t e (coal p a r t i c l e a l s o i n Figure 21), t h e p e n e t r a t i o n o f hydrogen i n t o t h e p a r t i c l e i s poorer compared t o bituminous coal. Consequently, p a r t i c l e s i z e should have an even s t r o n g e r i n f l u e n c e on t h e h y d r o g a s i f i c a t i o n of lignite than w i t h bituminous coals. The c h a r d a t a i n Table 9 are v e r y i n t e r e s t i n g because t h e s u p e r f i c i a l hydrogen v e l o c i t y had n o e f f e c t on t h e carbon conversion. The mass t r a n s f e r rate i n t o t h e c h a r p a r t i c l e s must b e l a r g e compared t o t h e char-hydrogen r e a c t i o n rate. This i s not s u r p r i s i n g since t h e r e a c t i o n r a t e of Type 3 carbon is very slow, probably much slower than t h e d i f f u s i o n rates of hydrogen and gaseous r e a c t i o n products. The results o f HR-1C series experiments with char produced from P i t t s b u r g h seam hvAb c o a l are shavn i n F i g u r e 22. The carbon conversion i s of t h e Type 3 s p e c i e s e x c e p t f o r a small amount o f r a p i d i n i t i a l conversion. The k i n e t i c parareters f o r t h e s e d a t a are l i s t e d i n Table 1 . The results o f t h e HR-2C series experiments are 1 a l s o shown i n Table 1 and F i g u r e 22, and agree w e l l w i t h t h e HR-1C data. The two 1 c h a r s are d i f f e r e n t i n that t h e HR-2C c h a r was produced from I l l i n o i s #6 hvCb c o a l i n t h e d i l u t e phase r e a c t o r at 5 5 C whereas t h e HR-1C c h a r was produced from 8' P i t t s b u r g h seam hvAb coal by b a t c h c a r b o n i z a t i o n f o r 2 h o u r s i n helium a t 600 C. The HR-2C c h a r contained about 26 p c t v o l a t i l e matter compared t o t h e o r i g i n a l 36.5 p c t volatile m a t t e r i n t h e s t a r t i n g coal. Despite t h e s e d i f f e r e n c e s , except f o r t h e n e a r l y e q u a l d e v o l a t i l i z a t i o n temperatures, the r e a c t i v i t i e s of t h e two c h a r s are e s s e n t i a l l y t h e same. A s i g n i f i c a n t d i f f e r e n c e i n t h e d e v o l a t i l i z a t i o n temperatures could have r e s u l t e d i n t h e c h a r s having d i f f e r i n g r e a c t i v i t i e s (23,2). The Arrhenius graph i n F i g u r e 13 summarizes the r e s u l t s f o r a l l t h e c o a l s and c h a r s t e s t e d and Includes some of Johnson's d a t a (23)which was a d j u s t e d t o c a l c u l a t e k v a l u e s according t o Equation 4. Assuming t h a t i t i s v a l i d t o r e p r e s e n t t h e low temperature "hot-rod" r e a c t o r d a t a by t h e same Arrhenius l i n e as t h e FDP d a t a , t h e a c t i v a t i o n energy f o r h y d r o g a s i f i c a t i o n of Type 2 carbon i s 15.1 kcal/mole of carbon g a s i f i e d . The h y d r o g a s i f i c a t i o n rate of Type 3 carbon i s about t h r e e o r d e r s of magnitude lower than t h e rate o f h y d r o g a s i f i c a t i o n of Type 2 carbon. The a c t i v a t i o n energy f o r t h e HR-1, HR-lC, and HR-2C d a t a i s 24.7 kcal/mole of carbon g a s i f i e d (Type 3 carbon) compared to a v a l u e of 47.1 kcal/mole obtained by Johnson (23) u s i n g a thermobalance. A t 600Oand 8 0 C , t h e HR-2 d a t a was complicated by t h e t r a n s i t i o n t o Type 3 0' carbon conversion and a s i g n i f i c a n t amount of mass t r a n s f e r r e s i s t a n c e . A t t h e s e higher temperatures t h e apparent a c t i v a t i o n energy f a l l s o f f considerably as shown i n F i g u r e 13. Two-Stage I n t e g r a t e d Reactor The results of t h e two-stage tests where t h e f i r s t - s t a g e was a FDP r e a c t o r and t h e second-stage e i t h e r a moving-bed o r fluid-bed r e a c t o r have been presented elsewhere @). The k i n e t i c r e s u l t s a r e summarized i n Tables 1 2 , 13, and 14 and are a l s o p l o t t e d .in F i g u r e 1 3 . Because h e a t t r a n s f e r l i m i t a t i o n s w i t h i n t h e char p a r t i c l e s caused t h e t r u e p a r t i c l e temperature t o be h i g h e r than t h e measured temperature, t h e a c t i v a t i o n energy o f t h e moving bed d a t a is low, and t h e r a t e c o n s t a n t v a l u e s are r e l a t i v e l y h i g h a t t h e lower r e a c t o r temperatures. C o r r e l a t i o n of Char Y i e l d and Coal H. N, S. and 0 Conversion Data

1
I

I n o r d e r t o p r e d i c t t h e conversion of o t h e r c o n s t i t u e n t s i n t h e c o a l during h y d r o g a s i f i c a t i o n b e s i d e s carbon conversion, results from n i n e t y - f i v e experiments

117
TABLE 12.- Kinetic results from two-stage integrated reactor experiments (18) at 69 atm

Run
b.

Total C Conv., X 0.552 0.536 0.558 0.608 0.551 0.556 0.537 0.620 0.392 0.485 0.417 0.430 0.391 0.406 0.399 0.511 0.536 ,

Moving Bed C Conv., Z*

Fluid Bed C Conv., Z* 0.378 0.356 0.345 0.419 0.335 0.383 0.357

Bed
Temp.,
O K

k atm-lhr-l 0.0145 0.0284 0.0316 0.0450 0.0202 0.0218 0.0139 0.0573 0.0360 0.0396 0.0449 0.0395 0.0260 0.0307 0.0305 0.0299 0.0358

2 3 5 11 12 13 14 33 37 38 39 43b 44b 45b 46a 48 49

------0.457 0.131 0.264 0.167 0.186 0.130 0.151 0.151 0.301 0.337

-----

-----

---------------------

1158 1158 1158 1073 1118 1113 1183 1178 1173 1148 918 1038 923 933 957 1073 988

TABLE 13.- Hydrogasification of I l l i n o i s 1 6 hvCb c o a l i n a two-stage run c o n d i t i o n s r e a c t o r a t 1000 p s i g

Test Reactor Zone Temp., C Coal o r Char Rate, l b ( d r y ) / h r Bed Height, i n . Residence Time, min. Feed Gas, SCFH Vol. P c t . H2 He Product Gas, SCFH** Vol. Pct. H2
CH4
m 4 N2

46 FDP* 850 10.51

48

49

MB*
684 6.68
0

FDP
850 10.26 181.7 52.0 42.1 1.10 4.70 179.0 32.4 57.2

MB
800 5.08 36 10.4 152.0 99.0 1.00

FDP
850 10.32 166.2 50.9 42.8 1.50 4.70 169.8 30.1 58.0

MB
715 5.01 36 10.4 150.7 98.6 1.30 130.3 58.0 39.0 187

----

164.4 56.2 37.2 1.05 5.45 168.6 34.8 55.1

0 141.4 99.4

--

--

--

0.50 141.4 99.4 187

---

----

--

Run Time, min.

124.6 54.2 43.5 193

* FDP:

free-fall

d i l u t e phase r e a c t o r ( 3 f o o t heated l e n g t h ) ; MB:

moving-bed reactor.

**For runs 4 8 and 49, t h e i n d i v i d u a l product pas f l o w r a t e s and t h e composition of the MB product gas p r i o r t o mixing were estimated using t h e helium t r a c e r d a t a ,

TABLE 14.-

Hydrogasification of I l l i n o i s 16 hvCb c o a l i n a two-stape results r e a c t o r a t 1000 p i p .

T e s t HY Conversion, w t . p c t . MAF c o a l
C

46 43.1 33.0 75.4 66.7 59.4 91.0 3.01 0.11 0.43 0.10 -3.21 0.04 0.048 24.3 0.433

48 60.2 50.7 96.4 74.8 89.7 99.6 7.80 0.17 0.69 0.09 -11.63 0.03 0.041 47.7

49 60.4 53.6 93.4 76.3 86.4 90.0 7.58 0.13 0.80 0.11 -10.31 0.07 0.026 44.2 0.397

H
S

N
0

Gas Yields, SCF/lb dry c o a l

CH4 C2H6

co

co2
H2 H2S*

O i l Yield, l b / l b d r y coal Carbon t o Gas and O i l s , w t . p c t . Mean Char P a r t i c l e Diameter, m

--

About S X of t h e converted s u l f u r appears i n t h e gas product a f t e r O water scrubbing.

I19
i n t h e FDP r e a c t o r and FDP-Fluid Bed i n t e g r a t e d r e a c t o r s were c o r r e l a t e d w i t h carbon conversion t o y i e l d Figures 23-26. The c o r r e l a t i o n s i n Figures 23-25 show t h a t char y i e l d and r e m v a l of c o a l hydrogen and n i t r o g e n can be a c c u r a t e l y c a l c u l a t e d from carbon conversion, independent of r e a c t o r conditions and p o s s i b l y geometry. For carbon conversions above 20 p c t ( e s s e n t i a l l y d e v o l a t i l i z a t i o n ) t h e oxygen removal u s u a l l y exceeds 90 p c t and can be considered t o b e complete. The d a t a f o r s u l f u r removal are very s c a t t e r e d , p o s s i b l y because of t h e e r r o r i n determining changes in s m a l l amounts of s u l f u r i n t h e c o a l and c h a r samples. In a d d i t i o n , t h e hydrogen s u l f i d e t h a t is formed may be i n e q u i l i b r i u n w i t h s u l f u r i n t h e char such t h a t a Simple c o r r e l a t i o n w i t h carbon conversion i s n o t p o s s i b l e .

In Figure 27, t h e char y i e l d s have been recomputed in terms of Y F conversion so t h a t t h e r e l a t i o n s h i p between carbon conversion and MAF conversion can b e
shown. A curve is drawn through t h e d a t a such t h a t i t bows away from t h e u n i t s l o p e l i n e and passes through (0.0) and (100,100). The d a t a i n Figures 23-25 only covered t h e carbon conversion range 22-55 p c t a0 t h a t o r s i m p l i c i t y a s t r a i g h t l i n e was used t o f i t t h e data. As t h e range is widened, however, i t becomes obvious t h a t a curve gives a b e t t e r c o r r e l a t i o n of t h e data. The carbon conversion r a n r e covered by t h e HR-1 and IIR-2 series experirrents is complete, ranging from 0 t o 95 p c t . In Figure 28, t h e MAF conversion i s p l o t t e d v e r s u s carbon conversion and e s s e n t i a l l y t h e sme curve as used i n F i g u r e 27 f i t s t h e s e results. Based on t h e s e curves i t appears t h a t t h e c o r r e l a t i o n s of c o a l c o n s t i t u e n t conversions w i t h carbon conversion a r e n o t only independent o f r e a c t o r conditions, but a l s o r e a c t o r geometry. Figure 29 shows a s i m i l a r MAF-carbon conversion p l o t f o r t h e HR-1C and HR-2C series c h a r tests. The carbon conversion i n F i g u r e 29 does n o t include t h e carbon t h a t w a s l o s t during d e v o l a t i l i z a t i o n o f t h e c o a l t o prepare t h e char. The conversion of coal 11, N, and S in t h e HR-1 and HR-2 series experiments a r e shown i n Figures 30-32. In Figures 30 and 31, t h e s t r a i g h t l i n e f i t s of t h e H and N d a t a determined p r e v i o u s l y a r e shown t o be inadequate over a v e r y wide range of carbon conversion. These sets of d a t a a r e both f i t b e s t w i t h curves t h a t a r e concave downward, s i m i l a r t o t h e MAF curves. Despite t h e s c a t t e r i n t h e d a t a , t h e c o r r e l a t i o n with carbon conversion still appears t o b e v a l i d . Unlike i n t h e FDP and Two-Stage r e a c t o r experiments, u l t i m a t e analyses were n o t run on t h e c o a l f e e d f o r each test, b u t only on t h e e n t i r e b a t c h of coal. Consequently, some segregation in t h e f e e d s could have occurred causing scatter i n t h e c a l c u l a t i o n of t h e H , N, and s u l f u r conversions. These c o n s t i t u e n t s are p r e s e n t in r e l a t i v e l y small amounts and thus t h e i r c a l c u l a t e d conversions are very s e n s i t i v e t o f l u c t u a t i o n s i n t h e feed composition. The s u l f u r d a t a i n Figure 32 shows a more d e f i n i t e trend w i t h carbon conversion than w a s e v i d e n t i n F i g u r e 26 and shows t h e l a t t e r c o r r e l a t i o n t o b e conservative. Work is planned t o extend t h e l i n e a r c o r r e l a t i o n s i n Figures 23-26 t o a regression curve t h a t w i l l f i t a l l o f t h e data, i.e., FDP, HR-1, HR-2, and t h e Two-Stage reactors. These r e l a t i o n s h i p s a r e very valuable i n scale-up design c a l c u l a t i o n s because t h e displacement of t h e v o l a t i l e elements i n t h e c o a l and t h e char y i e l d can be a c c u r a t e l y p r e d i c t e d f o r t h e p l a n t flowsheet.

120
NOMENCLATURE
a
f r a c t i o n of t h e carbon t h a t is a v a i l a b l e f o r r e a c t i o n in t h e regime being considered. f r a c t i o n a l weight l o s s t h a t can be achieved in t h e r e a c t i o n regime being considered. E same a s a except t h e Type 1 carbon is excluded. s t o i c h i o m e t r i c c o e f f i c i e n t f o r the char-hydrogen gas Viscosity, l b / f t hr. char bulk d e n s i t y , l b / f t 3 . gas density, l b / f t 3 . c h a r particle d e n s i t y , l b / f t 3 . mean char p a r t i c l e diameter, in. f r a c t i o n of carbon instantaneously d e v o l a t i l i z e d . gravitational acceleration, ft/sec2. char-hydrogen r e a c t i o n r a t e c o n s t a n t , atm-' weight l o s s r e a c t i o n rate constant, atm-' reactor length, f t .
pH2
'

reaction.

hr-l. hr-l.

p a r t i a l p r e s s u r e o f hydrogen, atm. char particle Reynolds number. t i m e , sec. f r e e - f a l l v e l o c i t y of char p a r t i c l e s , fps.

Re P
t

' T S

s i n g l e char p a r t i c l e terminal v e l o c i t y , fps. c o a l mass f e e d r a t e , l b / h r f t 2 . f r a c t i o n a l carbon conversion based on t o t a l c o a l carbon. f r a c t i o n a l carbon conversion based on s t a r t i n g char carbon.

w
X

'

L
References

1 Feldmann, H. F , C. Y Wen, W. H. Simons, and P M Yavorsky. Supplemental . . . . . Pipeline Gas From Coal by the HYDRANE Process. Presented at the 71st National AIChE Meeting, Dallas, Texas, Feb. 20-23, 1972.
2 . 3 .
7

. . . . Feldmann, H F and P M Yavorsky. The HYDRANE Process. Presented at the 5th AGA/OCR Synthetic Pipeline Gas Symposium, Chicago, Illinois, Oct. 29-31, 1973.
Wen, C Y., C T Li, S. H. Tscheng, and W. S O'Brien. Comparison of Alternate . . . . Coal Gasification Processes for Pipeline Gas Production. Presented at the 65th Annual AIChE Meeting, New York, New York, Nov. 26-30, 1972.

,
I

4 Wen, C Y, coworkers. Optimization of Coal Gasification Processes, Research . . . and Development Rept. No. 66, Interim Rept. Nos. 1 and 2, O.C.R., U . S . Dept. of the Interior, Wash., D. C . 5 .

. . . . . . Feldmann, H F , W H Simons, J. A. Mlma, and R W Hiteshue. Reaction Model for Bituminous Coal Hydrogasification in a Dilute Phase. Preprints of Fuel Division, ACS, V. 14, No. 4, Part 11, Sept. 1970, pp. 1-13.

6 Feldmann, H F, J A Mlma, and P M Yavorsky. Pressurized Hydrogasification . . . . . . . of Raw Coal in a Dilute-Phase Reactor. Fuel Gasification, Advances in Chem. Series 131, ACS, Washington, D C., 1974, pp. 108-125. .
7 . Hiteshue, R W , S Friedman, and R Madden. Hydrogasification of High-Volatile . . . . .. A Bituminous Coal. U S Bureau of Mines Report of Investigation 6376, 1964. Hiteshue, R W , R B Anderson, and M D. Schlesinger. Hydrogenating Coal at . . . . . 8 0 C Ind. & Eng. Chem., 9 (Dec., 1957), pp. 2008-10. 0' . Hiteshue, R W , P S Lewis, and S Friedman. Gaseous Hydrocarbons from Coal. . . . . . Paper presented at the A G A . . . Operating Section Conference, 1960 (CEP-60-9).

8.

9 .

1 . Hiteshue, R. W, S Friedman, and R Madden. Hydrogenation of Coal to Gaseous 0 . . . Hydrocarbons. U.S. Bureau of Mines Report of Investigation 6027, 1962.
1 . Friedman, S., R W Hiteshue, and M. D Schlesinger. Hydrogenation of New 1 . . . Mexico Coal at Short Residence Time and High Temperature. US Bureau of Mines .. Report of Investigation 6470, 1964.
12. Hiteshue, R W , R B Anderson, and S. Friedman. Gaseous Hydrocarbons by . . . . Hydrogenation of Coals and Chars. Ind. 6 Eng. Chem.. 52 (July, 1960), pp. 577-9.

13. Hiteshue, R W, S Friedman, and R Madden. Hydrogasification of Bituminous . . . . Coals, Anthracite, and Char. U.S. Bureau of Mines Report of Investigation 6125, 1962.

1 . KaQa, W, R W Hiteshue, W A Budd, S. Friedman, and R. B. Anderson. 4 . . . . .

I

Agglomeration Studies in the Low-Pressure Hydrogenation of Coal in a Fluidized Bed. U . S . Bureau of Mines Bulletin 579, 1959. 15. Lewis, P S and R. W Hiteshue. Hydrogenating Coal in the Entrained State. . . . Ind. h Eng. Chem., 2 (Nov., 1 6 ) pp. 919-20. 90.

1 . Lewis, P S., S Friedman, B W Hiteshue. High Btu Gas by the Direct Conversion 6 . . . . of Coal. Fuel Gasification Advances in Chem. Series 69, ACS, Washington, D. C , . 1967, pp. 50-63.

122 17. Hiteshue, R. W. The Hydrogasification of Raw Coal. Paper presented a t t h e h e r . Gas Assoc. Symposium on Synthetic P i p e l i n e Gas, P i t t s b u r g h , Pa., Nov. 15, 1966. Wen, C. Y., S Mori, J. A. Gray, and P. M. Yavorsky. Application of t h e Bubble. Assemblage Model t o t h e HYDRANE Process Fluid-Bed Hydrogasifier. Paper presented a t t h e 67thAnnualAIChE Meeting, Wash., D. C., Dec. 1-5, 1974. Feldmann, 11. F., W. H. Simons, C. Y. Wen, and P. M. Yavorsky. Simulation of a Reactor System f o r t h e Conversion o f Coal t o Methane by t h e HYDRANE Process. Paper presented a t t h e 4 t h I n t e r n a t i o n a l Congress of Chem. Eng., Marianske Lame, Czechoslovakia, Sept. 11-15, 1972. Given, P. H. The D i s t r i b u t i o n of Hydrogen in Coals and Its R e l a t i o n to'Coa1 Structure. Fuel, 2 (1960), pp. 147-153. Zahradnik, R. L. and R . A. Glenn. (1971), pp. 77-90. The Direct Yethanation of Coal. F u e l s , No. 1,

18.

19.

20.

21. 22.

Moseley, F. and D. Paterson. The Rapid High-Temperature Hydrogenation of CoalChars P a r t 2: Hydrogen P r e s s u r e s up t o 1,000 Atmospheres. J. I n s t . o f Fuel, - (Sept., 19651, pp. 378-391. 38 Johnson, J. L. K i n e t i c s of Bituminous Coal Char G a s i f i c a t i o n w i t h Gases Containing Steam and Hydrogen. F u e l G a s i f i c a t i o n , Advances i n Chem. S e r i e s 131, ACS, Wash., D. C., 1974, pp. 145-178. Kunii, D. and 0. Levenspiel. New York, 1969, p. 76. F l u i d i z a t i o n Engineering. John Wiley h Sons, Inc.,

23.

24.
25.

Wen, C. Y. and J. Huebler. K i n e t i c Study of Coal Char Hydrogasification, Rapid I n i t i a l Reaction. Ind. & Eng. Chen. Design & Develop., 5 (April, 19651, pp. 142-147. Feldmann, H. F., K. D. Kiang, and P. M. Yavorsky. F l u i d i z a t i o n P r o p e r t i e s of Coal Char. P r e p r i n t s of F u e l Division, ACS, v. 15, No. 3, Sept. 1971, pp. 62-76. Ouarterly Technical Progress Report, Morgantown Energy Research Center, Morgantown, West V i r g i n i a , September-December, 1969, p. 2. Anthony, D. B. Rapid D e v o l a t i l i z a t i o n and Hydrogasification of Pulverized Coal. Sc.D. Thesis, Dept. o f Chem. Eng. , M.I.T., Cambridge, Mass. , Jan., 1974. Blackwood, J. D., B. D. C u l l i s , and D. J. McCarthy. R e a c t i v i t y i n t h e System Carbon-Hydrogen-&thane. Aust. J. Chem. 2 (1967), pp. 1561-70.

26. 27. 28. 29.

StFfinless steel type 3 0 4 Porous stainless steel p l o t e

T C =Thermocouple

pIo te

Porous stainless steel thick, meon pore diameter 165 microns

Low voltage transformer

Output- 700 amperes a t 8-9 volts Figure I

3E'r
"

From vorioble transformer

- " H o t - rod

reoctor.

L- 4753 12-12-56

124

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7
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i
Figure 4

Integrated hydrogasification unit.

L 12914 -

127

Coal feed hopper

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$2"

$" ID feed nozzle

3.26" ID x 6'

Simulated 2nd stageproduct gas

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Main tail gas to hot gas trap Moving bed sample

3
-Dilute

phase sample char transfer tube

.

'

Disengaging zone

3 . 2 6 1 0 x IO' Moving bed reacto

/ Char
Hydrogen feed-

ejector throat

Char receiver

Figure 5 -Integrated

two- stage hydrogasifier

L-13753

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100

I
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'

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GO + H 2 0

a
X

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x

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0 0 0

-Literature

Pittsburgh seam hvab coal data

0. I

Figure 6- Water-gas shift equilibrium in the FDP reactor.

of

carbon oxides

5-23-75

L- I4298

129

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PARTIAL PRESSURE OF HYDROGEN , a t m Figure

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5 -20-75

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Illinois #6 hvcb coal

A Pittsburgh seam hvab coal

400

500

600

700

800

900

1000

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WALL TEMPERATURE

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Figure 14- Corbon conversion in the FOP reactor for Illinois # 6 hvcb c o a l .

5-16-75

L-14292

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TIME

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RESIDENCE T I M E , minutes
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5-27-75

L-14301

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IO0

90

80

-Rate

model

70
60 50 40
30

- /

20
IO

I 0
I

Pittsburgh hvab coo I o 8 O O 0 C , 18.0 a t m A " ,35.0 atm 0 ,69.0 atm n 1 2 O O 0 C , 4.4 otm 0 I' , 18.0 atm 0 " ,35.0atm
I
I

1
I

IO

1 5
TIME

20
minutes

2 5

30

RESIDENCE

Figure 17- Carbon conversion data for the H R - I series experiment

.
L-14299

5-21-75

140

m
I

I
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I

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70

Pittsburgh hvab char Temperature - 8 0 0 C o 18.0 atrn

60-

o 35.0 otrn A 69.0atm

-Rate
0

50 40 30 20

model
I

6 9 . 0 otm ,HR-2C

IO
RESIDENCE

1 5

20

25

30

T I M E , minutes

Figure 22- Carbon conversion data for the HR-IC series experiments.

5-15-75

L- I4290

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r-----0

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9
i

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146

147

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A

I
HR - 2 series

HR - I series , Pittsburgh hvob cool

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IO

20

30
CARBON

40

50

60

70

80

90

100

CONVERSION

, percent

.Figure 28
I

- Cool

conversion (mof) os o function of carbon conversion during hydrogosificotion .

5-16-75

L- 14306

148

80
70

I
0

A H R - 2 C Series , Illinois #6 hvcb .char

H R - I C Series ,Pittsburgh hvab char

60
50
40 30

20

I O

20

30

40

50

60

70

CARBON

CONVER S l O N ,percent

Figure 29- Char conversion (maf )as a function of carbon conversion during hydrogasification.

5-15-75

L-14291

149

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b. O l 6 mm

X 3600

Figure 21

- SEM PHOTOGRAPHS OF FDP CHAR (LIGNITE) ,

(85OoC,69 atm)
I

155

KYDROGASIFICATION OF 1NDPAl-E CHAR IN FLUIDIZED AND

MOVING DEDS
C. Y . Wen,* S. Hori,* J. A. Gray,** and P. M. Yavorsky**
*West V i r g i n i a University Morgantown, West V i r g i n i a

1
7

**U. S. Bureau of Mines P i t t s b u r g h Energy Research Center P i t t s b u r g h , Pa. 15213

ABSTRACT To s a t i s f y f u t u r e p i p e l i n e gas requirements, c o n s i d e r a b l e process development work i s being aimed a t g a s i f y i n g c o a l t o produce s u b s t i t u t e n a t u r a l gas (SNG). The

h e a r t of many of t h e g a s i f i c a t i o n p r o c e s s e s b e i n g developed i s a fluid-bed g a s i f i e r i n which char is r e a c t e d w i t h steam/oxygen or hydrogen. b e i n g developed a t t h e U.S.

In t h e HYDRANE p r o c e s s ,

Bureau of Mines, P i t t s b u r g h Energy Research Center, char

i s r e a c t e d d i r e c t l y w i t h hydrogen i n t h e fluid-bed s t a g e of t h e h y d r o g a s i f i e r .

In

Order t o scale-up

t h e fluid-bed r e a c t o r t o p i l o t p l a n t or commercial s i z e w i t h con-

f i d e n c e , a fluid-bed r e a c t o r model has been developed u s i n g t h e bubble-assemblage concept and h a s been shown t o f i t e x i s t i n g d a t a reasonably w e l l .

Data from moving-

bed r e a c t o r experiments and t h e correspondinR model were compared eo t h e fluid-bed r e s u l t s and i l l u s t r a t e t h e d i f f e r e n c e s between plug-flow and well-mixed INTRODUCTION solid-gas reactors.

In order t o s a t i s f y f u t u r e p i p e l i n e gas requirements and a l l e v i a t e c u r r e n t

s h o r t a g e s , c o n s i d e r a b l e process development work i s underway f o r g a s i f y i n g c o a l t o produce s u b s t i t u t e n a t u r a l g a s (SNG).

The h e a r t of many of t h e g a s i f i c a t i o n

processes under development i s a fluid-bed g a s i f i e r i n which char is r e a c t e d w i t h steamloxygen or hydrogen. t h e U.S.

In t h e HYDRANE process ( f i g u r e l ) , b e i n g developed a t

Bureau of Mines, P i t t s b u r g h Energy Research Center, raw c o a l of bituminous

o r lower rank i s r e a c t e d d i r e c t l y with hydrogen i n a two-stage h y d r o g a s i f i e r t o produce 9 5 % of t h e product methane. The lower s t a g e o f t h e h y d r o g a s i f i e r i s Conceptually,

a f l u i d i z e d bed of char i n which hydrogen is t h e f l u i d i z i n g gas.

156

t h e gas e x i t i n g t h e bed c o n t a i n s about 46% methanqand t h e char l e a v i n g t h e f l u i d bed c o n t a i n s about h a l f t h e cnrhon i n i t i a l l y f e d t o t h e h y d r o g a s i f i e r i n t h e raw coal. Prevention of agglomeration i s of g r e a t importance because most of t h e

e a s t e r n and midwestern American c o a l s s o f t e n , s w e l l , and become s t i c k y a t t e r n p e r a t u r e s above 400 C . , e s p e c i a l l y i n t h e presence of hydrogen, and a r e t h e r e -

f o r e impossible t o p r o c e s s i n a f l u i d bed without some p r e t r e a t m e n t or d i l u t i o n . Thus, t h e t o p s t a g e of t h e h y d r o g a s i f i e r i s a dilute-phase, f r e e - f a l l r e a c t o r in

which t h e raw p u l v e r i z e d c o a l i s f e d i n a d i l u t e cloud c o n c u r r e n t l y with t h e g a s produced i n t h e bottom s t a g e , r e n d e r i n g t h e p a r t i c l e s nonagglomerating and produci n g a v e r y porous, r e a c t i v e char. Approximately 20% t o 30% carbon conversion o c c u r s

in t h i s s t a g e , a n d t h e product gas c o n t a i n s about 70% methane.

Experimental d a t a have been obtained from a 1 2 l b . / h r . process development

u n i t in which t h e bottom s t a g e of t h e h y d r o g a s i f i e r has been o p e r a t e d a s e i t h e r a f l u i d i z e d bed o r a moving bed r e a c t o r .

In d e s i g n i n g a scaled-up v e r s i o n of t h e

fluid-bed r e a c t o r , a model d e s c r i b i n g t h e movement of g a s and s o l i d s in t h e r e a c t o r and a r e a c t i o n r a t e model i s needed. The r e a c t o r model i s then i n t e g r a t e d with
In

the r e a c t i o n r a t e e q u a t i o n y i e l d i n g r e a c t o r s i z e and product gas composition.

t h i s Paper a fluid-bed r e a c t o r model h a s been developed using t h e bubble-assemblage concept o r i g i n a l l y developed by Kat0 and Glen experimental d a t a reasonably w e l l .

() 1 and

i s shown t o d e s c r i b e some

A moving-bed r e a c t o r model

i s a l s o developed

and used t o model experimental d a t a a s w e l l a s i l l u s t r a t e t h e d i f f e r e n c e s between plug-flow and w e l l mixed solid-gas Apparatus and Procedure The two-stage l a b o r a t o r y h y d r o g a s i f i e r i s shown i n f i g u r e 2. reactors.

It c o n s i s t s of

a dilute-phase r e a c t o r i n t e g r a t e d with a second s t a g e which can b e o p e r a t e d a s

e i t h e r a moving-bed o r f l u i d - b e d r e a c t o r .

The d i l u t e - p h a s e r e a c t o r i s a 3-inchThe p i p e is

diameter. schedule 10, t y p e 304. s t a i n l e s s s t e e l p i p e 6-feet l o n g . h e a t e d i n t h r e e 2-feet-long s e c t i o n s c o n t a i n i n g s i x 1,000-watt

s t r i p heaters

mounted d i r e c t l y on t h e p i p e w a l l .

The p i p e i s wrapped i n f i b e r f r a r i n s u l a t i o n s c h e d u l e 160, carbon s t e e l pipe which

and 1s contained i n s 10-inch-diameter, a c t s a s the pressure s h e l l . v i a a l/l-inch

P u l v e r i z e d c o a l is f e d i n t o t h e r e a c t o r by g r a v i t y l a e n t h e second

nozzle, which p r o t r u d e s one f o o t i n t o t h e reactor.

s t a g e was o p e r a t e d as a f l u i d bed, t h e char l e a v i n g t h e d i l u t e - p h a s e r e a c t o r was crushed t o reduce t h e p a r t i c l e s i z e t o a l e v e l a c c e p t a b l e f o r f l u $ d i z a t i o n . The

average diameter of c h a r p a r t i c l e s l e a v i n g t h e d i l u t e - p h a s e r e a c t o r can b e as much a s s i x t i m e s t h e a v e r a g e diameter of t h e p u l v e r i z e d feed c o a l p a r t i c l e s owing t o s w e l l i n g and p a r t i c l e agglomeration and consequently, p r e v e n t a d e q u a t e f l u i d i z a t i o n u n l e s s t h e p a r t i c l e s are crushed. i n t a b l e 1.
An example of p a r t i c l e s w e l l i n g is shown

The second s t a g e r e a c t o r is a l s o a +inch-diameter

pipe. b u t is 10-feet

l o n g and h a s f i v e h e a t e d zones. i n t o t h e 3-inch-diameter f o r t h e dilute-phase c o u p l e msasurements.

A s l e e v e having a 2-inch i n s i d e diameter is i n s e r t e d

Temperatures r e p o r t e d

p i p e f o r f l u i d i z e d - b e d experiments.

and fluid-bed r e a c t o r s correspond t o r e a c t o r p i p e wall t h e m -

In t h e moving-bed experiments, r e p o r t e d t e m p e r a t u r e s correspond

t o thermocouples suspended d i r e c t l y i n t o t h e c h a r bed.

Two fluid-bed r e a c t o r schemes were used and are s h a m in f i g u r e 3.

In scheme

A, hydrogen was f e d y i t h o u t p r e h e a t i n g i n t o t h e bottom of t h e bed by two gas nozzles,

and r e s i d u a l c h a r w a s r e m v e d a t t h e bottom of t h e bed.

A amall amount of f i n e s

was c a r r i e d o v e r i n t h e i n t e r s t a g e g a s .

The bed l e v e l was measured by t h r e e pres-

s u r e d i f f e r e n t i a l p r o b e s which were c o n t i n u a l l y purged w i t h a n i t r o g e n f l o w of about

6 8.c.f.h.

Some t y p i c a l temperature p r o f i l e s a r e shown

in f i g u r e 4 and i n d i c a t e

t h a t about 30 cm. of t h e f l u i d bed l a r e q u i r e d t o h e a t up t h e hydrogen f e e d gas and a t t a i n a uniform bed temperature.

In scheme B, t h e hydrogen was preheated t o r e a c t o r

temperature and was f e d through a d i a t r i b u t o r p l a t e a t t h e bottom of t h e r e a c t o r . The p r e h e a t e r t e m p e r a t u r e and hence hydrogen f e e d temperature was c o n t r o l l e d c l o s e l y by a c o o l i n g water c o i l i n s i d e t h e p r e h e a t e r i t s e l f and e x t e n d i n g t h e f u l l l e n g t h

of t h e preheat zone.

158

TABLE 1.Run No.

Typical P a r t i c l e Data f o r Dilute-Phase Char ( I l l i n o i s t 6 h.v.C.b.) Before Crushing* 162

Wt. % 0.05

163
Wt. % 0.03

164
Wt. %

U.S. Mesh S i z e On 1 / 4 "

0.05 0.49 5.62 10.27

1/4" x 4
4 x 6 6 x 8

1.16

0.57 4.89 14.77 12.09

a. 96
17.35 12.09 8.47

io

io. a i
8.51 9.40 20.00 17.76 14.31 2.45 0.18
0.18

10 x 1 2

a. 91 a. 89
19.34
13.78 10.52 5.47 0.47 0.25 0.866 0.141 Sieve S i z e ) ,

1 2 x 14 1 4 x 20
20 x 30 30 x 50 50 x 100 100 x 200 Thru 200

a. 34
17.35 13.27 9.52 3.11 0.18 0.15 1.031 0.109

P ' ' Pb., gm./cm?

nun.

0.897 0.111

*Feed Coal 50- x 100-mesh (U.S.

8.

0.223 mm.

159

Ihe r e s i d u a l c h a r was c a r r i e d o u t of t h e r e a c t o r w i t h t h e product gas v i a an overflow

p i p e and w a s s e p a r a t e d from t h e g a s .
A b a f f l e was i n s e r t e d a t t h e top of t h e

r e a c t o r t o prevent s h o r t - c i r c u i t i n g of feed c h a r d i r e c t l y t o t h e overflow p i p e . T y p i c a l temperature p r o f i l e s f o r t h i s mode of o p e r a t i o n are i l l u s t r a t e d i n f i g u r e 5. Again about 30 cm. of bed was needed t o a c h i e v e a uniform temperature b e c a u s e

t o o much c o o l i n g water wa3 c i r c u l a t e d through t h e p r e h e a t e r . The r e a c t o r scheme f o r t h e moving-bed experiments i s shown i n f i g u r e 6. The

c h a r from t h e d i l u t e - p h a s e r e a c t o r dropped i n t o t h e second-stage r e a c t a r which cons i s t e d of a f r e e - f a l l zone and a moving-bed zone. Hydrogen w a s f e d i n t o t h e bottom Char

of t h e moving-bed zone and flowed c o u n t e r c u r r e n t t o t h e movement of c h a r .

was removed from t h e bottom of t h e r e a c t o r by a s t a r w h e e l c r u s h e r and t h e residence time was v a r i e d by changing t h e c h a r bed h e i g h t . f o r t h i s echeme a r e shown i n f i g u r e 7. I n a l l experiments e x c e p t HY-3, t h e carbon conversion was determined from a n u l t i m a t e a n a l y s i s o f t h e c h a r product and t h e composition of t h e i n i t i a l c o a l assuming 100% a s h recovery. Typical temperature p r o f i l e s

In some experiments. t h e recovery of carbon, a s h , and hydrogen

The moving-bed product g a s composi-

were checked and were u s u a l l y b e t t e r t h a n 95%.

t i o n w a s n o t known a c c u r a t e l y because product gas from t h e d i l u t e - p h a s e r e a c t o r , cont a i n i n g about 70% methane, mixed w i t h t h e moving-bed product gas near t h e sampling point.

This y i e l d e d i n f l a t e d v a l u e s of methane c o n c e n t r a t i o n .

T h e r e f o r e , methane The mixing e f f e c t

y i e l d s based on t h e moving-bed

product g a s a n a l y s i s were n o t used.

is shown i n f i g u r e 8 where a c t u a l and c a l c u l a t e d methane c o n c e n t r a t i o n s are shown.

Carbon conversion f o r t h e o v e r a l l two-stage u n i t based on t h e s o l i d s a n a l y s i s was cheaked by c d l c u l a t i n g carbon conversion based on t h e t o t a l p r o d u c t gas and o i l yields. The u l t i m a t e a n a l y s e s f o r t h e I l l i n o i s 16 h.v.C.b. c o a l and t h e c h a r p r o d u c t The

f o r t h e fluid-bed t e s t s and t h e c h a r p a r t i c l e d a t a a r e t a b u l a t e d i n t a b l e 2.

161

corresponding run c o n d i t i o n s and c o n v e r s i o n d a t a a r e l i s t e d i n t a b l e 3. carbon conversion i n t h e d i l u t e - p h a s e r e a c t o r f o r tests HY-2,

The

3, 13, and 1 4 was

assumed t o b e about 28% based on p r e v i o u s d i l u t e - p h a s e d a t a w i t h I l l i n o i s 16 c o a l and t h e remaining c o n v e r s i o n o c c u r r e d i n t h e f l u i d bed.

e),

For t e s t s HY-5, 11, and

1 2 , e s s e n t i a l l y p u r e hydrogen was used 8s t h e f e e d gas i n s t e a d o f a hydrogen-methane mixture s o t h a t an a d d i t i o n a l 4.5 t o 5% carbon conversion occurred b r i n g i n g t h e d i l u t e - p h a s e v a l u e t o 33%. The c o n v e r s i o n of t h e o t h e r c o a l c o n s t i t u e n t s i n t h e d i l u t e - p h a s e r e a c t o r can b e c a l c u l a t e d u s i n g t h e c o r r e l a t i o n s g i v e n i n f i g u r e s

9-12,

which are based on 95 c o a l h y d r o g a s i f i c a t i o n experiments i n t h e HYDRANE PDU.

The d a t a f o r s u l f u r removal a r e s c a t t e r e d because of t h e e r r o r i n d e t e r m i n i n g changes i n small amounts of s u l f u r i n t h e c o a l and c h a r samples. Oxygen removal,

which u s u a l l y exceeds 90% for carbon conversions above 20%. can be c o n s i d e r e d t o b e complete. The c a l c u l a t e d c o n s t i t u e n t conversions i n t h e d i l u t e - p h a s e r e a c t o r

f o r 28% and 33% carbon conversion a r e shown i n t a b l e 4. The u l t i m a t e a n a l y s e s f o r t h e I l l i n o i s 06 h.v.C.b. c o a l used i n t h e movingThese d a t a

bed t e s t s and t h e a n a l y s e s of t h e c h a r p r o d u c t are shown i n t a b l e 5.

a r e presented on a d r y b a s i s f o r convenience i n c a l c u l a t i n g c o n v e r s i o n s . Reaction Rate of Coal-Char H y d r o g a s i f i c a t i o n

It has been demonstrated by a number of i n v e s t i g a t o r s

(J,&,A,&,z,g)t tha

coal

c o n s i s t s roughly of two p o r t i o n s g r e a t l y d i f f e r i n g i n r e a c t i v i t y :

a highly reactive

p o r t i o n r e l a t i n g t o t h e v o l a t i l e hydrocarbons p r e s e n t i n c o a l . and a r e l a t i v e l v low r e a c t i v i t y r e s i d u a l carbonaceous matter, coke.

In t h e p r e s e n c e of hydrogen, t h e

i n i t i a l phase of extremely r a p i d r e a c t i o n i s presumably due t o p y r o l y s i s followed by hydrogenolysis of t h e i n t e r m e d i a t e s t h a t a r e d e r i v e d from e s s e n t i a l l y a l i p h a t i c hydrocarbon s i d e c h a i n s and oxygenated f u n c t i o n a l groups. The remainder of t h e

carbon i n t h e c h a r i s converted t o methane much more slowly, a p p a r e n t l y a t t h e c h a r s u r f a c e almost s t o i c h i o m e t r i c a l l y a c c o r d i n g t o t h e graphite-hydrogen r e a c t i o n .

TABLE 3.-

S o l i d s Conversion For Fluid-Bed Tests, 50- x 100-Mesh I l l i n o i s 116 h.v.C.b. Coal, 1,000 p . s . i . g . 2 2270 3 2724 5 4631 1 1 5448 12 3087 13 2951 14 3042

Run
Coal Rate, gms./hr. (Dry) Dilute-Phase Reactor
C Temp., Feed Gas, s.c.f.h. % H2 CH4

Ar(He*)
N2

850 234 45 48 6 1

850 185 56 35 8 1

850 260 94.5 0.2 4.3 1.0

850 167 93
0

7 0

900 108 92.6 0 7.4 0

900 110 53.4 38.0 7.3* 1.2

9 00 110 47.8 39.0 11.o* 1.2

Fluid-Bed Reactor Feed Gas, s.c.f.h. % H2 N2 T o t a l Conversion 55.2 88.2 S 87.9 N 80.1 0 97.2 Fluid-Bed Height,cm. 143 0.436 Char Yield, gm./gm. dry coal
C H

310 97 3

215 94 6

320 99 1

330 91 9

249 91.1 8.6

240 88 12

240 88 12

53.6** 79.9 71.8 66.3 77.8 143 0.499

55.8 89.8 74.4 74.9 88.1 143 0.480

60.8 92.7 80.1 83.4 95.6 122 0.471

55.1 89.6 76.4 85.4 91.6 122 0.514

55.6 94.0 78.4 86.7 100 122 0.473

53.7 90.1 82.3 82.3 100 122 0.503

**Calculated based on c h a r recovered.

TABLE 4.-

C a l c u l a t e d C o n s t i t u t e n t Conversion i n the D i l u t e p h a s e Reactor

Conversion, X

28.0
65.2 47.5 29.6
92.5*
Char Y i e l d , &m./gm. dry c o a l

33.0 69.6
51.2

30.7
93.0* 0.639

0.677

*Estimated from Figure 13.

164

I; ; -. -.

u .0u 3 ' .

165

During t h e i n i t i a l phase of t h e coal-hydrogen

reaction, the coal particles

a r e q u i c k l y s o f t e n e d , become m e t a p l a s t i c g i v i n g o f f V o l a t i l e matter, and e r u p t i n a manner somewhat similar t o popping of popcorn. Wen and Huebler

(2) p r e s e n t e d
In

a k i n e t i c model f o r t h i s i n i t i a l rapid r e a c t i o n of c o a l h y d r o g a s i f i c a t i o n .

t h e f r e e - i a l l r e a c t o r o f t h e HYDRANE p r o c e s s , t h e i n i t i a l phase o f h y d r o g a s i f i c a t i o n of c o a l t a k e s p l a c e l e a v i n g a small p o r t i o n of v o l a t i l e matter i n t h e c h a r . T h i s c h a r is t h e n r e a c t e d w i t h hydrogen in a fluidized-bed process. r e a c t o r i n t h e HYDRANE

The r e a c t i o n r a t e i n t h i s second phase of h y d r o g a s i f i c a t i o n h a s been

d e s c r i b e d elsewhere

(z,z,x).
(1)

For t h e second phase r e a c t i o n , Char

+ AH2

CH,,

where ?, i s a s t o i c h i o m e t r i c c o e f f i c i e n t o b t a i n e d by an e m p i r i c a l c o r r e l a t i o n

(2.2)

1.0 f o r X<0.45 8 X

2.6 f o r 0.452 X
f o r 0.55<X

i 0.55

(2)

(1.8

and t h e average v a l u e of ,? is o b t a i n e d a s follows: h=S)Ldx/SdX

(3)

The r a t e of h y d r o g a s i f i c a t i o n of c h a r is g i v e n by

dz =
dt

k(1-Z)P
H2

(4)

where 2 is t h e carbon conversion in t h e second phase r e a c t i o n and i s e q u a l t o (X-Xo)/(l-Xo).

Here X i s t h e carbon conversion based on t h e raw c o a l , Xo i s t h e

2

carbon converted i n t h e f i r s t phase r e a c t i o n o r i n t h e p r e t r e a t m e n t , P p a r t i a l p r e s s u r e of hydrogen and k i s t h e r e a c t i o n r a t e c o n s t a n t .

1

is the

The above e q u a t i o n can b e w r i t t e n i n t h e f o l l o w i n g form a s d t = K(1-2) where YH

YH
2

(5)

PH2 /PH2, K = k p H i and PHo is t h e p a r t i a l p r e s s u r e of hydrogen a t t h e i n l e t .

166

Feldmann e t a 1 constant:

(s)s e n t e d pre
1

the following c o r r e l a t i o n f o r the reaction r a t e

I n k = -10.45 x 1 0 3 ( ~ ) 7.08, +

k:

atm.-lhr.-],

T:

A s w i l l b e shown l a t e r , t h e v a l u e s of k and a c t i v a t i o n energy c a l c u l a t e d from

experimental carbon c o n v e r s i o n s using t h e Bubble Assemblage model o r moving bed model developed a r e s i g n i f i c a n t l y smaller t h a n t h o s e c a l c u l a t e d from t h e above equation. Simulation of Fluidized-Bed H y d r o n a s i f i e r

1. Minimum F l u i d i z a t i o n V e l o c i t y
It has been shown by Feldmann e t a 1

(E,=) t h a t

t h e minimum f l u i d i z a -

Cion v e l o c i t y of c o a l c h a r s with popcorn-like s t r u c t u r e is g r e a t e r t h a n t h a t c a l c u l a t e d from the Wen-Yu c o r r e l a t i o n particles.

(2) which

is applicable only t o nonvesicular

The e m p i r i c a l c o r r e l a t i o n proposed by Feldmann e t a 1

(13)has

the

f o l l o w i n g form:

umf
where d
p

:f

d E = 0.0135 [dp3

is p a r t i c l e d i a m e t e r , i s gas d e n s i t y ,

p s is p a r t i c l e density,
y

is gas v i s c o s i t y

g is g r a v i t a t i o n a l a c c e l e r a t i o n .

and

Umf is t h e minimum f l u i d i z a t i o n v e l o c i t y . 2. Fluidized-Bed Model

I n t h e f l u i d i z e d bed h y d r o g a s i f i e r , t h e second-phase r e a c t i o n t a k e s P l a c e

e i t h e r c o u n t e r c u r r e n t l y , c o n c u r r e n t l y , o r w i t h overflow as s c h e m a t i c a l l y d e s c r i b e d i n f i g u r e 13. The Bubble Assemblage model (1,15,16,17,l&)

is used t o s i m u l a t e t h e

h y d r o g a s i f i c a t i o n of c o a l c h a r .

The e s s e n t i a l f e a t u r e s of t h e Bubble Assemblage model

are summarized a s f o l l o w s :

The f l u i d i z e d bed is d i v i d e d i n t o a number of compartments, each of which

has a h e i g h t t h a t is uniquely determined by t h e d i a m e t e r of t h e b u b b l e a t t h e COKKeSpOnding h e i g h t .

Each compartment is composed of t h e b u b b l e phase and t h e emulsion phase. The s o l i d s and g a s i n t h e emulsion phase and t h e b u b b l e phase of each compartment a r e completely mixed w i t h some exchange o f gas between t h e two phases.

The volume of t h e b u b b l e phase is assumed t o b e e q u a l t o t h e volume of

t h e bubbles i n t h i s paper. t h e bubble phase.

It is a l s o assumed t h a t no s o l i d s e x i s t i n

F i g u r e 14 d e p i c t s t h e Bubble Assemblage Model under v a r i o u s modes of flow a r r a n g e ment.

P

is a n index of s o l i d flow arrangement and is e q u a l t o u n i t y when s o l i d s

Under t h i s c o n d i t i o n , q ,

flow c o u n t e r c u r r e n t t o t h e gas. q

+ q2,

where q

and

are t h e r a t i o of s o l i d s downflow rate and s o l i d s upflow r a t e t o t h e s o l i d

feed r a t e , r e s p e c t i v e l y .

When s o l i d s a r e f e d from t h e t o p and withdrawn from t h e t o p of t h e bed

(overflow t y p e ) , Pc is 0 and q,

q2.
2

From t h e m a t e r i a l b a l a n c e of H

around t h e n-th compartment i n t h e bed,

t h e following e q u a t i o n s can b e w r i t t e n f o r t h e b u b b l e phase and emulsion phase.

wHo

( Y ~ ~yBn) ~+ -

vBn yH0 F~~

(yen

- Y Bn )
(l-Zn)

(7)
(8)

VBn YHo FOn (YBn

yen)

Ven

Yen

= 0

where

is an a p p a r e n t r e a c t i o n r a t e c o n s t a n t f o r H

consumption in t h e emul-

s i o n phase and can b e w r i t t e n as

\
u

a c (I-E

m f

) pc0

Yco K

(9)

i a t h e number of moles of H2 r e a c t e d w i t h o n e gram o f carbon in c h a r and is

related t o

x as

h/12.

168
From a m a t e r i a l b a l a n c e of carbon in t h e c h a r around t h e n-th compartment, e x c l u d i n g n = l and N , t h e f o l l o w i n g e q u a t i o n can be o b t a i n e d , ql~so~co(~n+l zn)

q2WsoYco (Zn-l

Zn)

=-Veri \
=

Yen

(l-Zn)/ac

(10)

For t h e top compartment of t h e bed (n=N), w e Eet ZW1 e q u a t i o n is o b t a i n e d :

1 - q w SOY COz N

0.0 and t h e f o l l o w i n g

+ w SOY CO

p2zN-1

('-'c)

zg
-ve ,'bye

= -VeN%YeN(l-ZN)/ac

(11)

For t h e f i r s t compartment ( n = l ) , t h e following e q u a t i o n can be w r i t t e n f o r t h e overflow type and t h e c o u n t e r c u r r e n t type: wsoyco(~lz2

- PCZ1) - ~2wsoycoz

(1-z

1) l a c

(12)

From e q u a t i o n s (7) and (8) we o b t a i n :

(13)

en = -!YBn

YBn-l!/:2

!l-Zn!

(14)

where a E Ft/VBnFon and a I V

2

enkb"H0.

From e q u a t i o n s ( l o ) , (11). zn+l= p q l where Z o = ZN+l t a b l e 6.

+

(12). and (14) w e g e t :

q2

zn

- qz2Zn-1

a 3 (YBn

- YBnd/"J

/q12

(15)

0.O.a

I Ven~/acWSOYCO

and t h e v a l u e s of q

i j are

in

If the s o l i d p a r t i c l e s in t h e bed a r e assumed t o b e completely mixed, t h e

b a s i c e q u a t i o n can be s i m p l i f i e d as follows:
Z

= ZU = c o n s t a n t

J =1

1 + (l+a ) a
1

(l-ZIF)

I
can be o b t a i n e d

where ZIF i s t h e c o n v e r s i o n in t h e bed and a t t h e o u t l e t .

From a n o v e r a l l material b a l a n c e . a n o t h e r e q u a t i o n r e l a t i n g YBN and ZIF

a s follows:

I69

TABLE 6.-

S,
J

i n equation (15)

qll

12

q2 1

q22

n Z 1 , N
q1

q1

q* q* 1-Pc

q2

n = l n = N

pc
q1

91
1.0

0.0
q2

170

ZIF = a3 (l-YBN)/ a2

(17)

From Hovmand and Davidson t h a n 0.2,

(x),t h e v a l u e of if

(uo-umf)/0.35

6 is
C,

less

t h e bed c a n be k e p t i n f r e e l y bubbling c o n d i t i o n .

When t h e v a l u e of When 6
f

i s g r e a t e r than 0.5, t h e bed i s i n a s l u g flow c o n d i t i o n .

t o 0.5,

i s between 0 . 2

t h e bed i s i n a t r a n s i t i o n c o n d i t i o n between bubbling flow and s l u g flow.

Recently, Mori a n d Wen

( 7 presented 1,) s

a new c o r r e l a t i o n of bubble growth

f o r a bubbling bed a s follows:

DB = DBM

(DBM-DBo) exp (-0.3 h/Dt)

(18)

where DBM i s t h e maximum bubble diameter, DBO i s the i n i t i a l bubble diameter and h i s t h e e l e v a t i o n above t h e d i s t r i b u t o r . Since t h e f l u i d i z e d g a s i f i c a t i o n u n i t used has a l a r g e bed h e i g h t t o diameter r a t i o (Lr>>Dt). e q u a t i o n (18) c a n be s i m p l i f i e d a s follows:

Then, t h e h e i g h t of e a c h compartment i n t h e bed, Ahn, a l s o can b e approximated a s : A n = DB = Dm, h From Kato and Wen Fon = l l / D B Based on t h e two-phase
(20)

(L),

the g a s i n t e r c h a n g e c o e f f i c i e n t ,

Fori,

i s given by

(21) theory, volume f r a c t i o n s o f bubble phase and emulsion phase

i n each compartment are given a s f o l l o w s , r e s p e c t i v e l y :

L~~

V Bn /Ah nA t

(uo-u mf)lUB

(22) (23)

Veri

= (l-cBn) AhnAt

Since t h e s o l i d p a r t i c l e s may b e assumed t o b e t r a n s f e r r e d upward i n t h e wakes behind t h e bubbles, t h e volumetric flow r a t e of s o l i d s upward c a n b e w r i t t e n a s
f w (uo-u

m f

)(l-c

mf ) A t ,

where fl, i s t h e volume r a t i o o f t h e wake and t h e bubble.

Thus, q2 can b e r e w r i t t e n a s ,

Using e q u a t i o n s (19),
q 2 and A h

(201,

(211, (221,

(23) and (24) t h e v a l u e s of VBn,

Veri,

n s o l u t i o n s of e q u a t i o n s ( 1 3 ) , (?."), and (15) are o b t a i n e d s i m u l t a n e o u s l y by an itera t i v e method.

A computer l o g i c diagram i s shown i n f i g u r e 15.

can b e c a l c u l a t e d f o r a s e t of o p e r a t i n g c o n d i t i o n s .

Thus, numerical

R e s u l t s of Fluidized-Bed

Performance Simulation

I n t a b l e 7, t h e c a l c u l a t e d r e a c t i o n r a t e c o n s t a n t s a r e shown based on t h e e x p e r i mental carbon conversions. The v a l u e s of r e a c t i o n r a t e c o n s t a n t s from t h e Bubble

Assemblage Model and t h o s e from t h e s i m p l i f i e d Bubble Assemblage Model w i t h c o b p l e t e mixing of s o l i d s a r e compared.

As f o r t h e a x i a l s o l i d s mixing, t h e l a r g e

h e i g h t t o d i a m e t e r r a t i o of t h e e x p e r i m e n t a l r e a c t o r used r e s u l t s i n a r e l a t i v e l y s m a l l degree of s o l i d mixing. The f o l l o w i n g e q u a t i o n d e r i v e d by Miyauchi ( 2 3 f o r a

backflow mixing model is used t o estimate t h e P e c l e t number f o r c o u n t e r f l o w c a s e ,

where N i s t h e t o t a l number of compartments.

For t h e overflow case, a n analogy

of e q u a t i o n (25) i s used t o c a l c u l a t e t h e P e c l e t number:

are t a b u l a t e d and vary between 0.3 t o 1.2, conI n t a b l e 8, t h e v a l u e s of NPe s i d e r a b l y d i f f e r e n t from t h e l a r g e v a l u e s o b t a i n e d f o r complete mixing. A s can
be s e e n from t a b l e 7, t h e k v a l u e s of c o u n t e r c u r r e n t o p e r a t i o n c a l c u l a t e d from t h e Bubble Assemblage model w i t h p a r t i a l mixing of s o l i d s d i f f e r v e r v l i t t l e from t h e Bubble Assemblage model w i t h complete mixing of s o l i d s i n d i c a t i n g t h a t t h e s o l i d mixing does n o t a f f e c t carbon conversion s i g n i f i c a n t l y . The r e a c t i o n

r a t e c o n s t a n t s a r e p l o t t e d on an Arrhenius P l o t shown in f i g u r e 16 based on

172

TABLE 7 . -

Comparison of Reaction Rate Constants Calculated fron Bubble Assenblage Models

Run
No.

Solid Flow

1F observed 0.608

ZIF
observed

Bed temp. K

kcal.,

atm-l hr- S o l i d complete mixed

Solid partial mixed

11

0.419 0.335 0.383 0.357 0.376

0.356

1073 1118 1113 1183 1158

1158

0.0450 0.0202 0.0216 0.0139

0.0145

0.0515 0.0220 0.0248 0.0152 0.0123 0.0140 0.0223

12

counter current

0.551 0.556 0.537 0.552

13
14

2
3 overflow

0.536 0.558

0.0284 0.0316

0.345

1158

173

.\
\

Run No.

1 1

92 19.9 25.1 20.3 25.8

INpe
0.64

11
12

32

34
39

0.76
0.53

13
14

41
38

0.64
1.22 0.30

2
3 5

46.4 16.0 20.5

54 40

0.51

t h e average t e m p e r a t u r e s of t h e bed. experiments

The d a t a i n c l u d e t h e r e s u l t s of I . G . T .

(1) shown

i n t a b l e 9 f o r c o u n t e r c u r r e n t and c o n c u r r e n t f l u i d i z e d The complete mixing model i s used f o r c a l experiments. The r e a c t i o n

bed h y d r o g a s i f i c a t i o n e x p e r i m e n t s .

c u l a t i o n of t h e r e a c t i o n r a t e c o n s t a n t s f o r t h e I.G.T.

r a t e c o n s t a n t s c a l c u l a t e d from moving-bed d a t a a r e a l s o p l o t t e d i n f i g u r e 16.

An e m p i r i c a l r e l a t i o n f o r t h e t e m p e r a t u r e e f f e c t on t h e r a t e c o n s t a n t can

be expressed as, I n k = -4.36($ where k: am.-' hr. x

-1

lo3 + 0.28
, and
T: K

(27)

.
(2).
data a r e considerably l a r g e r An

A a c t i v a t i o n energy of 8.63 Kcal/mole is e s t i m a t e d w h i c h . i s very much smaller n thaE 15-16 a x ! 2 1 K c a l / z o l c r e p o r t e d by Feldmann et a1 The r a t e c o n s t a n t s c a l c u l a t e d from t h e moving-bed

t h a n t h o s e from t h e f l u i d i z e d bed, p a r t i c u l a r l y i n t h e low t e m p e r a t u r e r e g i o n . e x p l a n a t i o n o f t h e d e v i a t i o n i s p r e s e n t e d i n t h e moving-bed s e c t i o n .

In f i g u r e 1 7 ,

t h e carbon c o n v e r s i o n s c a l c u l a t e d u s i n g e q u a t i o n ( 2 7 ) are compared w i t h experimental conversions. The s c a t t e r s . o f t h e p o i n t s shown i n f i g u r e s 1 6 and 1 7 are p a r t l y due

t o t h e nonuniformity and time dependency of t e m p e r a t u r e a l o n g t h e bed a x i s . Moving-Bed-Reactor Model

I n t h i s model t h e g a s and s o l i d a r e assumed t o move i n a p l u g flow manner and t h e t e m p e r a t u r e p r o f i l e of t h e bed is averaged t o approximate an i s o t h e r m a l reactor. The movement o f c h a r through t h e moving bed, V
s

*;
dt

i s assumed t o be

c o n s t a n t and c a n be combined w i t h e q k a t i o n (3) t o y i e l d a n e q u a t i o n d e s c r i b i n g t h e carbon c o n v e r s i o n i n terms of p o s i t i o n i n t h e moving bed (h = 0 a t t o p of b e d ) , dZ V -=kP s dh H p ('-')

(28)

The carbon c o n v e r s i o n i n t h e c o u n t e r c u r r e n t moving bed can b e r e l a t e d t o t h e change

i n methane c o n t e n t o f t h e gas by t h e carbon b a l a n c e e q u a t i o n ,

175

TABLE 9 .

Operating Condition of I.G.T. Experiments [Wen and Huebler (1965))

Operation Char.
d

. . . . Counterqurrent
60/325 mesh

Concurrent

......
* * * *

Consolidation Coal Co. Bituminous coal char

P'

Dt, cm.

T, K

. . . . . 4.88 . . . . . . 905 - 958

..
1.83

4.3(equivalent) 992

llP9

Ud,

cm./sec.

W 0 , g./sec..
F ~ , cm3/sec..

. . 0.61 - 1.07
137

0.28
29

. . 57 - 111 PT, atm.. . . . . Lf, cm. . . . . . 214

- 1.05
54

- 141
143, 215

176

'CO

'SO

. = h

dZ

- . ('gYM) h
r e a c t o r , Yco t h e

(29)

where W

so

i s t h e d r y c o a l f e e d r a t e t o t h e d i l u t e - p h a s e r e a c t o r (gm./hr.),

Xo

f r a c t i o n a l carbon conversion i n t h e dilute-Dhase carbon per gram of d r y c o a l , W

g

m. moles of
and YM t h e

t h e molar gas r a t e (gm.-moleslhr.),

mole f r a c t i o n o f methane i n t h e gas.

W have made t h e assumption t h a t t h e convere Previous work

sion o f carbon t o CO o r CO? j n t h e moving bed w i l l b e n e g l i g i b l e . with c h a r a p p e a r s t o support t h i s assumption hydrogen i s g i v e n by M T The (fi,g).

p a r t i a l p r e s s u r e Of

(30)

pHP =

where PT is t h e t o t a l p r e s s u r e and n i s t h e combined mole f r a c t i o n o f hydrogen and methane i n t h e g a s . The d i f f e r e n c e o f n from u n i t y r e p r e s e n t s t h e mole fKaCThe n e t change i n t h e molar g a s r a t e is

t i o n of i n e r t s i n t h e gas.

Equations ( 2 9 ) and (31) may b e i n t e g r a t e d over a n a r b i t r a r y d i s t a n c e h s t a r t i n g

a t t h e top of t h e moving bed r e s u l t i n g i n t h e e q u a t i o n s

'go

' K O

'gYM

'co 'so

(32)

Wg

- Wgo
= WgH

= Yco

Wso

(A-l)dZ

(33)

Evaluation o f e q u a t i o n s (32) and (33) using t h e boundary c o n d i t i o n s Z = Z H , y M = 0 and W

M.
g

a t h = H y i e l d s values f o r W

go

and YpIo.

Once W

Y and W

c a n b e e v a l u a t e d a t any p o i n t i n t h e moving bed.

and YMo a r e known, go Thus, t h e mole f r a c t i o n

of methane a t any p o s i t i o n h i s given i n terms of t h e carbon conversion a s

YM = 'go

' o M
+

'co
'so

'so

'go

'co

5
0

(34) (1-l)dZ

-i

177

Henceforth t h e i n t e g r a l in t h e denominator w i l l b e w r i t t e n a s F(Z).

Substitu-

t i o n Of equations (30) and (34) i n t o e q u a t i o n (28) and i n t e g r a t i n g over t h e l e n g t h of t h e bed, H, y i e l d s t h e following r e l a t i o n s h i p for t h e r e a c t i o n r a t e c o n s t a n t k:

=
'Te

5"
B

[l
[A

BFCZ)]

+ B(1-Z) -

dZ nBF(Z)]Cl-Z]

(35)

where 8

Vs/H

A = n-YMo

Equation (35) can b e solved a n a l y t i c a l l y in one, two, o r t h r e e p a r t s , depending on t h e e v a l u a t i o n of A i n e q u a t i o n (1). , Appendix A. Moving-Bed R e s u l t s The conversion of t h e c o a l c o n s t i t u e n t s are p l o t t e d in f i g u r e 18 v e r s u s r e s i d e n c e time i n t h e moving bed. Zero r e s i d e n c e t i m e corresponds t o s o l i d m a t e r i a l r e a c t o r followed by f r e e - f a l l through t h e The s o l u t i o n of e q u a t i o n (35) i s shown i n

f r e e - f a l l i n g through t h e dilute-phase empty moving-bed r e a c t o r .

Such a c o n d i t i o n should approximate t h e conversion

in t h e dilute-phase r e a c t o r p l u s t h a t in t h e f r e e - f a l l p o r t i o n of t h e moving-bed
r e a c t o r when a char bed l e v e l is maintained. Char conversion in t h e f r e e - f a l l sec-

t i o n of t h e moving-bed r e a c t o r is probably low because t h e r e a c t i v i t y is much lower compared t o t h e s t a r t i n g c o a l and t h e r e s i d e n c e time is less t h a n a second. Zero

r e s i d e n c e time tests y i e l d e d a carbon conversion o f 30%. and t h i s v a l u e is used

1

as X

in t h e moving-bed model c a l c u l a t i o n s .

These r e s u l t s a r e summarized in t a b l e

10 and t h e r a t e c o n s t a n t s a r e shown on f i g u r e 1 6 as a n Arrhenius plot.The e f f e c t

of temperature on t h e moving-bed

r a t e c o n s t a n t v a l u e s can b e d e s c r i b e d by t h e

m 0, 0

0 0 m

m m h

Ln W U

m h rr)

0 m u3

0
10

m
u3

0 0 (0

m
PI 3

n r. 0 m

n W

m u3
n
0

m
u 0 U

0 u3 N 0

r 0

0 1

0 N

m m n
0

N 0

m m

'I -

9
U
u3 a

rl

rl

rl
Ln

m
0 r(

9
0 3

0
W OJ

.r

m
u3

m
rc)

r. m
rr)

.r
u3 0

r.

.r

m
rr)

m
W

m
w

m
.r 3
PI

w
rl rc) rl

4
rl m rl

0,
h h rl

?
m
h 4

m
. I rl

n
.3 r

.r 4

CI

m w rl

m
n .r 3

N
CI
rc) rl

m
rl

m
r4 h

m
m
r rl .

0 .
2

\D

u .
rc)

rl

r. rl

r;
r rl .

.r .r 3

rl r.

X0
rl

.r

*rc)

N N m
\o

0 .r

m
0 1

W rl

y1

U L o

m m
U

.r U

0 U U Ln

m
U rc)

II

C
U yl

. I
v

X
I

n
3

U N L c

.r W

\D

-!
. r
r rl -

rl

SI rl
rl

m rl

1
W

4 m

rl m 0

r.

L) 0)

I 1
N

5
m m n
3 IPI rl
W

n m

m U 0

0
(?

?
7 c .

n o \

U 0

.r

.
I 1

0 n 0 0 I I

0 OD

n m

e -f u

R U

U W

m
U

U 0,

xQ.

equation In k

-2.21

(L) T

lo3

-1.19

(36)

The discrepancy between t h e moving-bed and f l u i d - b e d d a t a i n f i g u r e 16 was f i r s t b e l i e v e d t o b e a r e s u l t of hydrogen mass t r a n s f e r r e s i s t a n c e between t h e bulk gas and t h e c h a r p a r t i c l e s u r f a c e . The Reynolds number f o r t h e moving-bed

tests

ranged from 0.882 t o 1.146 w h i l e t h e Schmidt number v a r i e d from 0.569 t o 0.933.

Using t h e s e v a l u e s and a v a i l a b l e mas6 t r a n s f e r c o r r e l a t i o n s , t h e mass t r a n s f e r

c o e f f i c i e n t , kg, was e s t i m a t e d t o be 0.119 t o 0.132 moles H2/hr.cm.2atm. Correc-

t i o n of t h e s e v a l u e s t o t h e same form as k y i e l d e d mass t r a n s f e r c o e f f i c i e n t s in e x c e s s of 1,400 atrn.-hr.- significant factor. confirming t h a t p a r t i c l e f i l m r e s i s t a n c e was not a

The discrepancy is b e l i e v e d t o b e a r e s u l t of h e a t t r a n s f e r

r e s i s t a n c e from t h e c h a r p a r t i c l e s t o t h e b u l k gas phase r e s u l t i n g i n t h e p a r t i c l e temperature b e i n g h i g h e r t h a n t h e temperature of t h e g a s and t h e measured bed temperature.

This c a n b e v e r i f i e d by a simple h e a t t r a n s f e r model i f w e assume

t h e r e a c t i o n r a t e , t h e a v e r a g e p a r t i c l e t e m p e r a t u r e , and t h e a v e r a g e g a s temperat u r e i n t h e bed a r e c o n s t a n t , and t h e h e a t g e n e r a t e d by r e a c t i o n is d i s t r i b u t e d uniformly w i t h i n t h e p a r t i c l e s . dT A dn h A Q a ( T g -T)+& P

A H
A h e a t b a l a n c e around a p a r t i c l e g i v e s t h e e q u a t i o n

5-s

QT

(37)

where t h e e q u a t i o n f o r t h e h e a t g e n e r a t i o n r e t e p e r u n i t volume of bed, QT is

Using t h e boundary c o n d i t i o n s T

P t h e s o l u t i o n of e q u a t i o n (37) is,

T when n = 0 (t = 0) and T = T when rl = 1 ( t g p PI

- Q)

E v a l u a t i o n of e q u a t i o n (39) u s i n g t h e parameter v a l u e s l i s t e d i n t a b l e 1 y i e l d s 1
Tpl/Tg = 1 . 2 and T = 1120 K. This means t h e t e m p e r a t u r e of t h e p a r t i c l e s a t PI t = 0 = 30.6 s e c . i s 187 K above t h e t e m p e r a t u r e o f t h e gas, which i s 933 K.

The log-mean average temperature of t h e p a r t i c l e s i s 990' K,

so t h a t on the average

che d i f f e r e n c e i n t e m p e r a t u r e between t h e gas and p a r t i c l e s is 5 7 K f o r t h i s case. Thus, t h e moving-bed k v a l u e s a t t h e lower t e m p e r a t u r e s i n f i g u r e 16 should

be more toward t h e l e f t s i n c e t h e p a r t i c l e t e m p e r a t u r e was probably h i g h e r t h a n t h e gas t e m p e r a t u r e . The measured temperature approximates t h e gas temperature

s i n c e t h e g a s c h a n n e l s a l o n g t h e thermocouple s h e a t h sweeping i t s s u r f a c e t o a l a r g e extent. The c o n t a c t a r e a between t h e c h a r p a r t i c l e s and t h e thermocouple s h e a t h i s

small compared t o t h e a r e a swept by t h e gas.

CONCLUSIONS

H y d r o g a s i f i c a t i o n r e a c t i o n r a t e c o n s t a n t v a l u e s were c a l c u l a t e d using p a r t i a l mixing and complete mixing v e r s i o n s of t h e Bubble Assemblage model of t h e f l u i d i z e d bed. These r e s u l t s i n d i c a t e d t h a t s o l i d mixing d i d n o t have a s i g n i f i c a n t e f f e c t T h i s was n o t unexpected because t h e carbon c o n v e r s i o n s Thus, t h e r e a c t o r was o p e r a t i n g i n a regime where The k v a l u e s

on' t h e carbon c o n v e r s i o n . i n the bed were under 40%.

changes i n a x i a l mixing e x h i b i t o n l y a minor i n f l u e n c e on c o n v e r s i o n .

f o r the complete mixing model with c o u n t e r c u r r e n t o p e r a t i o n are s l i g h t l y h i g h e r t h a n t h e v a l u e s f o r t h e p a r t i a l mixing model because t h e carbon c o n t e n t i n t h e

TABLE 11.-

Parameter Values Used in Equation 39 3.5 cal./gm. K 0.10

\
U
0

2.5 cm./sec. 933 K 30.6 sec.

0.04 cm.

cP f
2
1

yco Pr Re

0.68
12.6 1.11 0.01 2.5 x 1.0 0.3 cal./cm? see. K

C
PS

b '

0.15 gm./cm.
0.4 cal./gm. K

Nu
hf

pf

4 x 10- 3 gm./cm. 3

3.6 x 1.0 x 1.5 x

poise

cal./cm.sec.

=- - 0.3
wSO

lo3

cal./gm.

carbon reacted

wS

182

completely mixed bed i s lower t h a n i n most l o c a t i o n s i n t h e p a r t i a l mixed bed, t h u s , r e q u i r i n g a l a r g e r rate c o n s t a n t i n o r d e r t o o b t a i n t h e same amount of conversion.

In t h e case of overflow o p e r a t i o n of t h e f l u i d bed, l a r g e r k v a l u e s

are obtained f o r t h e p a r t i a l mixing c a s e t h a n f o r complete mixing because some

of t h e c h a r p a r t i c l e s have a very s h o r t r e t e n t i o n t i m e i n t h e bed b e f o r e overflowi n g out. The k v a l u e s must t h e n b e l a r g e r i n o r d e r t o o b t a i n t h e same conversion

a s t h e complete mixing case. Mixing w a s important, however, from t h e s t a n d p o i n t of h e a t removal from t h e c h a r p a r t i c l e s and m a i n t a i n i n g a n approximately i s o t h e r m a l bed. of heat removal was v e r y e v i d e n t i n the moving-bed The importance

r e s u l t s where h e a t t r a n s f e r

from the c h a r p a r t i c l e s w a s a p p a r e n t l y poor, c a u s i n g t h e p a r t i c l e t e m p e r a t u r e t o be h i g h e r t h a n t h e measured temperature. This e f f e c t was dominant i n t h e low-

temperature r e g i o n where moving-bed k v a l u e s were s i g n i f i c a n t l y l a r g e r t h a n f l u i d bed k v a l u e s . T h i s h e a t t r a n s f e r problem may b e t h e reason why Peldmann, e t a l l a r g e v a l u e s of k and a l a r g e a c t i v a t i o n energy when t h e y f i t t h e

(12) b t a i n e d o

k i n e t i c model g i v e n by e q u a t i o n (3) t o t h e moving-bed d a t a of Lewis, e t a1

( ) 1 .

Obviously, h y d r o g a s i f i c a t i o n d a t a i s b e s t o b t a i n e d i n a f l u i d i z e d bed o r i n a thermobalance such as t h a t used by Johnson

(22)

where t h e r e a c t i o n h e a t can b e

removed so t h e c h a r t e m p e r a t u r e is e q u i v a l e n t t o t h e g a s temperature and i s i s o thermal.

NOMENCLATURE
A P A -t . Cpf C

s p e c i f i c surface area, A

% ( I - E ) ~, cm.2lcm.3
P

c r o s s s e c t i o n a l area of t h e bed, cm.* a v e r a g e h e a t c a p a c i t y of g a s , callgm. K a v e r a g e c h a r h e a t c a p a c i t y , callgm. K p a r t i c l e d i a m e t e r , cm. a x i a l s o l i d d i s p e r s i o n c o e f f i c i e n t , cm. 2 / s e c .

pa

d P
EZp

183

Fori
Ft

gas i n t e r c h a n g e c o e f f i c i e n t p e r u n i t volume of b u b b l e phase in rl-th compartment, sec.-l v o l u m e t r i c g a s flow r a t e in t h e bed. ~ r n . ~ / s e c . a x i a l d i s t a n c e along bed, cm. moving-bed h e i g h t , cm. h e a t t r a n s f e r c o e f f i c i e n t , cal.lcm.2 l e n g t h of t h e n-th compartment, cm. carbon
K. sec.

H
hf Ahn

-AH

h e a t of r e a c t i o n , cal.lgm.

k Lf N
n
PH 91.92

r e a c t i o n r a t e c o n s t a n t of carbon, atm.-hr.- fluid-bed h e i g h t , cm. t o t a l number of compartments n-th compartment

OK

one minus i n e r t s mole f r a c t i o n

hydrogen p a r t i a l p r e s s u r e , atm. r a t i o of s o l i d downflow rate and s o l i d upflow rate t o t h e s o l i d f e e d rate, respectively

QT
t

h e a t g e n e r a t e d in t h e moving bed, cal./sec. ~ m . ~

time, sec.
average bed temperature. K. average g a s t e m p e r a t u r e , K. average p a r t i c l e temperature. K. s u p e r f i c i a l g a s v e l o c i t y . cm./sec. bubble r i s i n g v e l o c i t y , cm./sec. s u p e r f i c i a l gas v e l o c i t y a t minimum f l i d i z
311,

T T

g T P
0

UB

f m
V b,ven

cm.1sec.
compartment.

volume of t h e b u b b l e and emulsion phase a t t h e n-th downward c h a r rate in moving bed. cm./sec.

~ r n . ~

v
W

W W g, go. g H

t o t a l g a s r a t e through t h e bed, m o l e s l s e c .

WHO

feed rate of hydrogen g a s , moleslsec.

Wso

c o a l f e e d rate, gm./sec. average c h a r r a t e in moving bed, gm./sec. t o t a l f r a c t i o n a l carbon conversion nondimensional p a r t i a l p r e s s u r e of hydrogen in bubble and emulsion phase a t n-th compartment, respectively

Ws
X YBn,Yen

YHo

hydrogen c o n c e n t r a t i o n in f e e d g a s , molelcm.3 i n i t i a l c a r b o n c o n t e n t in f e e d c o a l , Y methane c o n c e n t r a t i o n . m o l e / ~ m . ~ carbon c o n v e r s i o n based on t h e f e e d c h a r , Z f (X-X )I(l-Xo) co

YAo YM
7 .

Y:o(l-Xo)

Z1,ZIF o u t l e t c a r b o n conversion from moving bed and f l u i d i z e d bed, r e s p e c t i v e l y

a number of moles of hydrogen r e a c t e d w i t h one gram of carbon, molelgm. void f r a c t i o n i n emulsion phase

n
9

nondimensional t i m e r e s i d e n c e time in moving bed, a e c . number of moles of hydrogen r e s c t e d w i t h one mole of carbon, m l e l m o l e char bulk d e n s i t y , gm./~rn.~ char p a r t i c l e d e n s i t y , g m . l ~ m . ~ d e n s i t y of f e e d c o a l , g m . / ~ m . ~

pb
pp

pc0

Subscript
0

inlet outlet bubble p h a s e emulsion phase n-th compartment

B
e
n

BIBLIOGRAPHY

1.
2.

Kato, K.

and C. Y. Wen. F.,

Chem. Engrg. S c i .

26,

1351 (1969). Coal G a s i f i c a t i o n . p. 108 (1074). Advances

Feldmann, H.

J. A. Mima and P. M. Yavorsky.

Nash., D.C., Fuel,

I n Chemistry S e r i e s , 131, A.C.S.,

3.
4.

Chermin, H. A. G. and D. W. VanKrevelen. Van Krevelen, D.W., P i t t , G. J. Fuel,

C.

3, 85

(1957). F u e l , 30, 253 (1951).

Van Heerden and F. J. Huntjens.

(1962).

5.
6.

4 , 267 1

F e l d k i r c h n e r , H. L. and H. R. Linden.

I. h E.C. P r o c e s s Design and Development,

21,
7.

153 (1963).
I. h E.C.

Wen, C. Y. and J. Huebler. and 149 (1965).

P r o c e s s Design and Development,

A,

142

8.

Wen, C. Y.,

R. C. B a i l i e , C. Y. Lin, and W.

S. O'Brien.

Coal G a s i f i c a t i o n , p. 9 (1974). A.C.S. Div. of

Advances i n Chemistry S e r i e s , 131, A.C.S., 9. Feldmann, H. F., Fuel Chem.

10.

Wash.,

D.C.,

W.

H.

Simons, J. A. Mima and R. W. Hiteshue.

P r e p r i n t s . v. 14, No. 4, P a r t 11, p. 1, Sept. 1970. Paper p r e s e n t e d at the 5 t h A.G.A./O.C.R.

Feldmann, H. F. and P. M. Yavorsky.

S y n t h e t i c P i p e l i n e Gas Symposium, Chicago, Ill., Oct. 1973.

11.

Feldmann. H. F.,

W. H. Simons, C. Y. Wen and P. M. Yavorsky.

Paper p r e s e n t e d

a t t h e 4 t h I n t e r n a t i o n a l Congress of Chem. Engrg., Chemical Equipment, Design and Automation, Marianske L a m e , Czechoslovakia, Sept. 1972. 12.
,

Feldmann, H.

F.,

C. Y. Wen, W.

H. Simons and P. 11. Yavorsky.

Paper p r e s e n t e d

a t t h e 71st N a t i o n a l Meeting, A.I.Ch.E., Feldmann, H.

F..

D a l l a s , Tex., A.C.S.

1972. Div. of F u e l Chem.

13.

K. D. Kiang and P. M. Yavorsky.

P r e p r i n t s , v . 15, No. 3. p. 67, Sept. 1971. 14. 15. Wen, C. Y. and Y. H. Yu. yoshida, K. and C. Y. Wen. I s h i d a , M. and C. Y. Wen. Mori, S. and C. Y. Wen. A.1.Ch.E.
J9 .

6, 220

(1960). (1970).

Chem. Engrg. S c i . , Chem. Engrg. S c i . ,

2, 1395
23.

16. 17.

125 (1968). Annual Meeting,

Paper p r e s e n t e d . a t t h e 67th A.1.Ch.E.

186

Wash., D.C.,

Dec.

(1974). P a p e r submitted i n I. & E.C. P r o c e s s Design and

18.

Mori, S. and C. Y. Wen. Development (1974).

19.

Hovmand, S. and J . F. Davidson. Miyauchi, T. Chem. Engrg..

F l u i d i z a t i o n , Chapt. 5, Academic P r e s s (1971).

20.
21.

Tokyo,

26, 999
D.C.,

(1962). Fuel G a s i f i c a t i o n , Advances i n

. Levis, P. S ,

S. Friedman and R. W. Hiteshue.

Wash.,

Chemistry S e r i e s , 69, A.C.S., 22.

p. 50, (1967).

Johnson, J. L.
Wash..

C o a l G a s i f i c a t i o n . Advances in Chemistry S e r i e s , 131, A.C.S.,

D.C.,

p. 1 4 5 (1974).

APPENDIX A
S o l u t i o n of Equation (35) T h e h ~ ~ c t i oF(Z> in e q u a t i o n (35) lras t h r e e d i f f e r e n t forms a s d e f i n e d by n e q u a t i o n s (2) and (34) depending upon t h e t o t a l f r a c t i o n a l carbon conversion. When t h e t o t a l f r a c t i o n a l carbon conversion. X, i s less t h a n 0.45, s t a n t v a l u e 1.0 and F(Z) = 0. When X is between 0.45 and 0.55.
A h a s t h e con-

The i n t e g r a l f o r t h i s c a s e i s t h e n very simple.

X h a s a v a l u e t h a t v a r i e s l i n e a r l y w i t h X and
For t h i s c a s e t h e i n t e g r a l of equa-

F(Z) t u r n s o u t t o be a p a r a b o l i c f u n c t i o n . t i o n (35) is e v a l u a t e d in two s t e p s :

f i r s t . f o r X up t o 0.45 and P(Z) = 0; and

second, f o r 0.45 up t o t h e measured v a l u e of X and F(Z) as a p a r a b o l i c f u n c t i o n . Thus kl and kp c o r r e s p o n d t o t h e v a l u e s o f t h e f i r s t and second p a r t s o f t h e i n t e gral. When X i s l a r g e r t h a n 0.55, h a s t h e c o n s t a n t v a l u e 1.8 and F(Z) is a l i n e a r

f u n c t i o n o f Z.

For t h i s c a s e t h e same p r o c e d u r e a s used p r e v i o u s l y r e s u l t s in t h r e e These r e s u l t s are summarized

p a r i s f o r t h e i n t e g r a l c o r r e s p o n d i n g t o k l , k2, and k3.

by t h e f o l l o w i n g e q u a t i o n s .

187

Case 1:

xa.45
F(Z)

Case 2:

0.45950.55
F(Z)

aZ2

+ bZ

where a = 4(1-Xo)
b = 8X
0

3.6

c = 4(0.45

- Xo)2/(1 - X

k = k,

+ k2

where 8 = -4nB(1-Xo)

6 - B(1-nb')

-= C
q

- nBC'

4at - 5 2

, q>o

b' = -(2a t b)
C'=

(a+b+C)
a 1 - Z H ) 2 t b(1-Z")

+c

188

Case 3:

X>O.45
F ( 2 ) = 0.82 i (0.8X0 -

0.40)/(1-X0)

k = k + k
1 2

+ k
3

where

D = 0.80B

0.8B

B(0.8Xo

- 0.40)/(1

XJ

G = (1

+ 0.8n)B

J = A

+ n(E-1)

Unpretreoted cool feed

I

purifier

4 pipeline

90s

FIGURE I

- The

hydrone process for producing high BTU gos by the

direct reoction of cool with hydrogen .

1-21-74

L- 13603

190

- _ .

Q
I

4
cu

7
ul

Dilute phose reoctor Product g o r ( 7 0 ~ m e t h a n e ) Chor crusher

lnterstoqe gas

--- - - - - - -Fluid bed reactor Hydrogen feed

-fl x L L 4

Chor reciever

Figure 2 - Integrated hydroqosificotion unit.

L 12914 -

191

A
I
Char from dilute phase reoctor lnterstage gas

e
Char

2' ID\
Free foil zone

Fluid bec zone

"2

i1

-H2

Cha; out

Figure 3-Schematics

of f l u i d bed reactors

L-14051

192

0 0
O

0 0

I 0
a0

I
0

0
u)

I
0 0 m

I 0 0 e

193

1000

9001/
800
7 00

<
a W a
W

3 I -

600

i-

'1
4 00

/
HY 2 3 HY 2 AHY 5
0

0 0

Top of bed

i
1
1
160

3 OOl 0

20

I 40

60

80

10 0

120

140

POSITION ABOVE DISTRIBUTOR P L A T E , cm FIGURE 5 - Ternperoture profiles for scheme 8 fluid bed reactor.
L-14043

Char from dilute phase r e a c t o r

..

..

..

. ...- F rzeoen ef a l l
* . .

I"

I.

3.26'1 D-

**,

1
?
Char F i g u r e 6-Schematic

Moving bed zone

-H2

of moving bed reactor

L-14056

II
I

I
O -

I
f

I
n 0

I
0

I
P -

I
0
U )

0 0

0 0

0 0

0 0

0 0

0 0

I 0 0

0 0

c3 LL

196

v)

U
(3

I -

.50.
40 -

Measured Colculoted coo I 14 SCF Ib.dry cool

3 0

a Q

30 20

I O

IO

20

30

40

50

60

70

CARBON CONVERSION , percent FIGURE 8 - Mixing effect on the moving bed product gas near the sampling point.

L-14,042

I.

I n

I
0

t n

5:
0

0
U

m
r o

z
m
N

4'

198
I n

lo

0 1 0

0 0

8
m
d

u
. c

W W

0 a
W

z
0

v)

0
d

s
B a
z
0

> z

I n
0

m
rr)

!d o O

02, O

3
rr)

n
N

3
N

n a
3
; D

'u
pc

11 '
1 0 n
I

5 :
1 0 U

m r+)

x
i n
N

1
o

I
~ r

1
c

1
~

I
-

I
t r

R
r

0
)

\
\
0 0

'\

Oo0

6
0
Q,

S G

Counter-'current

Over flow

Go -current

S : solids

G: gos

FIGURE 13- Modes of the fluidized bed operotions.

202

YEN

ZIF=zN4

(only when

- - c char flow

gas f l o w

Figure 1 -Bubble assemblage model f o r 4 f l u i d i z e d char g a s i f i c a t i o n

L- I4 04 6

203

la
CalcZ, Y,,
Y,,

t l
PRINT
Figure 15 -Cornputor
logic diagram
L-14049

204

O'I

I Moving bed 0 Bureou of Mines

Fluidized bed I Bureou of Mines ,counter current 0 Bureou of Mines ,over - flow 0 I.G.T. ,co-current I.G.T. ,counter current

L- 14047

205

Bureau of Mines ,co'unter current Bureau of Mines ,over -flow o I.G.T. ,co-current B I G.T. ,counter current
0

//
0.0

I
I .o

0.5 OBSERVED CARBON CONVERSION

, Z,,

FIGURE 17- Comparison of calculated and observed carbon conversions in fluidized char hydrogosificatian experiments.

L-14048

A
2o

oxygen hydrogen 0 sulfur A nitrogen 0 carbon . Press 69 a t m Temp 684-800'C

0 5 IO CHAR RESIDENCE TIME

15

20

IN MOVING BED, minutes

8 Figure 1

- Cool constituent
residence t i me

conversion as function of

L-13954

207 (HYDRO) GASIFICATION O BATTELLE TREATED COAL (BTC) F

S. P. Chauhan, H. F. Feldmann, E. P. Stambaugh, and J. H. Oxley

505 King Avenue, Columbus, Ohio

INTRODUCTION

B a t t e l l e Columbus L a b o r a t o r i e s 43201

,
'

Conversion of c o a l t o SNG i s one of t h e o p t i o n s a v a i l a b l e f o r a l l e v i a t i n g t h e c r i t i c a l supply s h o r t a g e of n a t u r a l gas. T h i s g a s supply problem i s most extreme i n our e a s t e r n i n d u s t r i a l a r e a s . However, t h e only commercial SNG p l a n t s u s i n g c o a l as a feed s t o c k proposed t h u s f a r have been planned f o r t h e western s t a t e s . A primary reason f o r u s i n g western c o a l is t h a t t h e only commercially a v a i l a b l e technology t h a t is being considered f o r SNG is Lurgi technology which works b e s t N w i t h t h e western noncaking c o a l s . Rapid expansion of a coal-based S G i n d u s t r y i n t h e w e s t i s l i m i t e d by f a c t o r s o t h e r t h a n f i n d i n g c o o p e r a t i v e c o a l . For example, t h e i s s u e s of r e c l a i m a t i o n of strip-mined land i n a r i d r e g i o n s , p o t e n t i a l water supply problems, as w e l l a s t h e r e l u c t a n c e of t h e r e s i d e n t s t o have t h e s e areas undergo r a p i d i n d u s t r i a l i z a t i o n can be expected t o have a r e t a r d i n g e f f e c t on t h e c o n s t r u c t i o n of coal-conversion p l a n t s . A v a i l a b i l i t y of w a t e r , l a r g e r e s e r v e s of h i g h - s u l f u r c o a l s which c a n n o t ' b e . b u r n e d without exceeding allowable SO2 emission l e v e l s , proximity t o areas where g a s s h o r t a g e s are most s e v e r e , t h e a v a i l a b i l i t y of an e x i s t i n g i n d u s t r i a l and mining b a s e and adequate r a i n f a l l t o i n s u r e r e c l a i m a t i o n of strip-mined l a n d a r e a l l f a c t o r s t h a t should encourage t h e u t i l i z a t i o n of e a s t e r n c o a l s as SNG f e e d s t o c k s . However, t h e u t i l i z a t i o n of e a s t e r n c o a l s i s complicated by i t ' s h i g h l y agglomerating n a t u r e . Another c o n s t r a i n t on t h e development of an SNG from c o a l i n d u s t r y whether i t Recent estimates p l a c e t h e i n estment r e q u i r e d f o r b u i l d i n g a p l a n t t h a t w i l l produce approximately 280 x 1 0 SCF/day of p i p e l i n e g a s from c o a l i n t h e neighborhood of $800 m i l l i o n .

is l o c a t e d East o r West is t h e c a p i t a l r e q u i r e d t o b u i l d t h e s e p l a n t s .

E:

Thus, t h e r e is a s t r o n g d r i v i n g f o r c e t o develop technology t h a t w i l l allow both t h e economic s o l u t i o n t o t h e agglomeration problems t h a t complicate t h e u t i l i z a t i o n of e a s t e r n c o a l and t h a t allows t h e investment r e q u i r e d t o b u i l d these p l a n t s t o be reduced. One approach t o lowering investment c o s t s is by c a t a l y s i s of t h e coal-steamhydrogen r e a c t i o n s t o a l l o w t h e coal-steam r e a c t i o n t o occur a t lower temperatures and t h e coal-hydrogen r e a c t i o n a t lower p r e s s u r e s . Numerous a t t e m p t s have been made s i n c e t h e beginning of t h i s century t o c a t a l y z e t h e r e a c t i o n of c o a l and o t h e r carbonaceous m a t t e r w i t h steam (1-9). A few a t t e m p t s have been made r e c e n t l y t o c a t a l y z e t h e r e a c t i o n of c o a l and o t h e r carbonaceous m a t t e r w i t h hydrogen--called h y d r o g a s i f i However, i t is of c o n s i d e r a b l e importance t o develop even b e t t e r c a t i o n (8-12). catalyst systems t o promote b o t h t h e h y d r o g a s i f i c a t i o n and t h e steam-carbon r e a c t i o n s . I n t h i s p a p e r , w e d i s c u s s t h e p r e l i m i n a r y r e s u l t s of a novel t r e a t m e n t p r o c e s s t h a t , i n a d d i t i o n t o enhancing t h e r e a c t i v i t y of c o a l t o steam and hydrogen, e l i m i n a t e s t h e s w e l l i n g and caking p r o p e r t i e s of even t h e most h i g h l y caking E a s t e r n U.S. c o a l s .

208
PROCESS DESCRIPTION B a t t e l l e ' s p r o c e s s i n v o l v e s t h e chemical and p h y s i c a l i n c o r p o r a t i o n of a s u i t a b l e c a t a l y s t i n c o a l . * T h i s p r o c e s s i s t h e outgrowth of a development e f f o r t t o reduce the s u l f u r c o n t e n t of c o a l by chemical e x t r a c t i o n t h a t has been supported by t h e B a t t e l l e Energy Program. G a s i f i c a t i o n t e s t s o f t h e BTC showed t h a t i t had a r e a c t i v i t y f a r g r e a t e r than t h a t p r e d i c t a b l e from t h e r e s u l t s of ongoing i n v e s t i g a t i o n s described i n t h e l i t e r a t u r e . I n a d d i t i o n , BTC was found t o be nonswelling and noncaking. Because of t h e s e promising r e s u l t s , a s e p a r a t e e f f o r t was undertaken t o develop g a s i f i c a t i o n concepts and t o conduct experimental f e a s i b i l i t y s t u d i e s t o e s t a b l i s h t h e t e c h n i c a l and economic f e a s i b i l i t y of t h i s approach f o r t h e production of SNG. The r e s u l t s of t h i s study have exceeded our e x p e c t a t i o n s and, we b e l i e v e , provide t h e N b a s i s f o r a breakthrough i n S G technology. The c a t a l y s t u s u a l l y c o n s i s t s of a conventional g a s i f i c a t i o n c a t a l y s t and a r e a g e n t t h a t r e a c t s w i t h c o a l t o a l t e r and open up t h e s t r u c t u r e of c o a l f a c i l i t a t i n g t h e p e n e t r a t i o n of t h e c a t a l y s t throughout t h e volume of c o a l . During t h e t r e a t m e n t , a s i g n i f i c a n t amount of c a t a l y s t (normally 1 t o 3 weight p e r c e n t ) chemically binds t o the c o a l while a c o n t r o l l e d q u a n t i t y of c a t a l y s t i s p h y s i c a l l y incorporated i n t o t h e c o a l . The r e a g e n t used t o a l t e r t h e s t r u c t u r e of c o a l can be reclaimed by washing of treated coal. EXPERIMENTAL RESULTS A l a r g e number of g a s i f i c a t i o n experiments were conducted w i t h hydrogen and steam t o determine t h e e f f e c t s of c a t a l y s t i n c o r p o r a t i o n , using t h e B a t t e l l e p r o c e s s , on t h e r e a c t i v i t y and caking p r o p e r t i e s of c o a l , on t h e g a s a n a l y s i s , and on t h e p h y s i c a l and chemical c h a r a c t e r i s t i c s of t h e c h a r . Most of t h e experiments were conducted on 70 p e r c e n t minus 200 U.S. mesh c o a l from t h e E a s t e r n United S t a t e s , c o n t a i n i n g about 30 p e r c e n t v o l a t i l e m a t t e r . The p r o c e s s was found t o b e a p p l i c a b l e t o c o a r s e r c o a l s , e . g . , p l u s 2 5 U.S. mesh, a l s o . I n t h i s p a p e r , we d i s c u s s t h e r e s u l t s w i t h l i m e (CaO) a s a g a s i f i c a t i o n c a t a l y s t u s i n g c o a l from t h e Plontour mine ( P i t t s b u r g h Seam No. 8) s i z e d t o 70 p e r c e n t minus 200 U.S. mesh. The r e a g e n t and t h e c o n d i t i o n s f o r t r e a t m e n t w i l l be d i s c l o s e d a t a l a t e r date*. The B T C . w a s washed p r i o r t o g a s i f i c a t i o n t o remove t h e r e a g e n t used d u r i n g treatment. The experiments were conducted i n a thermobalance r e a c t o r , designed f o r highp r e s s u r e (1500 p s i g ) and high-temperature (12OO0C) o p e r a t i o n , shown schematically i n F i g u r e 1. The r e a c t o r system i s very similar t o t h e one described by Gardner, e t a 1 (9). The use of t h e thermobalance r e a c t o r a l l o w s t h e monitoring of t h e mass of a sample a s a f u n c t i o n of time d u r i n g r e a c t i o n . I n t h i s manner, p r e c i s e d i f f e r e n t i a l r a t e d a t a can b e o b t a i n e d . The catalyst-impregnated c o a l was formed i n t o 3/16-inch-diameter by 1/16-inch-long c y l i n d r i c a l p e l l e t s , without u s i n g a b i n d e r , s i n c e the sample c o n t a i n e r w a s made of 100-mesh s t a i n l e s s s t e e l s c r e e n . During a r u n , a 2-gram sample of c o a l was lowered i n t o t h e preheated r e a c t o r zone from t h e l o a d i n g zone i n a few seconds u s i n g a motor-operated w i n d l a s s . Thus, t h e r e a c t i o n time w a s p r e c i s e l y known. The g a s i f i c a t i o n system included a steam condenser, a water . t r a p , flowmeters, a methane-analyzer (I@, and a g a s chromatograph (GC). Prevention of Caking and S w e l l i n g The B a t t e l l e t r e a t m e n t makes even t h e h i g h l y caking c o a l s , e . g . , c o a l s with a f r e e s w e l l i n g index (FSI) g r e a t e r than 6 , completely noncaking. F i g u r e 2 i s a photograph comparing t h e s w e l l i n g and caking of BTC with both raw c o a l and c o a l

Coal t r e a t e d by t h e B a t t e l l e p r o c e s s i s a b b r e v i a t e d i n t h i s paper a s BTC. This process i s d e s c r i b e d more f u l l y i n a n o t h e r paper t i t l e d "The B a t t e l l e Hydrothermal Coal Process" t o b e p r e s e n t e d by E. P. Stambaugh a t t h e 8 0 t h AIChE Meeting.

2 09 t r e a t e d by impregnating i t w i t h CaO as i s c o n v e n t i o n a l l y done. As can be seen, B C T c o n t a i n i n g 7 . 5 p e r c e n t calcium (some of which was p r e s e n t a s an oxide w i t h t h e r e s t chemically bound t o c o a l ) d i d not swell, cake, o r f u s e t o g e t h e r during h y d r o g a s i f i c a t i o n o r steam g a s i f i c a t i o n w h i l e t h e conventionally-impregnated c o a l c o n t a i n i n g 14.5 weight p e r c e n t calcium (20.3 p e r c e n t CaO) s w e l l e d , caked, and s e v e r e l y fused t o g e t h e r on steam g a s i f i c a t i o n . The s w e l l i n g and agglomeration of t h e conventionallyt r e a t e d c o a l would have been even more extreme under h y d r o g a s i f i c a t i o n c o n d i t i o n s . The scanning e l e c t r o n micrographs of raw c o a l and BTC c o a l b e f o r e and a f t e r g a s i f i c a t i o n a r e compared i n F i g u r e 3. I t can be seen t h a t BTC does n o t expand o r swell during h y d r o g a s i f i c a t i o n w h i l e raw c o a l expands and swells s e v e r e l y .
The use of t h e B a t t e l l e p r o c e s s t o make t h e c o a l noncaking i s much more a t t r a c t i v e than t h e e x i s t i n g s t a t e of t h e a r t which i n v o l v e s t h e p r e o x i d a t i o n of c o a l o r t h e use of r a t h e r complicated g a s i f i e r s t o e l i m i n a t e t h e need f o r p r e o x i d a t i o n of c o a l which r e s u l t s i n t h e l o s s of v o l a t i l e matter, a r e d u c t i o n i n t h e r e a c t i v i t y The of c o a l , and subsequently a lowering of t h e e f f i c i e n c y of t h e SNG process. B a t t e l l e p r o c e s s , on t h e o t h e r hand, i n v o l v e s no l o s s of v o l a t i l e matter and subs t a n t i a l l y simpler r e a c t o r systems.

Hydrovasification Rates The r e a c t i v i t i e s of BTC under v a r i o u s c o n d i t i o n s r e l a t i v e t o raw ( u n t r e a t e d ) c o a l were determined from t h e f r a c t i o n a l conversion v e r s u s time d a t a obtained from t h e p r e s s u r i z e d thermobalance. The f r a c t i o n a l c o n v e r s i o n of c o a l on an ash-free b a s i s can be d e f i n e d as
=

(mass of c o a l a t any time) (mass of t h e a s h ) ( i n i t i a l mass of c o a l ) - (mass of t h e a s h )

1)

For t h e purpose of determining t h e e f f e c t of B a t t e l l e t r e a t m e n t on t h e r e a c t i v i t y of c o a l , r e l a t i v e t o raw c o a l , one can d e f i n e an average r e l a t i v e r e a c t i v i t y , R X f o r a given f r a c t i o n a l conversion, X , a s

tx r a w tx9 BTC

where tx,raw,and tx BTc are t h e time r e q u i r e d f o r a f r a c t i o n a l conversion, x , of raw and B a t t e l l e - t r e a t e d coal, respectively.

BTC was found t o have a much higher h y d r o g a s i f i c a t i o n r e a c t i v i t y t h a n raw c o a l . The d a t a i n F i g u r e 4 show t h a t t h e average r a t e of g a s i f i c a t i o n a t 850C and 500 p s i g hydrogen p r e s s u r e based on 70 p e r c e n t conversion (moisture-free b a s i s ) of BTC c o n t a i n i n g 7.5 weight p e r c e n t calcium, w a s about 40 t i m e s f a s t e r t h a n t h e raw c o a l . The BTC was found t o be more than a n o r d e r of magnitude more r e a c t i v e t h a n c o a l t h a t w a s impregnated w i t h c a t a l y s t by t h e conventional s l u r r y mixing a t room temperature, a s shown i n F i g u r e 5. The importance of t h e i n c r e a s e d h y d r o g a s i f i c a t i o n r e a c t i v i t y i s t h a t high c o n c e n t r a t i o n s of methane should be a c h i e v a b l e i n t h e r a w product g a s thereby reducing t h e amount of methane t h a t has t o be produced by methanation. One of t h e most important results of t h i s work from a p r o c e s s economics p o i n t of view i s t h e reduced p r e s s u r e a t which t h e BTC can b e h y d r o g a s i f i e d compared t o raw coal. Figure 4 shows t h a t even at p r e s s u r e s of 150 p s i g t h e BTC is much more r e a c t i v e than r a w c o a l a t 500 p s i g . Furthermore, comparison of methane y i e l d s by g r a p h i c a l i n t e g r a t i o n of g a s a n a l y s i s d a t a (Figure 6) i n d i c a t e t h a t t h e methane y i e l d , defined a s t h e r a t i o of t h e carbon converted t o methane t o t h e t o t a l carbon

210
g a s i f i e d , of BTC a t 250 p s i g is t h e same as f o r t h e raw c o a l a t 500 p s i g . Thus, because c o a l can be converted t o methane a t p r e s s u r e s much lower than had been p r e v i o u s l y thought p o s s i b l e , investment c o s t s f o r SNG p l a n t s u s i n g BTC can be s u b s t a n t i a l l y reduced. I n a d d i t i o n , t h e r e l i a b i l i t y of t h e p l a n t should be s i g n i f i c a n t l y i n c r e a s e d because of t h e lower p r e s s u r e o p e r a t i o n . Steam G a s i f i c a t i o n Rates Providing h e a t f o r t h e endothermic steam-carbon r e a c t i o n i s one of t h e f a c t o r s that c o n t r i b u t e s s u b s t a n t i a l l y t o t h e c o s t of SNG f r m c o a l . The reason f o r t h e c o s t l i n e s s of t h i s s t e p is p r i m a r i l y t h a t oxygen is u s u a l l y used t o combust p a r t of the carbon t o p r o v i d e t h e h e a t . Thus, anything t h a t can lower t h e temperature r e q u i r e d f o r g a s i f y i n g c o a l with steam w i l l reduce oxygen requirements and, thereby, the SNG c o s t s . Experimental d a t a show t h a t t h e Battelle c a t a l y s t i n c o r p o r a t i o n p r o c e s s allows a s u b s t a n t i a l r e d u c t i o n i n g a s i f i c a t i o n temperature over t h a t r e q u i r e d f o r e i t h e r r a w coal g a s i f i c a t i o n o r c o a l t h a t c o n t a i n s a l k a l i c a t a l y s t s t h a t are impregnated i n t o t h e c o a l by c o n v e n t i o n a l means. For example, F i g u r e 7 compares t h e time req u i r e d t o achieve v a r i o u s g a s i f i c a t i o n conversion l e v e l s f o r BTC, c o a l conventionC l e a r l y , t h e r e a c t i v i t y of a l l y impregnated w i t h CaO and raw c o a l a l l a t 825'C. BTC i s s u b s t a n t i a l l y b e t t e r t h a n e i t h e r of t h e o t h e r s even though t h e B C c o n t a i n s T only about h a l f t h e c o n c e n t r a t i o n of Ca a s i n t h e c o n v e n t i o n a l l y impregnated c o a l . The e f f e c t of temperature on g a s i f i c a t i o n r a t e is shown i n F i g u r e 8. I n t e r p o l a t i o n i n d i c a t e s t h a t , w i t h BTC, g a s i f i c a t i o n r a t e s a t approximately 675'C are e q u i v a l e n t t o t h o s e at 825C w i t h raw coal. More important i n reducing oxygen consumption t h a n t h e lowering of s e n s i b l e h e a t requirements is t h e h i g h e r methane y i e l d t h a t one e x p e c t s from lower temperat u r e o p e r a t i o n and t h e c a t a l y s i s of t h e carbon-hydrogen r e a c t i o n . The higher r a t i o of methane t o carbon o x i d e s a c h i e v a b l e a t t h e lower temperature s u b s t a n t i a l l y reduces t h e endothermicity of t h e carbon-steam r e a c t i o n .

,/

Reactor Systems f o r (Hydro) G a s i f i c a t i o n )

BTC's important advantages ( i . e . , low temperature and p r e s s u r e o p e r a b i l i t y , and no s w e l l i n g o r caking) w i l l have a very important impact n o t o n l y on t h e r e a c t o r s y s t e m t h a t is developed f o r i n t e g r a t i o n w i t h t h e c o a l treatment s t e p but a l s o on o t h e r supporting o p e r a t i o n s . Obviously, BTC could be used i n any of t h e r e a c t o r systems c u r r e n t l y b e i n g developed. However, because of t h e noncaking n a t u r e of t h e BTC and i t s h i g h r e a c t i v i t y a much simpler r e a c t o r system than more c u r r e n t l y being developed f o r handling e a s t e r n c o a l s should s u f f i c e .

CONCLUSIONS The B a t t e l l e - t r e a t e d c o a l (BTC) is a p o t e n t i a l l y s u p e r i o r g a s i f i c a t i o n feeds t o c k t h a n raw ( u n t r e a t e d ) c o a l o r c o a l impregnated i n a c o n v e n t i o n a l manner with catalysts

The s p e c i f i c advantages of BTC demonstrated by t h i s g a s i f i c a t i o n s t u d y a r e : 1. The prevention of caking and s w e l l i n g of c o a l during h y d r o g a s i f i c a t i o n and steam g a s i f i c a t i o n High rates of steam g a s i f i c a t i o n allowing steam g a s i f i c a t i o n t o proceed a t s u b s t a n t i a l l y lower temperatures than with raw c o a l o r c o a l t r e a t e d w i t h c a t a l y s t s i n a c o n v e n t i o n a l manner

2.

211
3.
Rates of h y d r o g a s i f i c a t i o n a s h i g h as 40 times t h o s e of raw c o a l and t h e maintenance of t h i s h i g h r e a c t i v i t y even a t p r e s s u r e s a s low as 250 p s i g .

Because of t h e s e advantages w e b e l i e v e t h a t t h e development of a (hydro) g a s i f i c a t i o n process based upon t h e use of BTC w i l l r e s u l t i n a s u b s t a n t i a l lowering of both investment and o p e r a t i n g c o s t s as w e l l a s a l l o w t h e r e l i a b l e u t i l i z a t i o n of our l a r g e e a s t e r n U.S. c o a l r e s e r v e s f o r t h e production of c l e a n gaseous f u e l s . AK O LD MNS C N WE G E T This work was supported by t h e B a t t e l l e Energy Program. The t e c h n i c a l a s s i s t a n c e provided by D r . John F. F o s t e r is g r e a t l y a p p r e c i a t e d .

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REFERENCES E l l i o t t , M . A . , P r e p r i n t s of F u e l D i v i s i o n , American Chemical S o c i e t y Meeting, 140 (1974). Kroger, C . , Melhorn, Gunter, Brennstoff-Chem, Kroger, C . , Angew, Chem.,

- (3), 19

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(1938).

52,

1 2 9 (1939). Ind. Eng. Chem.,

L e w i s , W. K . , G i l l i l a n d , E. R . , Hipkin, H.,
Kislykh, V.

9, 1697

(1953).

I., Shishakov, N. V . ,

Gaz. Prom.,

5,

1 5 (1960).

W i l l s o n , W. G . , e t a l . , Coal G a s i f i c a t i o n , Advances i n Chemistry S e r i e s 131, E d i t e d by L. G. Massey, American Chemical S o c i e t y , Washington, D . C . , 1974, p . 203. (7) Haynes, W. P . , G a s i o r , S. J . , Forney, A. J . , Coal G a s i f i c a t i o n , Advances i n Chemistry S e r i e s 131, E d i t e d by L. G. Massey, American Chemical S o c i e t y , Washington, D . C . , 1974, p . 179. Renwick, R. T . , Wentrcek, P. R . , Wise, H . ,

u, 53, 274

(October 1974).

Gardner, N., Sarnuels, E., Wilks, K. , Coal G a s i f i c a t i o n , Advances i n Chemistry S e r i e s 131, Edited by L. G . Massey, American Chemical S o c i e t y , Washington, D.C., 1974, p . 217. Wood, R. E . , H i l l , G. R., P r e p r i n t s o f Fuel Division, American Chemical Society Meeting, (1),August, 1972.

1 7

Dent, F. J . , Blackburn, W. M. Millet, H. C . , Trans. I n s t . Gas Engrs.,

(1937). Dent, F. J . , Blackburn, W. M . , 69 (1938). M i l l e t , H. C . , I n s t . Gas Engrs.,

87,

231

Commun.,

190,

213

I n .U
c

? ! a

?8
I

r4

! %
W

215

Raw Coal, Before Hydrogasification

BTC, Before Hydrogasification

Raw Coal, After Hydrogasification

BTC, After Hydrogasification

FIGURE 3.

SCANNING ELECTRON NICROGRAPBS OF F W COAL AND BTC A BEFORE AND AFTER HYDROGASIFICATION

216

1.0

\Row

Cool at 500 w i g

L
0.2

1 1 ' 1 1

Hydrogosificotionot 850 *c

'

'

'

'

'

20

x)

40

50

60

70

80

90

!O

Time, minutes

FIGURE 4 .

DEPENDENCE OF THE RATE OF HYDROGASIFICATION OF BTC ON PRESSURE

0.8
c

Conventional Catalyst Impregnation ; Coa7.5 Ye

-Row

Coal

LL

Hydragasificotion a t 850% and 500 psig

0.2

r
&

0.0 . 0.

I 5

'

I IO

I
15

I
40

I
45

I
60

20

25 30 Time, minutes

3s

FIGURE 5.

COMPARISON OF THE REACTIVITY OF BTC WITH RAW COAL AND A COAL THAT WAS CONVEWIONALLY IMPREGNATED WITH CATALYST

217
1.0r

FIGURE 6 .

RATE OF METHANE PRODUCTION DURING HYDROGASIFICATION AT 8 5 O o C F O R COAL WEIGHING ONE GRAM (ASH-FREE) BEFORE G A S I F I C A T I O N

Steam Gasification at 82% and 500psig

0 0

1 0

20

30 Time. minutes

40

Y )

FIGURE 7.

COMF'ARISON O F THE R E A C T I V I T Y O F BTC W I T H R A W COAL AND A COAL THAT WAS CONVENTIONALLY IMPREGNATED W I T H CATALYST

218

z
w

219
FACTORS AFFECTING THE THERMAL EFFICIENCY OF A GASIFICATION PROCESS C . Y . Wen, P. R . Desai and C. Y . Lin

Department of Chemical Engineering, West V i r g i n i a University, Morgantown, WV

26506

Abstract - Two main f a c t o r s a f f e c t i n g t h e thermal e f f i c i e n c y o f t h e g a s i f i c a t i o n process a r e t h e amount of methane formed i n t h e g a s i f i e r and t h e kind of coal used. Thermal e f f i c i e n c i e s a r e c a l c u l a t e d f o r t h e various coal g a s i f i c a t i o n processes having p o t e n t i a l f o r commercialization. Another way o f comparing d i f f e r e n t processes, based on t h e second law of thermodynamics c o n s i d e r a t i o n s i n terms of a v a i l a b l e work i s introduced. The r e s u l t s show t h a t higher amounts o f methane formed by d i r e c t methanation i n t h e g a s i f i e r w i l l r e s u l t i n higher thermal e f f i c i e n c y of t h e process. Thermal e f f i c i e n c y of Lurgi Process decreases cansiderably when higher ranking coals a r e used. The a v a i l a b l e work e f f i c i e n c y can be used n o t only f o r comparison but a l s o t o pinpoint i n e f f i c i e n c i e s inherent i n c e r t a i n process s t e p s . Introduction Coal g a s i f i c a t i o n processes f o r production of S G can be divided i n t o s e v e r a l N i n d i v i d u a l sub-systems, such as c o a l p r e p a r a t i o n , pretreatment g a s i f i c a t i o n , s h i f t conversion, gas p u r i f i c a t i o n and methanation which may be followed by compression t o d e s i r e d p i p e l i n e gas p r e s s u r e i f necessary. A s t h e products of g a s i f i c a t i o n a f f e c t t h e o v e r a l l thermal e f f i c i e n c y o f t h e process g r e a t l y , g a s i f i c a t i o n sub-system is described b r i e f l y i n t h e following s e c t i o n . Gasification

In g a s i f i c a t i o n , coal is converted i n t o gases t h a t can be converted l a t e r i n t o a p i p e l i n e q u a l i t y gas having a heating value of more than 900 Btu/SCF. In a g a s i f i e r , following reactions take place:
Coal Pyrolysis

Char

aCH4

BC2H6 + yC0 + 6H2 + Moisture 1) 2) 3)

Char + Steam + CO + H2
CO
+

Steam
+

C02
+

H2

Char

2H2

CH4

Steam-char r e a c t i o n is highly endothermic while water gas and h y d r o g a s i f i c a t i o n r e a c t i o n s a r e exothermic. Heat required i n r e a c t i o n 1) can be supplied d i r e c t l y by coal-oxidation o r i n d i r e c t l y by h e a t i n g . (13) The major f a c t o r a f f e c t i n g t h e thermal e f f i c i e n c y is t h e amount o f methane formed i n the g a s i f i e r . Amount of methane produced depends on p r e s s u r e , temperature and t h e kind of g a s i f i e r used. E f f e c t of Methane Concentration i n Gas from G a s i f i e r on t h e Thermal E f f i c i e n c y of t h e Process: In Figure 1, heating value of t h e gas a t t h e g a s i f i e r e x i t i s p l o t t e d a g a i n s t t h e c a l c u l a t e d values o f o v e r a l l thermal e f f i c i e n c y f o r various processes ( 2 ) , (6). The r e s u l t s c l e a r l y show t h a t when t h e amount o f methane produced i n t h e g a s i f i e r i s h i g h e r , t h e thermal e f f i c i e n c y o f t h e process i s c o n s i s t e n t l y higher. The reason f o r t h i s is t h a t t h e amount of hydrogen r e q u i r e d t o produce methane is l e s s i f hydrogen r e a c t s with carbon i n coal r a t h e r than with carbon i n carbon monoxide o r

' \

220

dioxide a s i t occurs i n methanator l a t e r on. Also t h e h e a t generated i n t h e g a s i f i e r because of h y d r o g a s i f i c a t i o n r e a c t i o n can be u t i l i z e d t o c a r r y out t h e carbon-steam endothermic r e a c t i o n i n t h e g a s i f i e r . This h e a t u t i l i z a t i o n i s more e f f i c i e n t than u t i l i z a t i o n o f heat recovered i n t h e form of high p r e s s u r e steam i n methanation. In a d d i t i o n , h e a t generated due t o h y d r o g a s i f i c a t i o n r e a c t i o n reduces t h e oxygen r e q u i r e ments reducing the consumption of energy i n t h e oxygen p l a n t . Coal contains c e r t a i n amounts of a l i p h a t i c compounds and hydrogen i n t h e form o f v o l a t i l e m a t t e r . This v o l a t i l e matter decomposes i n t o low hydrocarbon compounds such a s methane, ethane, e t c . , by r e a c t i n g with hydrogen during t h e p y r o l y s i s and t h e i n i t i a l s t a g e o f g a s i f i c a t i o n . For example, i n Lurgi.Process using moving bed g a s i f i e r , coal and gas f l o w s a r e countercurrent and hence, l a r g e amounts o f hydrogen is contacted with coal i n t h e d e v o l a t i l i z a t i o n zone ( t o p of t h e r e a c t o r ) producing methane. E f f e c t o f Temperature and P r e s s u r e on Methane Production: Amount of methane produced decreases with i n c r e a s e i n temperature, e . g . , i n Koppers-Totzek Process, due t o high temperature (3200F) very l i t t l e methane i s produced ( 3 ) . And, t h e r e f o r e , i n t e n s i v e methanation i s required. However, due t o high temperature, tar and h i g h e r hydrocarbons decomposes i n t o carbon monoxide and hydrogen eliminating complications i n t h e p u r i f i c a t i o n s e c t i o n found i n o t h e r lower temperature processes. Amount of methane produced i n c r e a s e s with t h e i n c r e a s e i n p r e s s u r e . This increase i n methane concentration continues a t pressures above 400 p s i g . (used i n Lurgi g a s i f i e r s ) and q u a n t i t a t i v e d a t a on t h i s phenomenon have been reported by B.C.R.(4). The o t h e r f a c t o r a f f e c t i n g t h e thermal e f f i c i e n c y i s t h e kind o f coal g a s i f i e d . Coal can be c l a s s i f i e d i n t o p e a t , l i g n i t e , sub-bituminous, bituminous, semi-bituminous and a n t h r a c i t e . L i g n i t e and sub-bituminous c o a l s a r e u s u a l l y caking coals and form n m - p r o u s cuke on h e a t i n g . E f f e c t o f Coal on t h e E f f i c i e n c y o f t h e G a s i f i c a t i o n Process: In coal-steam r e a c t i o n , t h e o r e t i c a l l y t h e following two forms o f r e a c t i o n s can take p l a c e . Coal
+

Steam A ; R

CO + H 2 + COz

HZS

4)

Coal + Steam AR ;

COz + CH4 + H2S

Even though r e a c t i o n 4 and 5 a r e extremes, they t a k e p l a c e simultaneously i n a g a s i f i e r with few exceptions. For example, i n Koppers-Totzek g a s i f i e r only r e a c t i o n 4 occurs while i n Hydrane g a s i f i e r r e a c t i o n 5 occurs t o l a r g e e x t e n t . Both of t h e above r e a c t i o n s are endothermic. Endothermicity o f t h e r e a c t i o n r e p r e s e n t s t h e amount o f hear r e q u i r e d t o complete t h e r e a c t i o n and i n g a s i f i c a t i o n , t h i s h e a t is supplied by o x i d a t i o n o f c o a l with oxygen. The endothermicity of t h e r e a c t i o n i s d i f f e r e n t f o r d i f f e r e n t c o a l and s i n c e h e a t i s supplied by oxidation of c o a l , i t may be expected t o be d i r e c t l y r e l a t e d t o t h e e f f i c i e n c y of t h e process.
For t h r e e d i f f e r e n t c o a l s , d a t a shown i n Table 1 were reported by Koppers company ( 3 ) . These d a t a show t h a t t h e amount of oxygen and steam required f o r g a s i f i c a t i o n increases with t h e i n c r e a s e i n v o l a t i l e m a t t e r . The d a t a a l s o show t h a t t h e composition and t h e h e a t i n g value of t h e g a s i f i e r product a r e almost s i m i l a r i n a l l cases and thus a r e n e a r l y independent of kind o f coal used. Carbon conversion i s a function of r e a c t i v i t y of coal. L i g n i t e and sub-bituminous coals can be converted almost completely while conversion of high v o l a t i l e coals approaches95%-97% ( 3 ) . The same kind o f d a t a c o l l e c t e d from t r i a l s a t Westfield, Scotland, were r e p o r t e d by Lurgi f o r Montana, I l l i n o i s 5 , I l l i n o i s 6 and P i t t s b u r g h 8 c o a l s . ( l ) , ( 1 1 )

22 1
TABLE 1 E f f e c t o f Coal on G a s i f i e r Products,Koppers-Totzek Process ( 3 Sub-bituminous Western High V o l a t i l e B- Bituminous I 11i n o i s High V o l a t i l e A-Bituminous Eastern

Coal Composition (wt. %)

C

H 0

N S
Ash Moisture Heating Value BTU/lb. Gasification Oxygen required TIT of coal Steam required TIT of c o a l Gas Composition Dry Basis (Vol %)

56.76 4.24 13.18 1.01 0.67 22.14 2.00 9,888.

61.94 4.36 6.73 0.97 4.88 19.12 2.00 11,388.

69.88 4.90 7.05 1.37 1.08 13.72 2.00 12,696.

0.649 0.136

0.704 0.27

0.817 0.294

co
co2 *2 N2 H2S

cos

58.68 7.04 32.86 1.12 0.28 0.02 100.00 295.1 136.4

55.38 7.04 34.62 1.01 . l . 83 0.12 100.00 290.2 156.6

55.90 7.18 35.39 1.14 0.35 0.04 100.00 294.4 174.8

L
\

Gas Heating value BTU/SCF No. of moles/ton of coal Efficiency % Heating value of gas/ Heating value of coal Heating value of gas/ Heating value of coal + + coal used f o r production of steam and power required.

77.3 69.7

75.8 67.9

77.0 68.7

222
These d a t a a r e shown i n Table 2 . I t can be concluded t h a t higher o p e r a t i n g temperature i s necessary with decreasing coal r e a c t i v i t y . Oxygen and steam consumpt i o n s i n c r e a s e with t h e decrease i n coal rank. However, y i e l d of methane remains f a i r l y constant f o r d i f f e r e n t kinds o f c o a l . I t a l s o shows t h a t e f f i c i e n c y of g a s i f i c a t i o n , allowing f o r t h e coal equivalent of steam and oxygen s u p p l i e s , decreases s u b s t a n t i a l l y with t h e i n c r e a s e in c o a l rank. The type o f coal processes a l s o a f f e c t s t h e amount of water required i n a g a s i f i c a t i o n process. The f a c t o r s a f f e c t i n g t h e water requirements a r e : a) Moisture content b) Reactivity of c o a l and c) S u l f u r content o f coal

For a p l a n t producing 250 MMSCF o f p i p e l i n e gas, t h e t o t a l water requirement i s roughly about 19,000 gpm. when l i g n i t e coal is used while f o r bituminous coal water r e q u i r e d i s about 22,500 gpm.
Thermal e f f i c i e n c y c a l c u l a t i o n s done on t h e b a s i s o f f i r s t law of thermodynamics a r e u s e f u l f o r comparison of c o a l g a s i f i c a t i o n processes. Another way of comparing d i f f e r e n t a l t e r n a t i v e s i s t o c a l c u l a t e energy u t i l i z a t i o n e f f i c i e n c y based on t h e second law of thermodynamics, which i s defined a s t h e r a t i o of t o t a l output of work equivalent i n a l l outgoing streams t o t h e t o t a l input. The main advantage of t h i s approach is i t s a b i l i t y t o compare energy u t i l i z a t i o n e f f i c i e n c y o f d i f f e r e n t processing schemes and a l t e r n a t i v e s , which may s t a r t from d i f f e r e n t energy resources and may produce d i f f e r e n t products, i n a c o n s i s t e n t way. ~t a l s o p i n p o i n t s t h e i n e f f i c i e n c i e s i n h e r e n t i n c e r t a i n process s t e p s .
From secoiid laii of theiiiiody-nzaics, t h e a v a i l a b l e vork, d s , can bc cxprcssed i n terms of enthalpy change (dH) and entropy change (ds) a s :
'

dE = dH - Tods where To i s t h e temperature o f t h e surrounding.

For a closed system i n e q u i l i b r i u m a t To, when no work can be obtained from i t i n t h e given surroundings,
E = H

- H - T(S-So)

i s t h e maximum amount of work which can become a v a i l a b l e from t h e system i f o i t can exchange h e a t only with a h e a t r e s e r v o i r a i T o . A process stream c a r r y i n g n moles of i p e r u n i t of time and performing work w I n t h e same time is equivalent t o a f l u x of a v a i l a b l e work

E;' ;..

"
+

1 1 1

s
gin
entering t h e system i s

A t steady s t a t e , f o r any system, t h e a v a i l a b l e work

0 0

a l w a y s - g r e a t e r than o r equal t o t h a t leaving t h e system 'in

-> 'out

Then, t h e a v a i l a b l e work e f f i c i e n c y rl can be defined a s

rl =

Pout /Fin

The f r a c t i o n (1-n) i s being l o s t due t o i r r e v e r s i b l e processes causing an entropy production u

223
(1-n)

Pin

T ,

a = I

Where 1 is t h e i r r e v e r s i b l e work a s s o c i a t e d with t h e entropy change. The datum l e v e l used i n a v a i l a b l e work e f f i c i e n c y c a l c u l a t i o n s , i s defined a s one i n which an e x i s t i n g substance, when i n equilibirum with t h e surrounding, w i l l have zero a v a i l a b l e work. Under The bases used for c a l c u l a t i o n s a r e air and water a t 1 atm. and 25'C. t h e s e conditions, it may be assumed t h a t a v a i l a b l e work from C02 and SO2 i s zero.

Table 2

1 \\
\

E f f e c t of coal on GBsifier Products Lurgi Process ( 1 ) Rosebud Montana 50.56 3.18 9.80 0.91 1.09 9.76 24.70 I11i n o i s #5 64.11 4.36 7.04 1.22 3.13 8.20 11.94 100.00 11456. 0.46 2.25

Coal Composition w t % C H 0

I 11i n o i s #6
64.16 4.34 8.10 1.21 2.80 9.16 10.23

Pittsburgh #8 74.15 5.04 4.52 1.35 2.52 7.84 4.58

N S
Ash Moisture Heating value Btu/lb

100.00
8611. 0.24 1.25

100.00
11464. 0.45 2.51

100.00
13442. 0.59 3.24

Gasi fi'cat ion Oxygen required T/T o f coal Steam required T/T of coal Gas composition D r y Basis (%)

co

co2

C H-

15.1 30.4 41.1 1.2 0.5 11.2 0.5

CiH:

Gas heating value excluding H2S Btu/SCF 239. No. of moles/ton o f c o a l 212.6 Efficiency % Heating value of gas/ h e a t i n g value o f coal 79.9 Heating value of gas/ (Heating value of coal gasi-58.7 f i e d + coal used f o r product i o n o f steam and power r e quired)

1oo.o

17.6 31.0 38.8 1.5 1.1 9.2 0.5 0.3 100.0 291. 160.6 77.5 52.8

100.0
290. 158. 75.8 50.9

17.3 31.2 39.1 1.2 1.1 9.4 0.7

16.9 31.5 39.4 1.6 0,. 8 9.0 0.7 0.1 100.0 285. 187. 75.3 48.8

2 24
Based on above datum l e v e l , t h e corresponding work equivalent o f t h e chemical elements a r e c a l c u l a t e d and are shown i n Table 3. Table 3 Substance Coal* C Available Work o f Chemical Elements State Solid Solid Solid Gas
E

a t 25'C & 1 atm. Btu/mole

224,460 (Btu/mole-C) 168,000' 127,560 1,670 250 101,210 3,700 109,780
0

S
0 N2 $0

Gas
Gas

,
d

Gas
Gas Gas

C8

co2
CH4 *Pittsburgh seam coal i s used.

d
J

Gas

348,570
/

Entropy of c o a l is about 4 cal/gmole-carbon

OK.

Energy u t i l i z a t i o n e f f i c i e n c y based on a v a i l a b l e work and percentage d i s t r i b u t i o n o f i r r e v e r s i b i l i t y f o r d i f f e r e n t process s t e p s of Lurgi, Koppers-Totzek and Hydrane Processes were c a l c u l a t e d . The r e s u l t s a r e shown i n Table 4. Table 4 Evaluation of i r r e v e r s i b l e work d i s t r i b u t i o n i n t h e coal g a s i f i c a t i o n processes t o produce pipeline gas. (Feed Coal = 1 t o n b a s i s , P i t t s b u r g h seam) LurgiGasifier Feed coal a v a i l a b l e work x 10' B t u Product p i p e l i n e gas, a v a i l a b l e work x 106 Btu I r r e v e r s i b l e l o s t work x lo6 Btu Thermal e f f . Available work e f f . I r r e v e r s i b l e l o s t wor d i s t r i b u t i o n , x 10 Btu Gasifier Heat exchanger and spray tower S h i f t. converter Purification unit Methanation unit Oxygen p l a n t Steam and power p l a n t 25.74 15.30 10.44 64% 59% 3.82 0.96 0.33 1.16 1.09 1.34 1.74 Koppers-Totzek Gasifier 25.74 13.49 12.25 54% 52% 4.03 1.06 Hydrane Process 25.74 16.72 9.02
72% 65%

4.16 0.81 0.30 1.os 0.13 0.86 1.71

1.41 1.28 1.80 2.06 0.61

I
1

225

Acknowledgment
I

This work was supported partially by National Science Foundation and partially by ERDA. References 1. Elgin, D. C., "Results of Trials of American Coals in Lurgi Pressure-Gasification Plant at Westfield, Scotland", proceedings of Sixth Synthetic Pipeline Gas Symposium, Chicago, Illinois, October 1974. 2. Feldmann, H. F., Wen, C. Y., Simon, W. H., Yavorsky, P. M., "Supplemental Pipeline Gas from Coal by the Hydrane Process", paper presented at the 71st National AIChE Meeting, Dallas, Texas, February 20-23, 1972. 3. Fransworth, J. F., Mitsak, D. M., Kamody, J. F., "The Production of Gas from Coal Through a Commercially Proven Process", Koppers Company, Inc.. Pittsburgh, August, 1973. 4. Hendrickson, T. A . , "Synthetic Fuels Data Handbook", pp. 168-182, Cameron Engineers, Inc., 1975. Howard, H. C., Ind. & Eng. Chem. Vol. 44, No. 5 , p. 1083, 1952. Huebler, J., Lee, B. S . , and Schora, F. C., Jr., "Hygas Coal Gasification Process", For Publication in the Handbook of Energy Technology, June, 1974. 7. Lowry, H. H., Chemistry of Coal Utilization, p. 208, p. 250-260. 8. Mazumdar, B. K., Coal Science, p. 475, 1966. 9. Mudge, L. K., Schietelbein, G. F., Li, C. T., and Moore, R. H., "The Gasification of Coal, A Batelle Energy Program Report, July, 1974. 10. Riekert, L., Chem. Eng. Sci., Vol. 29, p . 1613, 1974. 11 * Rudolph, R. F. H., "Processing of Americans Coals in a Lurgi Gasifier", Proceedings of Sixth Synthetic Pipeline Gas Symposium, Chicago, Illinois, October, 1974. 12. University of Michigan, "Evaluation of Coal Conversion Processes to Provide Clean Fuels", Final Report, p. 376-379, Feb. 1974. Interim Report to 13. Wen, C. Y., "Optimization of Coal Gasification Processes1f, Office of Coal Research, 1972.

f,

226

80
'herma1 If i c i e n c y

70

2 Ei&i
0 Bigas

e
60

Hygas Synthane Hydrane

50

200

300

400

500

600

700

800

900

BTU/SCF a t t h e G a s i f i e r E x i t

Figure 1 E f f e c t o f Amount of Methane Produced i n t h e G a s i f i e r on t h e Thermal . E f f i c i e n c y o f t h e Process.

227
LABORATORY EVALUATION O PROPERTIES F O F Y ASH-IRON OXIDE ABSORBENTS F R H 2 S F L O RENOVAL FROM HOT LOW-BTU G S A

E. C. Oldaker, A. )I. Poston, J r . , and \I.

L. F a r r i o r , Jr.

U.S. Energr Research and Development Administration

hlorgantown Energy Research Center Morgantown, West V i r g i n i a
1NTRODUCTIO;J

The Morgantown Energy Research Center is conducting r e s e a r c h on s o l i d , regenerable absorbents t o remove 1I.S from hot (1,000-1,5000F) low-Btu f u e l gas made by g a s i f y i n g c o a l with air and steam. The h e a t i n g value o f low-Btu gas r a n e e s from 100 t o 150 Btu p e r cubic f o o t , which makes it uneconomical f o r l o n g d i s t a n c e t r a n s p o r t b u t i s s u i t a b l e f o r "on-site'' u t i l i z a t i o n t o f i r e powerplant o r i n d u s t r i a l b o i l e r s . Removal of t h e s u l f u r ( l a r g e l y H2S) from t h e gas while s t i l l hot a f f o r d s two b e n e f i t s f o r t h e u t i l i z a t i o n of low-Btu gas as a f u e l . F i r s t , t h e gas can be d i r e c t l y f i r e d i n b o i l e r s and meet environmental s t a n d a r d s concerning s u l f u r emissions t o the atmosphere. Second, t h e s e n s i b l e h e a t o f t h e gas is r e t a i n e d , t h e r e b y i n c r e a a i n g t h e o v e r a l l thermal e f f i c i e n c y o f t h e f u e l . The use o f i r o n oxide t o remove 112s from i n d u s t r i a l gases has been p r a c t i c e d f o r many y e a r s . Coke oven gases have been d e s u l f u r i z e d by f i x e d o r f l u i d beds o f . i r o n oxide at temperatures up t o 752OP (1) Abel e t a l . ( 2 ) and S h u l t z ( 3 ) r e p o r t e d t h e r e s u l t s of l a b o r a t o r y s t u d i e s i n which s o l i d absorbents were used t o remove H2S from h o t , simulated and a c t u a l producer gas. Clay and Lynn ( 4 ) d e s c r i b e d t h e use o f i r o n oxide supported on alumina t o remove NOx and SOx from powerplant s t a c k gases at temperatures approaching, 1,OOOOF. They i n j e c t e d a stream o f s y n t h e s i s gas (CO + H z ) t o reduce t h e SO2 t o HzS and NO t o 112 b e f o r e p a s s i n g t h e f l u e gases over the c a t a l y s t . Laboratory i n v e s t i g a t i o n s a r e being d i r e c t e d toward developing a s o l i d , regenerable absorbent composed of i r o n o x i d e supported on a matrix of f l y a s h which has both t h e a b s o r p t i o n c a p a c i t y and p h y s i c a l s t r e n & h b e l i e v e d t o be r e q u i r e d f o r a commercial a p p l i c a t i o n i n removing HzS from low-Btu f u e l gases at temperatures above
l.OOOF.

Mechanical problems i n v o l v i n g a t t r i t i o n of t h e i r o n oxide l e a d i n g t o unacceptable carry-over and absorbent replacement, and plugging or f o u l i n g of system components were some of t h e shortcomings of previous work using i r o n oxide t o remove H2S from various type gases. By supporting t h e i r o n oxide upon a m a t r i x of f l y a s h , t h e s e p r o b l e m are overcome. The development o f a s o l i d , p e l l e t - s i z e d absorbent having adequate s u r f a c e area o r pore volume which e f f e c t i v e l y removes II2S e l i m i n a t e s t h e need f o r f l u i d i z a t i o n and/or t h e use of very small i r o n oxide p a r t i c l e s . Another advantage i s t h e lower c a p i t a l and o p e r a t i o n a l c o s t s when u s i n g a f i x e d bed f o r absorbing, i n which continuous r e c y c l i n g and replacement of i r o n oxide is n o t r e q u i r e d . The process described h e r e i n i s designed t o remove H2S from r a w producer gas above l,lOOF by passing it through a f i x e d bed of f l y ash-iron oxide absorbents. The H2S r e a c t s with t h e Fez03 t o form FeS and FeS.. When t h e absorbents are f u l l y s u l f i d e d , t h e FeS-FeSp i s e a s i l y r e t u r n e d t o Fez03 by p a s s i n g air through t h e bed f o r a s h o r t period. MATERIAL, EQUIP!CQTT AND PROCEDURES
Fly ash from a c o a l - f i r e d powerplant n e a r Korgantown, West V i r g i n i a , w a s used e x c l u s i v e l y as supporting m a t e r i a l for t h e f l y ash-iron oxide absorbents. T h i s f l y a s h w a s similar t o t h e f l y ash from t h r e e o t h e r l o c a l sources. A t y p i c a l a n a l y s i s

of t h e f l y ash was: s i o , - 5 1 . 7 ~ , A l 2 0 ~ 2 4 . 6 5 , Feros-15.95, cao-3.065, 1&0-2.385, The GET s u r f a c e a r e a w a s 0.95 mz/ MgO-0.945, Ti02-0.84%, 11a,0-0.66~, and P20,-0.34$. gm. The f l y ash was d r i e d and screened t o remove agglonerates b u t w a s not otherwise processed. The i r o n oxides used were F i s h e r C e r t i f i e d o r I4CB Technical Grade with BFT s u r f a c e areas of 10 and 8.5 m Z / @ r e s p e c t i v e l y . (These i r o n oxides were used t o maintain c o n s i s t e n t d a t a throughout t h e i n v e s t i g a t i o n s . Commercial i r o n oxides w i l l b e used f o r l a t e r tests. ) Laboratory grade, high-swelling b e n t o n i t e ( 2 grams t o 24 m i l l i l i t e r s ) o f 632 S i 0 2 and 19%A120s c o n t e n t , and t e c h n i c a l grade 40-42O Baume (3.22 SiOr/NaaO) sodium s i l i c a t e s o l u t i o n , were used as a d d i t i v e s t o improve p h y s i c a l s t r e n g t h . The d r j i n g r e d i e n t s were thoroughly mixed using a s p l i t - s l e e v e mixer, then t r a n s f e r r e d t o a s m a l l p o r t a b l e - t y p e cement mixer. Water w a s added t o t h e mixture t o o b t a i n c o r r e c t consistency f o r e x t r u s i o n . The e x t r u s i o n apparatus produced 3/16inch diameter by 3/4-inch l o n g e x t r u d a t e s through a m u l t i p l e d i e arrangement a t t h e end of a 2-inch diameter by 6-inch long b a r r e l and auger. The s o l i d e x t r u d a t e s were d r i e d , t h e n s i n t e r e d a t temperatures and times r e q u i r e d . The crush s t r e n g t h ( f o r c e a p p l i e d a c r o s s t h e d i a m e t e r ) was measured on a Tinius-Olsen t e s t i n g machine. Figure 1 i s a flowsheet o f t h e equipment used t o conduct absorption and r e g e n e r a t i o n experiments with t h e i r o n oxide-fly ash absorbents. An entrainment carbonizer, used i n p r e v i o u s c o a l carbonization r e s e a r c h ( 5 ) was adapted t o simulate on a s m a l l s c a l e t h e production of h o t , raw producer gas ( c o n t a i n i n g c o a l - r e l a t e d t a r s and p a r t i c u l a t e s ) o r c l e a n , hot producer gas. Various gases t o make up t h e producer gas were supplied from b o t t l e d gases metered i n t o a manifold and i n t o t h e gas prehe&t.ter. Water w a s metered and i n j e c t e d i n t o t h e gas p r e h e a t e r t o simulate t h e amount of steam i n a c t u a l producer gas. When tars and p a r t i c u l a t e s were required i n t h e experiment, c o a l was f e d i n t o t h e carbonizer by a screw-type f e e d e r . The coal e n t e r e d t h e t o p of t h e carbonizer, 4-inch diameter by 18-inches high which was e l e c t r i c a l l y h e a t e d , and w a s charred as it f e l l through; char and ash were removed through a l o c k hopper at t h e bottom. The o u t l e t gas contained t a r s , l i g h t o i l s , and p a r t i c u l a t e s and t h e gas make up was s i m i l a r t o a c t u a l producer gas. Eighty percent of t h e t o t a l gas passed through t h e absorption bed; t h e o t h e r 20% provided a sample of t h e input f o r a n a l y s i s . The absorption v e s s e l was 2-inches i n s i d e diameter by 45-inches long. A s t a i n l e s s s t e e l screen 31-inches down from t h e t o p supported t h e absorbent bed. The v e s s e l was e x t e r n a l l y heated by high temperature h e a t i n g t a p e s . Both the v e s s e l and heating t a p e s were covered with i n s u l a t i o n t o prevent excessive heat l o s s e s . Five i n t e r n a l thermocouples were used t o monitor bed temperatures. The i n p u t gas sample system c o n s i s t e d of a h e a t e d ' d u s t f i l t e r , an e l e c t r o s t a t i c P r e c i p i t a t o r , a water-cooled condenser, a s i l i c a g e l t r a p and a dry gas meter. The input gas w a s analyzed f o r IIzS only using t h e Tutwiler method ( 6 ) . The gas sample system following t h e a b s o r p t i o n bed was i d e n t i c a l t o t h e i n p u t sample system except t h e gas stream passed through a bank of i n f r a - r e d gas a n a l y z e r s and w a s analyzed f o r C o , C O z . CHu and H 2 . H z S w a s a g a i n analyzed by t h e Tutwiler method. On s t a r t - u p , t h e p r e h e a t e r w a s heated t o 95OoF and t h e carbonizer chamber preheated t o 1,300F. The absorbent bed w a s heated t o l,lOOoP before s t a r t i n g t h e absorption period. The gas flow w a s allowed t o proceed u n t i l a predetermined amount of H z S was found i n t h e gas p a s s i n g through t h e absorption bed, u s u a l l y 400 g r a i n s HzS Per 100 standard c u b i c f e e t of gas. The input H2S c o n c e n t r a t i o n , as near as p o s s i b l e , w a s maintained at a l e v e l decided upon before t h e s t a r t o f t h e experiment. HzS concentrations much higher than normal producer gas were used t o shorten t h e time r e q u i r e d t o complete an experiment. Results have been c r o s s checked with those

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made with producer gas Ii2S concentrations and no major d i f f e r e n c e s i n r e s u l t s were obtained. Total gas flow throuch t h e system v a r i e d with t h e experiment and ranged from 25 t o 35 scfh. When t h e predetermined 1i2S concentration w a s reached, t h e input gases were turned o f f and a nitrogen purp,e s t a r t e d . The system w a s purged f o r 30 minutes with nitrogen t o prepare t h e system f o r t h e regeneration c y c l e . Figure 2 is a flow diagram f o r t h e absorption t e s t s made u s i n g a 1,500 scfh s i d e stream from t h e LERC s t i r r e d , fixed-bed g a s i f i e r ( 7 ) . The gas was maintained at i t s e x i t temperature of l , l O O + by means o f e l e c t r i c h e a t e r s and i n s u l a t i o n surrounding t h e pipe. The hot gas was broueht i n t o contact with t h e i r o n oxide-fly ash absorbents i n R 6-inch d i a n e t e r , k f o o t h i c h s t a i n l e s s s t e e l absorber equipped with e l e c t r i c s h e l l h e a t e r s and i n s u l a t e d f o r temperature c o n t r o l . The s u l f i d e d absorbents were regenerated by introducing air a t 7O0F i n t o t h e 1-inch i n l e t of t h e absorber and p i p i n g t h e SO,-rich gas t o t h e s t a c k through t h e 1-inch e x i t l i n e . I n e r t gas was a l s o piped i n t o t h e absorber i n l e t f o r bed temperature c o n t r o l during r e g e n e r a t i o n . The complete system w a s maintained above l,OOOF t o prevent condensation o f t h e t a r which would a f f e c t the absorbents or plug t h e l i n e s t o and from t h e absorber. The absorber contained 7 3 pounds o f 3/16-inch diameter a b s o r b e n t s , composed of 25:; i r o n oxide and 755 f l y ash with 35, by weight, o f b e n t o n i t e added as a binder. A space v e l o c i t y ( s c f h gas/cu. f t . absorbent) of 1 , 9 0 0 was maintained throuehout t h e tests.
EXPERIbIENTU RESULTS

Four important c r i t e r i a must be met before an absorbent can be considered optimum f o r process c o n s i d e r a t i o n . The absorbent must b e p h y s i c a l l y s t r o n g t o w i t h s t a n d handling, loading and c y c l i c thermal degradation. The absorbent must have t h e necessary s u r f a c e area containing i r o n oxide p a r t i c l e s t o e f f e c t i v e l y r e a c t w i t h H2S and provide enough absorptive c a p a c i v j f o r economical o p e r a t i o n s . The absorbent should be regenerable so t h a t m a t e r i a l and replacement c o s t s are at a minimum. F i n a l l y , and equally important, t h e absorbent should have a s a t i s f a c t o r y l i f e expectancy.
\

Absorbents containing a d d i t i v e s such as b e n t o n i t e , sodium s i l i c a t e and magnesium s u l f a t e were prepared and t e s t e d f o r t h e i r e f f e c t on p h y s i c a l s t r e n g t h . The a d d i t i o n of b e n t o n i t e g r e a t l y increased both hardness and crushing s t r e n g t h . However, t h e a d d i t i o n of 35 b e n t o n i t e caused a sharp decrease i n IInS absorption c a p a c i t i e s . The d a t a , as shown i n Table 1, i n d i c a t e t h a t b e n t o n i t e does n o t adversely e f f e c t absorpt i o n capacity u n t i l 1.55 i s added and t h e l e s s e r amounts a r e e f f e c t i v e i n providing s t r e n @ h t o t h e absorbent. Sodium s i l i c a t e a l s o produced an e x t r u d a t e having a crush s t r e n g t h of approximately 7 0 pounds p e r one centimeter l e n g t h , as opposed t o around 16 pounds for a n u n t r e a t e d e x t r u d a t c , k-ithout a7preciable loss i n absorption capacity. On t h e o t h e r hand, t h e a d d i t i o n of magnesium s u l f a t e decreased t h e absorption capacity without b e n e f i t i n g t h e p!yrsical s t r e n g t h of t h e absorbent. The v a r i a b l e s e f f e c t i n g absorption c a p a c i t y t h a t were t e s t e d included p o r o s i t y , mount of i r o n oxide contained i n t h e absorbent and steam concentrations of t h e hot gas being desulfurized. Ten p e r c e n t , by weight, of ordinary s t a r c h w a s added t o and burned out from t h e f l y ash-iron oxide absorbent mixture t o determine i f a d d i t i o n a l p o r o s i t y could be obtained. This absorbent showed n e a r l y twice t h e absorption c a p a c i t y of t h e u n t r e a t e d absorbent, however, it d i d not develop t h e c r u s h s t r e n g t h observed e a r l i e r with a similar absorbent containing 1% b e n t o n i t e . A f t e r s i n t e r i n g f o r 2 hours, the absorbent showed a decrease i n absorption c a p a c i t y with very l i t t l e i n c r e a s e i n physical s t r e n g t h . By addinc varying amounts o f i r o n oxide mixed with f l y ash i n p r e p r i n g an absorbent mixture, it was found t h a t 252 i r o n oxide with 757 f l y ash showed t h e b e t t e r absorption capacity. When 332 i r o n oxide was used, a s i g n i f i c a n t decrease i n absorption capacity w a s noted ( 2 ) . I?hen 13;; i r o n oxide w a s used, t h e same s i g n i f i c a n t decrease was observed. I t i s believed t h a t p a r t i c l e s i z e d i s t r i b u t i o n o f t h e i r o n

2 30
oxide and f l y ash c o n t r o l s t h i s phenomenon. Another disadvantage of higher amounts of i r o n oxide was t h e lesser p h y s i c a l s t r e n g t h i n d i c a t e d by n o t i c e a b l e amounts of absorbent degradation during t e s t i n g while those a t l e s s e r percent were q u i t e r e s i s t a n t t o degradation. Abel ( 2 ) reported t h a t producer gas containing steam reduced t h e c a p a c i t y of t h e absorbent t o r e a c t w i t h IIzS. A t 1,500F t h e absorption capacity w a s reduced about 25% i n w e t (8%)simulated gas. This phenomenon is not s u r p r i s i n g s i n c e steam is a product o f r e a c t i o n i n t h e absorption of HzS. Tests performed under t h e present i n v e s t i g a t i o n s using improved absorbents a l s o showed reduced capacity. The water-gas s h i f t r e a c t i o n , CO + HzO = COz + Hz, occurred with t h e i r o n oxide-fly ash absorbent bed c a t a l y z i n g the r e a c t i o n t o show an approximate s h i f t of 2% f o r HZ and COZ. This e f f e c t may be b e n e f i c i a l when t h e end u s e is feed s t o c k f o r a methanation p l a n t since t h e Ha/CO r a t i o is brought c l o s e r t o t h e desired 3 t o 1 value f o r t h e dry COZ-free gas. Regeneration o f t h e s u l f i d e d absorbents v a s accomplished by using a i r o r mixtures of air and nitrogen. A i r r e g e n e r a t i o n a t 1 2 s c f h produced bed temperatures of 1,700 00 t o 1,900F i n t h e zone of regeneration. Lower flow rates reduced temperatures 1' 400F. Dilution o f a i r with n i t r o g e n had a similar e f f e c t .
A t 900F regeneration s t a r t e d immediately and proceeded r a p i d l y , depending on t h e space v e l o c i t y , t o completion. The higher t h e rate of air i n t r o d u c t i o n , t h a t i s , t h e g r e a t e r t h e flow of oxygen, t h e higher t h e temperature of regeneration. The temp e r a t u r e increased and. decreased r a p i d l y a s t h e zone of r e a c t i o n passed through t h e bed and it was not known how w c h damage t o t h e absorbent occurred a t high teEperatures f o r s h o r t durations. It was p o s t u l a t e d t o be around 1,800F but a s a f e r long-term maximum temperature f o r t h e absorbents should be 1,500F. The d i l u t i o n of t h e air with nitrogen was one method of c o n t r o l l i n g t h e maximum bed temperature without l o s i n g t i m e i n regeneration a t lower flow r a t e s . Figure 4 shows a t y p i c a l temperature prof i l e on regeneration using 1 2 s c f h a i r flow rate compared with using 1 2 s c f h a i r and 12 s c f h nitrogen o r a t o t a l of 24 s c f h flow rate. Number 1 thermocouple i s n e a r t h e i n l e t while 110. 5 thermocouple is l o c a t e d near t h e e x i t from t h e bed. TC-5 w a s c o n s i s t e n t l y lower i n a l l regenerations. This w a s b e l i e v e d t o have been caused by t h e p a r t i a l regeneration o f t h e bed by unreacted owgen from t h e main zone o f regene r a t i o n with possibly some c r e d i t given t o t h e endothermic r e a c t i o n between FeS and sO2. Elemental s u l f u r was found i n t h e e x i t p i p i n g and valves. I t would be produced according t o t h e following r e a c t i o n :

,1
i

3FeS

+ 2SO2

F e . 0 ~ + 2.552

S u l f u r balances c a l c u l a t e d u s i n g t h e HzS input versus SO2 i n t h e o u t l e t gas averaged about 95% recovery as S O a . S e v e r a l batches o f regenerated absorbents were analyzed f o r t o t a l sulfur after s e v e r a l c y c l e s o f absorption and regeneration and t h e s u l f u r : . content was found t o be less t h a n 1 This would i n d i c a t e t h a t v e r j l i t t l e s u l f a t e was formed at t h e high r e g e n e r a t i o n temperatures used. Regeneration was e s s e n t i a l l y completed i n 120 minutes when t h e a i r flow r a t e was 12 scfh. A t 6 s c f h , r e g e n e r a t i o n r e q u i r e d 190 minutes. A 1 t o 1 mixture of a i r and nit.rogen a t 24 s c f h flow r a t e r e q u i r e d a regeneration t i n e o f 150 minutes. Since t h e normal absorption c y c l e r e q u i r e d about 5 hours, enough time was a v a i l a b l e t o use any of t h e above flow rates. Aside from c r i t i c a l temperature design c r i t e r i a , another consideration w a s t h e SOz-enriclunent t h a t was needed f o r downstream conversion o r reduction. The SOz c o n c e n t r a t i o n i n t h e e f f l u e n t gas approximated 11?5-12$when using air f o r regeneration; however, when d i l u t i o n gas was used, t h e SOa concentration w a s proportionate t o t h e amount o f d i l u e n t used, being around 5k-h:; at 1 t o 1 d i l u t i o n of air with nitrogen. Typical regeneration curves, depicted by Figure 5 , showed t h a t maximum SO2 concentration w a s reached i n l e s s than 5 minutes and dropped from maximum t o b a s e l i n e i n approximately 20 minutes. These time f a c t o r s a r e noted f o r both a i r and d i l u t e d a i r r e g e n e r a t i o n schemes.

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The l i f e expectancy of a s p e c i f i c absorbent could only be determined with accuracy by continuous cycling u n t i l t h e absorption c a p a c i t y dropped below a c c e p t a b l e limits or degradation and fusion caused o p e r a t i o n a l problems. This was Costly i n terms of money and manpower. Iiowever, one absorbent bed has been through 30 absorption-regeneration c y c l e s using simulated producer Gas containing both c o a l - r e l a t e d tars and p a r t i c u l a t e s t o study t h e c y c l i c e f f e c t upon t h e absorbents. Absorbents used i n t h i s study were prepared by addinc lo$, by weight, of s t a r c h t o an absorbent miXtUre Containing 25: i r o n oxide and 755 f l y ash. The absorbent w a s s i n t e r e d a t 1,800F f o r 30 minutes i n an oxidizing atmosphere. The producer gas was naintained a t l,lOOoP throughout t h e absorption cycle at an average flow rate of 15 S C f h . The HzS concentration i n t h e i n l e t gas stream was maintained at 2% and t h e steam content between 7 and u , . :' Regeneration a f t e r each absorption cycle w a s accomplished by u s i n g a 12 S C f h a i r flow r a t e f o r approximately 2 hours. The average absorption c y c l e l a s t e d 5 hours. Figure 3 i n d i c a t e s t h e absorption c a p a c i t y of each cycle. The i n c r e a s i n c absorption c a p a c i t y throu&h t h e f i r s t few cycles w a s believed due t o t h e r e s u l t of burn-out of t h e r e s i d u a l s t a r c h during regeneration where temperatures approached 1,%OF f o r s h o r t periods. The continuing starch-char burnout would open more pores f o r b e t t e r g a s p e n e t r a t i o n t o t h e i r o n oxide p a r t i c l e s i n t h e absorbent. After 30 c y c l e s , t h e absorbent was i n good condition without v i s i b l e signs of d e t e r i o r a t i o n o r caking. Table 2 l i s t s 6 of t h e 30 runs which were r e p r e s e n t a t i v e of t h e t y p i c a l information computed from t h e raw d a t a obtained during operations. Abel ( 2 ) e a r l i e r reported t h a t s i n t e r e d p e l l e t s containing 25% i r o n oxide and ( l , O O O o - l ,5OO0F), c l e a n simulated producer gas without v i s i b l e damage t o t h e p e l l e t s o r appreciable l o s s i n absorptive a c t i v i t y . The absorption c a p a c i t y averaged 85 f o r t h o s e t e s t s conducted a t l,lOOF. The pore volume reached a constant value of 0.12 cubic centimeters per gram after 30 absor2tion-regeneration cycles.

75s f l y ash underwent 174 absorption-regeneration c y c l e s using hot

Four 15-hour absorption runs were completed using a 1 , 5 0 0 s c f h sidestream of h o t (l,lOOF) r a w producer gas made by g a s i f y i n g high v o l a t i l e bituminous coal with a i r and steam i n a 42-inch s t i r r e d , fixed-bed e a s i f i e r ( 7 ) . These runs were made p r i m a r i l y t o demonstrate t h e f e a s i b i l i t y of t h e process a t much higher gas flow r a t e s and a t a c t u a l process conditions. The four 15-hour runs were com9leted s u c c e s s f u l l y IIinety t o 945 o f t h e Has was w i t h an average absorption capacity of 6.25 wt.-pct. removed f r o m t h e hot producer gas which averaced 0.5" H . e n t e r i n g t h e absorber. S Table 3 shows t h e d a t a and run conditions f o r t h e 11 periods. The absorbents remained i n good condition f o r t h e duration of t h e t e s t s and were not adversely a f f e c t e d by t h e tars and p a r t i c u l a t e s i n t h e e f f l u e n t eas. The t a r s could be t o l e r a t e d i f t h e absorber bed temperature remained above l,OOOor. The f i n e carbonaceous p a r t i c u l a t e accumulated i n t h e absorber bed during absorption w a s burned o f f during t h e regenera t i o n cycle. An i n s i g n i f i c a n t amount o f ash r e s i d u e remained i n t h e bed after regene r a t i o n which w a s determined by v i s u a l i n s p e c t i o n of t h e bed a f t e r completion o f t h e 4 cycles. Pressure drop across t h e bed increased t o 8-9 p s i g at t h e end of t h e absorption periods but returned t o 1 . 5 p s i g a f t e r regeneration of t h e absorbent bed.

coIIcLusIoI:
The l a b o r a t o r y tests conducted t h u s f a r i n d i c a t e t h a t t h e f l y ash-iron oxide absorbent containing b e n t o n i t e i s an adequate absorbent f o r removing H2S from raw producer gas at temperatures between l,OOOF and 1,500F. The p h y s i c a l s t r e n g t h , expressed as t h e c r u s h s t r e n g t h (measured a c r o s s t h e d i a m e t e r ) , of 50 t o 100 pounds per one centimeter of l e n g t h i s considered adequate t o withstand handling, t r a n s p o r t a t i o n and placement of t h e absorbents. The absorbent i s regenerable and has an average capacity of 1 0 wt.-pct. This amount o f absorptive capacity coupled w i t h an e f f i c i e n c y of 90-945 permits ample t i m e "on l i n e " and provides an e f f l u e n t gas which meets t h e e x i s t i n g environmental a i r standards.

T h i r t y and 174 absorption-reeeneration c y c l e s were completed without v i s i b l e d e t e r i o r a t i o n or loss of a b s o r p t i v e capacity. Although not conclusive, t h e s e t e s t s i n d i c a t e t h a t t h e absorbents could withstand many more c y c l e s . Eventual pore closing by *ion due t o long time thermal c y c l i n g and/or micron s i z e p a r t i c u l a t e exposure needs t o be i n v e s t i g a t e d f u r t h e r . These two occurrences would be t h e most l i k e l y l i m i t i n g f a c t o r s on l i f e expectancy of t h e absorbents. Laboratory work is now being performed t o f i n d a s u i t a b l e s u b s t i t u t e for t h e fly ash so t h a t higher temperatures and f a s t e r regeneration w u l d be permissible. Finding cheaper sources of i r o n oxide and comparing r e s u l t s of t h e s e oxides should be i n v e s t i g a t e d so t h a t a v a i l a b i l i t y of i r o n oxide would be assured. F i n a l l y , a p i l o t p l a n t hot gas cleanup f a c i l i t y should be operated so t h a t its f e a s i b i l i t y for commercial a p p l i c a t i o n would be demonstrated along with hardware development and scale-up design c r i t e r i a e s t a b l i s h e d . REFELlENCES
I'

1 Reeve, L. D e s u l f u r i z a t i o n of Coke-Oven Gas at Appleby-Frodingham. J. I n s t . . Fuel. vol. 31, No. 210, July 1958. pp. 319-324. 2. Abel, W. T., F. C. S h u l t z , and P. F. Langdon. Removal of Hydrogen S u l f i d e from Hot Producer Cas by S o l i d Absorbents. BuMines R I 7947, 1974, 23 pp. 3. S h u l t z , F. 0. Removal of Hydrogen S u l f i d e from Simulated Producer G a s a t Elevated Temperatures and Pressures. Proc. 2d I n t e r n a t i o n a l Conf. on Fluldired-Bed Combustion, Hueston Woods S t a t e Park, College Corner, Ohio, Oct. 4-7, 1970. U.S. Environmental Protection Agency, Office of A i r Programs, 1972, pp. II1-5-1--111-5-5. 4. Clay, D. T. and S c o t t I g m . Iron-Catalyzed Reduction of NO by CO + H s in Simulated Flue Cas. General Motors Symposium on NO Reduction, Oct. 7-8, 1974. 5. B e l t , R. J. and M. M. Roder. "Low S u l f u r Fuel by Pressure Entrainment Carbonization of Coal," Chap. 1 , pp. 121-134. P o l l u t i o n Control and Energy 1 Needs, R. M. Jimeson and R. S. Spindt. Advances i n Chemistry S e r i e s 127-, ACS, Washington, D. C., 1973. 6. A l t i e r i . V. J. Cas Analyses and Testing of Gaseous M a t e r i a l s , American Gas ASSOC.. New York, 1st E d i t i o n , 1945. pp. 339-340. 7. Oldaker, E. C., A. M. Poston, and W. L. F a r r i o r . Removal of Hydrogen S u l f i d e from Hot Low-Btu Cas w i t h I r o n Oxide-Fly Ash Sorbents. MERC/TPR-75/1, Feb. 1975.

233
TABLE 1.

E f f e c t of Bentonite on Absorption Capacity of Fly AshI r o n Oxide Absorbent Using Apparatus Shown i n Figure 1

S absorption

Bentonite, percent

Cas flow rate, std. cu.ft./hr.

RUII

Space

Total

duration, h - r. -

0.5
1.0

17.19
15.30

4.11

5.75 4.52 3.15

454

11.9

1265

11.70 10.5 (1.20 97.2 94.1

1.5
3.0

14.27 17.58

Absorption temperature l,lOOF S a t u r a t i o n p o i n t -- 400 grains/100 s c f Weight of absorbent 700 grams

--

--

TABLE 2.

Typical Data from Six of ThirtyAJbsorption Capacity Tests (Figure 1) Using Same Fly Ash-Iron Oxide Absorbent . . Containing 1 0 Percent S t a r c h

Gas flow r a t e , std. cu.ft./hr.

HzS absorption Run Space duration, velocity, Gf f i ciency hr. vol/vol/hr g r a i n s w t . - p t . pct.

_. -

-.___-

Total quantities through bed

14.27 15.97 16.37

16.38

6.28 5.75 5.75 5-50 6.00 7.25

501 563
570

1118
1133 1100

10.35
11.04

92.5 95.0 93.5

?3.1

31.5.

10.92 10.51
10.73

20.2 33.5

587 529 549

1135 1159
1332

15.23 '15.09

94.2 92.2

12.33

: z 1 ::

.5

Absorption temperature l,lOOF S a t u r a t i o n break-through point Weight o f absorbent -- 700 grams

--

--

400 gr/100 s c f

234

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235

'\

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l 4 V D R W f I SULFlDf NETHAHE . CARBON IONOXIOf CARBON OlOXlOf

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* * *

Figure 1.

- Flow Diagram of

ApparatuI Measuring Absorption Capac it

To flare stack

!
,

Figure 2 .

Flow Diap.ram of Apparatus f o r Testing S o l i d Absorbents Using Hot Producer Gas

2 36

161 I
I

z
4K

1
I

RUN NUMBER

Figure 3.

Absorption Capacities Achieved During T h i r t y A ~ s o r p t i o n - R e R e n e r a t i o ~ ~ e s t Using t . Runs Same Absorbent, with Operating Conditions L i s t e d i n Table 2

2.000
Y

1.800

J
a 1,600

1,000

30

60 90 120 TIME, minutes

150

180

Figure 4.

Comparison of Bed Temperature P r o f i l e s T i t h and Without D i l u t i o n Gas f o r Regeneration of Sulfided Absorbents

_ _ I _ _

14

12

10

I
I

Lo - Averaged data for nine runs

I
I

I I
I

-Regenerating air - 1 2 scfh

30 60 90
120

I I

I
150

0
i

180

TIME, minutes

Figure 5 .

Typical Curve Sliowini;-,PX2 Concentration int- .e _ _ h _ Lffluent Gas Durinf _._ ReLenerntion - -I - _ _ of t h e Dulfided Absorbents

__-

238
INVESTIGATIONS ON THE REmVAL OF HYDROGEN SULFIDE AT HIGH TEMPERATURE FROM COAL GAS Keshava S . Murthy B a t t e 1l e ' s Columbus Labor a t o r i e s 505 King Avenue Columbus, Ohio 43201

WHY HOT-GAS CLEANUP?

At c u r r e n t consumption l e v e l s , proven U.S. n a t u r a l gas r e s e r v e s a r e e s t i mated t o last 8 y e a r s . ( l ) * G a s i f i c a t i o n of oils w i t h n e g l i g i b l e s u l f u r content i s not f e a s i s i n c e t h e U.S. o i l supply, slowly dwindling, i s s u f f i c i e n t f o r only 10 years.?'! Thus, i f continued gas supply i s d e s i r e d , c o a l g a s i f i c a t i o n may be t h e only immdiately f e a s i b l e a l t e r n a t i v e . Lurgi and Kopper-Totzek (K-T) g a s i f i e r s a r e among t h e o l d e r c o m r c i a l l y proven processes. The Lurgi process produces low- or medium-Btu gases contaminated with varying amounts of s u l f u r compounds such a s hydrogen s u l f i d e (H2S) and carbonyl s u l f i d e (COS). The Lurgi gas is a t a higher p r e s s u r e (350 p s i ) and lower temperat u r e (750 t o 1100 F depending on c o a l type) than K-T gas which i s a t 1 atmosphere and 2500 F. Both processes produce gas with a heating value (HHV) of 300 Btu/scf when u s i n g oxygen. The Lurgi process can a l s o produce a 180 Btu/scf gas when a i r blown. These medium- and low-Btu gases can be used i n many ways. The highpressure-low-temperature Lurgi gas, a f t e r removal o f i t s H2S, t a r , and d u s t content is w e l l suited f o r s y n t h e s i s of methane t o produce s u b s t i t u t e n a t u r a l gas (SNG). Also, because of i t s high p r e s s u r e , t h e gas can be d e s u l f u r i z e d by any of t h e est a b l i s h e d wet processes, although t h i s r e q u i r e s cooling t h e gas t o 200 F o r -50 F , depending on t h e l i q u i d scrubbing process chosen. In c o n t r a s t , i f t h e gas is des u l f u r i z e d and cleaned u n t i l f r e e of p a r t i c u l a t e s a t c l o s e t o t h e g a s i f i e r e x i t temperature, t h e s e n s i b l e heat of t h e gas can be u t i l i z e d t o e f f i c i e n t l y generate e l e c t r i c power i n a combined-cycle power p l a n t or t o avoid t h e l a r g e heat-exchange hardware requirements i n a SNG production scheme. The K-T gas, a t atmospheric pressure and 2500 F , needs compression t o 450 psig and coaling before t h e wet d e s u l f u r i z a t i o n and subsequent methanation s t e p s i f SNG i s t h e desired product. The p r i o r compression and cooling may be less a t t r a c t i v e compared with t h e d i r e c t u t i l i z a t i o n of t h e K-T gas in a power p l a n t b o i l e r i f a means can b e found t o d e s u l f u r i z e and c l e a n t h e crude gas a t near g a s i f i e r e x i t temperature. In t h e l a t t e r e v e n t , t h e s e n s i b l e h e a t of t h e medium-Btu gas (45 Btu/scf o r 15 percent of i t s h e a t i n g value) could b e u s e f u l l y employed. The K-T g a s i f i e r can g a s i f y any type of s o l i d f u e l (caking c o a l s , c h a r s , petroleum coke, t a r , o i l s , and s l u r r i e s ) and has quick s t a r t u p and shutdown c a p a b i l i t i e s . The K-T g a s i f i e r i s expected t o b e a s u i t a b l e source of f u e l gas t o many power p l a n t s in western United S t a t e s now using n a t u r a l g a s ; t h e r e t r o f i t d i f f i c u l t i e s a r e estimated t o be minimal. I f t h e e l e c t r i c u t i l i t y i n d u s t r y and other i n d u s t r i a l markets now using over 65 percent of t h e n a t u r a l gas supply convert t o low-Btu gas, about 5 t r i l l i o n cu f t ( 3 5 p e r c e n t ) of n a t u r a l gas would be freed f o r o t h e r u s e s . ( l ) Doubtless, t h e K-T gasifier--hot-gas-cleanup approach needs t o compete with t h e emerging f l u e - g a s d e s u l f u r i z a t i o n (FGD) processes which permit t h e use of s u l f u r containing c o a l . C u r r e n t l y , t h e F D processes generate l a r g e volumes of G secondary wastes, including sludges and l i q u i d purge streams. A d e t a i l e d evaluation of F D versus t h e K-T gasifier--hot-gas-cleanup system may demonstrate t h e l a t t e r G

References a r e l i s t e d a t t h e end.

239
I

approach t o be favorable, s i n c e it does not produce s i g n i f i c a n t secondary wastes; t h e choice could be largely s i t e s p e c i f i c . I f hot-gas-cleanup systems can be developed t o remove s u l f u r compounds i n crude gases, t o l e s s than t h e 0.1-ppm l e v e l , they may a l s o be a p p l i c a b l e t o the SNG production processes. S i g n i f i c a n t savings appear p o s s i b l e by e l i m i n a t i n g t h e cooling s t e p or minimizing t h e degree of cooling and heat exchange.
T h e above arguments suggest t h a t t h e development of a hot d e s u l f u r i z a t i o n process has merit. Also, a s evidenced i n t h e development of F D processes and t h e i r G wide but slow acceptance, a f a c t o r t h a t favors t h e development of new systems is t h a t when a well-proven system e x i s t s , t h e b e s t use w i l l be made of i t . The Energy Research and Development Admin's r a t i o n (ERDA) has been i n v e s t i g a t i n g hot-gas H2Sremoval techniques s i n c e 1967.t2f Others independently involved i n t h e study a r e t h e University of Kentucky ( s i n c e 1972), A i r Products and Chemicals, Inc., and Conoco. B a t t e l l e ' s work began i n 1974 a s a r e s u l t of funding under t h e B a t t e l l e Energy Program" i n i t i a t e d e a r l y i n 1973. This paper d e s c r i b e s t h e r e s u l t s of t h e B a t t e l l e i n v e s t i g a t i o n s on t h e development of sorbents f o r removal of H2S a t high temperature from c o a l gases.

EXPERIMENTAL FACILITY T h e B a t t e l l e experimental f a c i l i t y i s presented i n Figure 1. It c o n s i s t s of a gas-mixing s e c t i o n , a p r e h e a t e r , and a fixed-bed t u b u l a r g l a s s r e a c t o r . Both t h e r e a c t o r and preheater operate i n t h e range 100 t o 1800 P, and p r e c i s e c o n t r o l of temperature of t h e gas and sorbent bed i s p o s s i b l e . The p r e h e a t e r and reactor used a r e made of c l e a r quartz t u b e , 50-rmn I D . Quartz was chosen a f t e r s t a i n l e s s s t e e l r e a c t o r s (Types 304 and 446) were found t o r e a c t severely with H2S. No p a r t i c u l a r hazard was observed with t h e o p e r a t i o n of t h e u n i t when t h e gases were properly scrubbed and vented.

EXPERIMENTAL PROCEDURES

C e r t i f i e d standard gas mixtures** were used t o obtain simulated c o a l gas of t h e following composition i n volume percent: H , 1 7 ; CO, 26.0; C O , 5.0; N p , 50.5; and H S, 1.5. T h e l a r g e amount of n i t r o g e n suggeszs simulation of a ?ow-Btu gas obt a i n e i by air-blown process. The gas does not resemble any a c t u a l producer gas e x a c t l y ; the H 2 S content i s r a t h e r high and a l s o f r e e of t h e u s u a l moisture, t a r , and dust present i n a c t u a l c o a l gases. The r a t i o n a l e f o r choice of t h i s composition w a s t h a t B a t t e l l e s t u d ' e were designed t o generate d a t a f o r comparison with t h e res u l t s of ERDA studies.t2f A gas chromatographic a n a l y s i s confirmed t h a t actu.al gas composition was c l o s e t o t h e desired values. Matheson flow c o n t r o l l e r s were h e l p f u l

* Research

described here was supported by The B a t t e l l e Energy Program (BEP). T h e Program has been e s t a b l i s h e d t o c a r r y out major R&D e f f o r t s aimed a t developing p r a c t i c a l s o l u t i o n s t o some of t h e extremely s e r i o u s energy s h o r t a g e and u t i l i z a t i o n problems expected t o e x i s t i n the United S t a t e s during 1975-1995. Battelle Memorial I n s t i t u t e has a l l o c a t e d m i l l i o n s of i t s m funds t o support t h i s e f f o r t . because of the importance of t h e energy problem t o t h e nation. The primary emphasis of BEP is on t h e development of c o a l as a c l e a n f u e l source s i n c e coal holds the g r e a t e s t promise f o r f i l l i n g t h e gap between the U.S. energy requirements and the a b i l i t y t o meet these requirements in t h e t i m e period of i n t e r e s t . Additional energy sources being i n v e s t i g a t e d under t h e program i n c l u d e s o l a r energy. Matheson Gas Products, J o l i e t , I l l i n o i s , was t h e vendor.

fi

240

FIGURE 1.

FLOW DIAGRAM OF THE HIGH-TEMPERATURE H2S-REMOVAL ASSEMBLY

24 1
i n maintaining flow accuracy and p r e c i s i o n t o w i t h i n 2 3 percent on t h e t o t a l flow. H2S was fed as a 2 5 percent gas mixture i n n i t r o g e n and t h e H2S i n t e s t gas was 950 grains/100 scf with a p r e c i s i o n of 210 g r a i n s .

H S i n t h e i n l e t and o u t l e t streams was measured by t h e T u t w i l e r method. ( 3 ) 2 The method c o n s i s t s of grab sampling 100 cc of t h e gas i n a g l a s s bulb connected t o a b u r e t t e containing standard iodine s o l u t i o n . The gas, c o l l e c t e d over s t a r c h solut i o n , is t i t r a t e d with t h e iodine to a blue end p o i n t . Each m i l l i l i t e r of the iodine s o l u t i o n (prepared by d i l u t i n g 13.5 m l of 0.1 N s o l u t i o n t o 100 m l w i t h d i s t i l l e d water) i s equivalent to 100 g r a i n s of H S/100 scf of gas. The method can d e t e c t H2S a s low as 2 grains/100 s c f of gas, or 33 ppm of H S . 2
The quartz preheater and r e a c t o r were packed with quartz wool t o provide The t e s t s o r b e n t , 100-gram charge, was supported on a honeycomb s t r u c t u r e made of quartz tube t o provide even gas d i s t r i b u t i o n . The sorbent bed was located +-2 inches about t h e c e n t e r of t h e r e a c t o r ' s length. The thermocouple t i p was about 0.5 c m above t h e bed. The temperature p r o f i l e through t h e bed i n d i c a t e d t h a t t h e bed was n e a r l y uniform i n temperature, and t h e gas entered and e x i t e d the bed a t n e a r l y t h e r e a c t i o n temperature. A 12-point r e c o r d e r provided temperature readout.

a h e a t - t r a n s f e r surface.

To insure a proper b a s i s f o r comparison of r e s u l t s on sorbent performance, t h e experiments were performed a t uniform o p e r a t i n g conditions (1500 F r e a c t i o n tempe r a t u r e , cold gas flow of 1 l i t e r / m i n . a t 7 0 F and 14.7 p s i a and 950 g r a i n s H2S/100 s c f ) . The cold-space v e l o c i t y was 600 gas volumes per volume of bed per hour, equival e n t t o an operating GSV of 2000 V / V / h r varying s l i g h t l y with bed volume. The acceptance run was terminated when t h e o u t l e t - g a s H S c o n c e n t r a t i o n approached 100 g r a i n s a t an i n l e t - g a s H 2S content of 950 g r a i n s . T i e r e g e n e r a t i o n run was ended when t h e s u l f u r dioxide i n t h e regenerator gas dropped from 6 volume percent t o 0.05 percent. S u l f u r dioxide was a l s o measured by t h e Tutwiler method. A f t e r one c y c l e of acceptance and regeneration, t h e sorbent was subjected t o s i e v e a n a l y s i s t o determine attrition. SORBENT PREPARATION Sorbents were prepared u t i l i z i n g CP o r reagent-grade chemicals. These, a s d r y powder (-200 U.S. s i e v e ) , were weighed and mixed together with 1 gram each o f s t a r c h , bentonite, and sodium s i l i c a t e per 100 grams of t h e mixture. The r e s u l t i n g mix was made i n t o a p a s t e w i t h d i s t i l l e d water. The p a s t e was e i t h e r p e l l e t i z e d o r extruded. The p e l l e t s , a f t e r oven-drying a t 250 F , were s i n t e r e d a t 1800 F (or 1600 F) f o r 2 hours. The s i n t e r e d p e l l e t s were screened t o - 6 + 10 U.S. s i e v e mesh. The e x t r u d a t e s (1/8 inch i n diameter and about 1 / 4 inch long) were a l s o d r i e d and s i n t e r e d s i m i l a r l y and screened t o remove a l l minus 10-mesh p a r t i c l e s . The sorbent was f r e e flowing and reasonably strong. The average d e n s i t y was about 0.9 cc/g. EXPERIbENTAL RESULTS AND DISCUSSION A s a f i r s t s t e p , f i v e blank runs were performed with t e s t gas. The rea c t o r was not charged with sorbent. R e s u l t s with Type 304 s t a i n l e s s s t e e l and o t h e r r e a c t o r m a t e r i a l s (Table 1) show t h a t s t a i n l e s s s t e e l s a r e u n s u i t a b l e as experimental r e a c t o r s but t h a t quartz r e s i s t s H S a t t a c k s a t i s f a c t o r i l y . The steel r e a c t o r walls 2 flaked o f f and thermocouple wells were damaged by corrosion.

b
\

1'

242

TABLE 1.

TEST RESULTS WITH BLANK REACTOR

Parameter Diameter ( I D ) , inches

Stainless Steel Type 304 Type 446 1.26 16.0 750 2.0 16.0 750

Quartz

2.1
16.0

Length of Hot Zone, inches G a s Flow R a t e A t 70F, 1 A t m , cm3/min

1000
0 5

H S absorbed, percent -_- innn 3 A t 1500 F

I+ _---

8
90
15 90

T e s t D u r a t i o n , hours A t 1000 F A t 1500 F

27

10

3 4

(a) During t h e f i r s t 11 hours, t h e removal was 99.5 percent; a g r a d u a l drop t o 15 percent occurred i n t h e next 4 hours. A t 1500 F , no s i g n i f i c a n t r e d u c t i o n i n removal w a s observed.

243
H2S Acceptance Experiments

With t h e quartz r e a c t o r (using quartz thermocouple w e l l s ) , 2 1 experiments were conducted t o study t h e H2S acceptance-regeneration c h a r a c t e r i s t i c s of t h e 11 sorbents l i s t e d in Table 2. The USBM sorbent was provided by t h e Morgantown Energy Research Center (ERC)." The f l y ash used i n t h e sorbent contained approximately 52 percent S i O 2 , 25 percent Al2O3, 15 percent FepO3, w i t h t h e remainder being CaO, NO, K20, e t c . ( 4 ) This sorbent w a s s t u d i e d i n four experiments t o e s t a b l i s h basel i n e performance d a t a a t 1500 F s i n c e t h e reported d e s u l f a c i t y w r e s u l t s obtained with s t a i n l e s s steel reactors(21 were suspected t o be t o o high.

A comparison of d a t a reported by USBM (now ERDA) with those obtained i n BCL s t u d i e s (Table 3) f o r t h r e e sorbents, including f l y a s h - - i r o n oxide sorbent, ind i c a t e s t h a t t h e influence of H S uptake by t h e r e a c t o r at 1500 F i s a s i g n i f i c a n t f a c t o r i n the reported d e s u l f a c2 t y r e s u l t s . Contrary t o a reported i n c r e a s e i n dei s u l f a c i t y a t higher temperature, t h e BCL d a t a e s t a b l i s h t h a t a s i g n i f i c a n t l y higher H s removal occurs a t 1000 F than a t 1500 F. Thermodynamic c o n s i d e r a t i o n s support tiese d a t a in t h a t t h e predicted equilibrium conversion i s high (approaching 100 per. c e n t ) a t temperatures of 1000 F and higher. This i s modified by t h e f a c t t h a t t h e r e a c t i o n i s exothermic, h e p g lower temperatures permit a c t u a l r e a l i z a t i o n of t h e p r e d i c t e d high conversion.
The d a t a i n Table 3 a l s o i n d i c a t e a s i g n i f i c a n t l y low e x i t H S c o n c e n t r a t i o n f o r a l l sorbents containing component X (used i n BCL sorbents) a t a l l Zemperatures. Also, BCL experiments show t h a t pure i r o n oxide a t 1000 F permits a very low exit-H S 2 concentration. I n c e r t a i n a p p l i c a t i o n s of c o a l gas, t h e low H S l e v e l may be an advantage. A graphical comparison of t h e low e x i t H S concentragion of v a r i o u s sor2 b e n t s i s presented i n Figure 2 . Regeneration R e s u l t s A comparative p l o t of t h e r e g e n e r a t i o n curves of v a r i o u s s o r b e n t s i s presented i n Figure 3. A l l of t h e s e experiments were performed a t uniform conditions of 1 l i t e r / m i n u t e of a i r inflow a t 70 F, 1 atm,.and 1000 F sorbent bed temperature. The d a t a do not provide conclusive evidence on comparative r e g e n e r a t i o n c h a r a c t e r i s t i c s of t h e sorbents. T h i s i n d i c a t e s t h a t t h e need f o r f u r t h e r experimentation i s more pronounced i n t h e a r e a of regeneration than i n t h e a r e a of H2S acceptance. The major ambiguity is i n r e f e r e n c e t o Curves 5 and 6 f o r t h e r e g e n e r a t i o n of sorbent BCL 29 E . These two curves, which should have been c l o s e l y s i m i l a r because of r e p l i c a t i o n of t h e same experiment, a r e obviously very d i f f e r e n t . However, while t h e sorbent i n Curve 5 was regenerated immediately a f t e r t h e end of t h e acceptance run (with no overnight cooling of t h e sulfided s o r b e n t ) , t h e sorbent i n Curve 6 w a s cooled overnight between t h e acceptance and r e g e n e r a t i o n runs. Neither of t h e s e occurrences was d e l i b e r a t e . Although t h e reasons f o r t h e s u p e r i o r regeneration c h a r a c t e r i s t i c s of Curve 5 a r e not c l e a r , t h i s curve r e p r e s e n t s a d e s i r a b l e r e g e n e r a t i o n t r e n d . The 3 percent SO2 i n e x i t gas f o r over 5 hours followed by a sudden c o n c e n t r a t i o n drop should help i n f u r t h e r processing of t h e SO -bearing gas t o e i t h e r s u l f u r i c acid or 2 s u l f u r . The s u l f u r balance, based on 23.7 grams of H S absorbed by t h e s u l f i d e d

* **

Courtesy of Ernest Oldaker, E R G , ERDA, Morgantown, West V i r g i n i a . Desulfacity is defined as grams of H S removed from t h e gas by 100 grams of sorbent charge, o r weight percent H2z-removal c a p a c i t y e i t h e r a t breakthrough or when e x i t gas H2S concentration reaches 100 grains/100 s c f .

244

TABLE 2.

LIST OF SORBENTS STUDIED

Siz

Sorbent Designation USBM #0074* BCL #8WB**

BCL 1/20 BCL P20E BCL # 2 1

-&lo

Pellet U.S. Sieve

Extrudate, 1/8" Diam., 1/4" Long

3/16" diam. x 1 / 2 " long

X X

X
X X

BCL 1/23
BCL #25E

BCL #26E
BCL #27E

X X X X X

BCL #28E
BCL #29E

U.S. Bureau of Mines Sorbent Batch No. 0074 c o n t a i n s 75 percent f l y ash and balance i r o n oxide.
BCL ( B a t t e l l e Columbus Laboratories) Sorbents. The composition of these Sorbents a r e withheld f o r prop r i e t a r y reasons.

**

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100scf

USEM 0074, Curve I BCL 20, Curve 2

ECL 29 E, Curve 7

Time of

H2S Acceptance Run, hours

I$S

FIGURE 2 .

- ACCEPTANCE CURVES

USBM 0074, Curve I

BCL 21. Curve 2

ECL 29 E , Curve

ECL 2 0 Curve

30

60

90

120 150 180 2 0 240 1 Regenerotion Time, rnlnutes

270

XX)

FIGURE 3 .

SORBENT REGENERATION CURVES

For these runs, %S acceptance temperature was 1000 F, w h i l e f o r the remaining, i t was 1500 F. A l l r e g e n e r a t i o n runs were done a t 1000 F. Gas and a i r flow r a t e s and a l l o t h e r c o n d i t i o n s were t h e same f o r a l l runs shown here. Also, Regeneration-Curves 5 and 6 a r e d i s c u s s e d on Page 6 .

247
sorbent, i n d i c a t e s t h a t 80 percent of t h e s u l f u r absorbed i s accountable i n t h e regenerator e x i t gas a s SO2. Also about 0.25 gram of s u l f u r was formed during regenerat i o n , thus accounting f o r another 1 percent of t h e s u l f u r . Sulfur balance c a l c u l a t i o n s f o r Curve 1 (USBM 0074) show t h a t 85 percent of t h e s u l f u r absorbed was accountable a s SO i n t h e r e g e n e r a t o r e x i t g a s . The formation 2 of s u l f u r i n t h e case of t h e sorbent represented by Curve 5 needs f u r t h e r e v a l u a t i o n t o determine whether d i r e c t s u l f u r formation is p o s s i b l e d u r i n g regeneration. S t u d i e s on Sorbent A t t r i t i o n

'

In an a c t u a l connnercial processing scheme, sorbent a t t r i t i o n i s an important property c o n t r i b u t i n g t o t h e r a t e of sorbent makeup required. I f a t t r i t i o n occurs during H2S removal, t h e c o a l gas w i l l c a r r y a d d i t i o n a l p a r t i c u l a t e load which may i n t e r f e r e with t h e u t i l i z a t i o n of t h e gas. I d e a l l y , an a t t r i t i o n loss of z e r o i s d e s i r a b l e . However, c a t a l y s t a t t r i t i o n - l o s s r a t e s of 0.3 w t % / h r (0.09 l b / b b l feed) i n f l u i d i z e d bed cracking a r e known t o be t o l e r a b l e . I n high-temperature c o a l gas d e s u l f u r i z a t i o n , an a t t r i t i o n loss o f , say, 1.0 l b / m i l l i o n s c f of gas t r e a t e d * may be perhaps t o l e r a b l e . It appears preferable t h a t such loss occur during r e g e n e r a t i o n . In t h e experiments reported here, t h e sorbents ( f r e s h and a f t e r one cycle of acceptance-regeneration) were subjected t o s i e v e a n a l y s i s . The r e s u l t s a r e suounarized i n Table 4 . Pure Fe203 and pure Component X d i s i n t e g r a t e a s w e l l a s agglomerate, a s t h e d a t a show. However, when t h e two a r e mixed, t h e r e i s n e i t h e r d i s i n t e g r a t i o n nor agglomeration. The USBM sorbent showed considerable p a r t i c l e d i s i n t e g r a t i o n and f l a k e formation on t h e extrudates. I n t h e case of sorbent BCL 29 E , t h e f i n e s formed i n Experiment 36 were very high, while i n Experiment 37, a r e p l i c a t e , no f i n e s were formed a t a l l . This could probably be due t o t h e overnight cooling of t h e absorbed sorbent before regeneration i n Experiment 37, whereas i n Experiment 36, t h e r e w a s no t i m e l a g between t h e acceptance and regeneration runs. Once a g a i n t h e s e d a t a i n d i c a t e t h e need f o r f u r t h e r s t u d i e s of t h e regeneration mode. The s t r e n g t h of sorbent BCL 20 appears b e t t e r i n comparison with t h a t of most o t h e r sorbents.
H S-Acceptance Thermodynamics -2

,
>

The performance of t h e mixture of Fe 0 -Component X is enhanced over the performance of i n d i v i d u a l components, p a r t i c u l & ? y i n regard t o p h y s i c a l s t r e n g t h . While t h i s i s an a c c i d e n t a l discovery, t h e a c t u a l reasons are s p e c u l a t i v e and Component X may be a s t a b i l i z i n g agent. The p a r t i a l p r e s s u r e of H2S i n t h e e x i t gas stream i s lower f o r t h e mixture than f o r both pure Fe203 and f l y ash-Fe203 sorbent formulations. The r e a c t i o n mechanism of H S with Component X is not understood. Also 2 free-energy d a t a f o r component X a r e not a v a i l a b l e t o compute e q u i l i b r i u m conversions. Experimental d a t a a t 1500 F show t h a t t h e e q u i l i b r i u m conversion of H S with Component 2 X i s hfgher than with Fe203; however, t h e e f f e c t of steam on H2S conversion with Component X cannot be predicted, and a c t u a l experiments a r e needed t o o b t a i n t h e d a t a . For Fe 0 considerable thermodynamic d a t a a r e a v a i l a b l e . According t o ICI, 'fresh i r o n oxide2$; 03) i s converted t o FegO4 i n t h e presence of hydrogen above 350 F.(6) Thus, i n t t e range of 650 t o 1500 F , Fe304 i s t h e sorbent.

A t 10 w t % d e s u l f a c i t y , f o r an i n l e t gas containing 280 grains/100 scf H2S (0.45 v o l %) t h i s i s equivalent t o an a t t r i t i o n loss of 0.025 w t % per cycle.

248

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3 Fe203

+ H2

2 Fe304

+ H20 +4
H20
2)

Fe304

+ H2 + 3 H2S

-, 3 FeS

According t o t h i s r e a c t i o n , each mole of Fe 0 r e a c t s with 2 moles of H2S; t h e t h e o r e t i c a l d e s u l f a c i t y i s 40 percent by we?ggt. However, USBM r e p o r t s t h a t t h e following r e a c t i o n t a k e s place: Fep03

+3

H2S

FeS

+ FeS2 i- H20 3

3)

+
'

on t h i s b a s i s t h e d e s u l f a c i t y of Fe 0 would be 60 percent by weight. The amount of water evolved by e i t h e r r e a c t i o n i s 2 t z e same. Actual experimental d a t a on t h e f l y ash Fe 0 s e n t (64 grams H S removed per 100 grams Fe 0 ) support t h e U B r e a c t i o n SM 2 3 . mxh:n?sm"' which can be u g i l i z e d f o r computing t h e equilibrium conversions.
0

For Reaction 3 ) . t h e standard free-energy change (AF a t 25 C and 1 Thus, t h e equilibrium constant atmosphere) i s -26,270 caljg-mole.
K = exp

(s)x = 1.85 R T
= - nH0 RT

loL9 a t

25 C.

K a t 1000 F (537 C) can be computed using t h e equation

dlnK dT

where P H , the h e a t of r e a c t i o n can be shown t o be s u b s t a n t i a l l y c o n s t a n t over the temperature range under study. Thus,
KIOOO

9 = 8.6 x 10

The high K value i n d i c a t e s t h a t conversions a r e very high and approach 100 percent. These r e a c t i o n s are heterogeneous and t h e change i n number of moles of gas i s zero. Therefore, t h e r e should be no e f f e c t of p r e s s u r e on conversion. The above c a l c u l a t i o n s f o r Fe 0 a l s o hold f o r o t h e r dry oxides. Thus, B a O , C a O , COO, Cu20, NaZO, N i O , and Zn02a$l show high e q u i l i b r i u m conversions. Two oxides (MgO and Z r O ) show p o s i t i v e standard free-energy changes, i n d i c a t i n g thermodynamic i n f e a s i b i l i z y . Regeneration ( r e a c t i o n with oxygen) of t h e s u l f i d e s of a l l t h e s e sorbents i s thermodynamically f e a s i b l e . E f f e c t of Steam on Conversion Coal gases u s u a l l y c o n t a i n steam, a t l e a s t 10 percent by volume. Since steam is a product of t h e r e a c t i o n of oxides w i t h H S , t h e presence of steam i n feed 2 gas can reduce H2S conversion. For t h e i r o n oxide sorbent, c a l c u l a t i o n s show t h a t a t 1000 F (K = 8.6 x l o 9 ) , f o r a gas containing 5000 ppm H S and 10 percent steam, t h e 2 equilibrium H2S content i n e x i t gas i s 4.6 ppm based on t h e U B r e a c t i o n mechanism. SM I f t h e IC1 r e a c t i o n i s used, t h e e q u i l i b r i u m H2S i n e x i t g a s i s >300 ppm. These calc u l a t i o n s cannot be made f o r Component X s i n c e thermodynamic d a t a are not a v a i l a b l e . F u r t h e r , t h e behavior of a mixture of m a t e r i a l s r e a c t i v e with H2S as a sorbent i n presence of steam i s more complex than thermodynamics can p r e d i c t .

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A CONCEPTUAL PROCESSING SCHEW

It i s important n o t only t o have a good sorbent but a l s o a processing scheme i n which it can be used. Many processing schemes can be v i s u a l i z e d t o des u l f u r i z e hot c o a l g a s e s . One such scheme i s presented i n Figure 4. The sorbent ( p e l l e t s or e x t r u d a t e s ) moves a t a slow r a t e i n a moving bed and discharges i n t o a fluidized-bed r e g e n e r a t o r . A i r a c t s a s t h e f l u i d i z i n g medium and supplies t h e oxygen f o r t h e s u l f i d e o x i d a t i o n . The scheme has t h e advantages of a continuous process but reduces a t t r i t i o n problems during H2S removal. Thus, no dust p a r t i c l e s a r e introduced i n t o t h e hot gas stream. T h i s scheme i s intended mainly f o r atmospheric pressure gases l i k e K-T gas. The design of t h e H S-acceptance zone can be 2 c r i t i c a l t o t h e s u c c e s s f u l performance of t h e process.
CONCLUSIONS

A good d e s u l f u r i z i n g sorbent should regenerate w e l l , have a long l i f e ( a c t i v i t y ) and high d e s u l f a c i t y . The SO c o n c e n t r a t i o n i n regenerator e x i t gas should be high with a sharp breakthrough? Also, t h e equilibrium H S concentration 2 i n e x i t gas during acceptance should b e low, even i n t h e presence of steam i n feed gas. The a t t r i t i o n r e s i s t a n c e should be high. The f l y ash--Fe O3 sorbent d i d not show as good a r e s i s t a n c e t o a t t r i t i o n a s BCL 20 sorbent. The B8L 20 sorbent showed lower e x i t e q u i l i b r i u m HZS concentrat i o n and performed b e t t e r a t 1000 F t h a n a t 1500 F . The s u p e r i o r performance a t lower temperature i s i n accordance with t h e thermodynamic r u l e t h a t f o r exothermic r e a c t i o n s , t h e a-ttained equFliSrium c m v e r s i o n i s higher a t lower temperacure. The a d d i t i o n of Component X improved t h e sorbent composition.

In conclusion, i n t h i s study, an e f f o r t has been made t o d e f i n e p r o p e r t i e s of a good sorbent, develop such a sorbent and conceptualize a processing scheme f o r i t s use. The commercial f e a s i b i l i t y o f the process c a n be demonstrated by using t h e sorbent i n such a scheme over a number of acceptance-regeneration c y c l e s . The following reconmendations a r e made toward achieving t h a t end.
RECOWENDATIONS The use of high-temperature H S removal technology should be i n v e s t i g a t e d 2 f o r t h e following c a s e s . Low-Btu g a s i f i c a t i o n and gas u t i l i z a t i o n i n e l e c t r i c power p l a n t s Packaged c o a l - g a s i f i c a t i o n p l a n t s (medium- and low-Btu gases) Synthetic n a t u r a l - g a s production. High-temperature'H S removal i s a novel technology with good p o t e n t i a l t o 2 compete with other d e s u l f u r i z i n g processes. An o v e r a l l process engineering and o t h e r processes ( l i k e R e c t i s o l ) i s economic study of the novel technology needed. Also needed i s an experimental program t o develop s o l i d sorbents t h a t can remove H 2 S t o l e s s than 1-ppm l e v e l s . Both t h e Process engineering/economics study and t h e experimental program t o screen sorbents should proceed concurrently. Intense e f f o r t s a r e needed t o e x p l o r e t h e f u l l p o t e n t i a l of t h i s emerging technology and measure i t s impact on t h e n a t i o n a l energy needs.

--=-e

ACKNOWLEDGEMENTS

This work was supported by t h e B a t t e l l e Energy Program (BEP). The encouragement and cooperation of D r . Frank G. Dawson and M r . Jack G. Conner o f BEP and M r . Herman Feldmann, D r . James E. Flinn, and D r . Edward W. Ungar of BCL a r e s i n c e r e l y appreciated.

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W

252
REFERENCES "Report of t h e C o r n e l l Workshops on The Major I s s u e s of a National Energy Research and Development Program", Published by C o r n e l l U n i v e r s i t y , I t h a c a , New York (December, 1973), p 76. Abel, W. T . , e t a l . , "Removal of Hydrogen S u l f i d e from Hot Producer gas by s o l i d Sorbents", R I 1947, Morgantown Energy Research Center, ERDA (1974). S e i l , G i l b e r t . , E . , DRY BOX PURIFICATION O GAS, American Gas Association, F New York, New York (1943), p 54. Oldaker, E. C., e t a l . , "Removal of Hydrogen S u l f i d e from Hot Low-Btu gas with I r o n Oxide-Fly Ash Sorbents", Report No. MRC/TPR-75/1, ERDA, MERC, Morgantown, West V i r g i n i a (February, 1975). Levenspiel, O., CHEMICAL REACTION ENGINEERING, 2nd E d i t i o n , John Wiley & Sons, Inc., New York (1972), p 215. CATALYST HANDBOOK, I m p e r i a l Chemical I n d u s t r i e s , Ltd., D i s t r i b u t e d by SpringerVerlag, Inc., N e w York (1970), p 53.

(1)

(2) (3)

1
1

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(5) (6)

25 3 SEPARATION O F COAL HYDROGASIFICATION GASES B Y PERMSELECTIVE MEMBRANES

VI. J. Schell
Chemic0 P r o c e s s P l a n t s Co. E l Monte, California 91734 INTRODUCTION It has been recognized f o r many y e a r s that non-porous polymer f i l m s exhibit a higher permeability toward s o m e g a s e s than towards o t h e r s . A s e a r l y a s 1831 (1) , investigations w e r e r e p o r t e d on the phenomenon of enrichment of air with rubber m e m b r a n e s ; however, not until 1950 ( 2 ) had t h e p r a c t i c a l possibility of this and other g a s separations with p e r m s e l e c t i v e m e m b r a n e s been s e r i o u s l y studied. Weller and Steiner (2, 3) in t h e i r c l a s s i c p a p e r s , demonstrated the feasibility of separating oxygen f r o m a i r and described p r a c t i c a l p r o c e s s e s for separation of hydrogen and helium from methane. Although t h e i r r e s u l t s w e r e highly valuable in the development of the science of m e m b r a n e separation, the calculated m e m b r a n e a r e a r e q u i r e m e n t s f o r industrial p r o c e s s e s w e r e enormous. The technical breakthrough in the application of m e m b r a n e s t o g a s separation c a m e with the development of a p r o c e s s f o r preparing cellulose a c e t a t e m e m b r a n e s in a s t a t e which r e t a i n s the permselective c h a r a c t e r i s t i c s of o r d i n a r y cellulose a c e t a t e but which yields vastly i n c r e a s e d g a s permeability. T h e s e cellulose a c e t a t e membranes a r e p r e p a r e d f r o m a solution of the polymer which is c a s t on a smooth surface, partially d r i e d then s e t o r gelled i n a n i c e - w a t e r bath. At this stage the m e m b r a n e s a r e heated i n w a t e r to improve t h e i r s e l e c t i v i t y c h a r a c t e r i s t i c s and a r e then d r i e d by a solvent exchange technique. The r e a s o n f o r the highly permeability values, together with t h e p e r m s e l e c t i v e c h a r a c t e r i s t i c s of ordinary cellulose acetate, i s the formation of a n "active" l a y e r on the a i r d r i e d surface of the membrane. This active l a y e r has c h a r a c t e r i s t i c s s i m i l a r t o those of ordinary cellulose a c e t a t e and has a thickness of the o r d e r of 0.1 m i c r o m e t e r ( p m ) o r less, whereas t h e total m e m b r a n e thickness m a y range f r o m approximately 75 t o 125 pm. Thus, the m e m b r a n e s a r e said t o be a s y m m e t r i c . T h e major portion of the m e m b r a n e is a n open-pore sponge-like support s t r u c t u r e through which g a s e s may flow freely. The permeability and selectivity c h a r a c t e r i s t i c s of t h e s e m e m b r a n e s a r e functions of casting solution composition, f i l m casting conditions, and post-treatment and a r e relatively independent of total membrane thickness. GAS SEPARATION THEORY The steady s t a t e m a s s flux (Ji) of component i through a homogeneous f i l m of uniform thickness separating two gaseous phases is given by F i c k ' s " F i r s t Law" of diffusion:

Ji = -Di dCi/dx = constant

where

2 Di = l o c a l diffusivity ( c m / s e c )
C. = local concentration of component i x

= the distance through the film

254
T h i s relationship c a n be simplified when t h e g a s e s do not chemically a s s o c i a t e with each other and when t h e g a s e s a r e sparingly soluble i n the m e m b r a n e material. In such c a s e s , t h e diffusivity of the permeating gas is constant through the film and the solubility of the g a s a t t h e m e m b r a n e surface is essentially d i r e c t l y proportional t o i t s p a r t i a l p r e s s u r e i n the g a s phase adjacent to that surface, i. e., Henry's L a w applies:

C. =
p r e s sure.

k.P.
1

w h e r e k. is the solubility p a r a m e t e r and Pi i s the p a r t i a l If we l e t s u p e r s c r i p t I r e f e r t o the high p r e s s u r e o r u p s t r e a m side of the m e m b r a n e and s u p e r s c r i p t I1 r e f e r to the low p r e s s u r e pr downstream side of the membrane, Equation 1, a f t e r integration between C . a t x = 0 and C I1 a t i x = 1 . becomes: kiDi (Pi - PiI1 ) I

J. =

3)

The product kiDi is t e r m e d t h e permeability coefficient ( P . ) of the m e m b r a n e f o r component i. T h i s coefficient i s independent of membra'ne thickness and p r e s s u r e differential and the frequently used units a r e , c c ( S T P ) - c m / c m 2 - s e c - c m Hg. which Another p a r a m e t e r of i n t e r e s t is the permeability rate, defined as P./P, i s a m e a s u r e d c h a r a c t e r i s t i c of a given m e m b r a n e with units, cc(ST$)/ c t n Z - s e c - c m Hg T h e total p r e s s u r e s , P I and PII, a r e given by the sums, Pi1 P.I a n d PJ1 PjII, respectively.

The ratio of fluxes of two g a s e s through a m e m b r a n e i s given by:

4)

P.
J

(P.1

P I1 ) j
113

The ratio P./P. i s defined a s the ideal separation factor f o r component i with r e s p e c t to ckrnbonent j in the m e m b r a n e and i s written cy.

..

F r o m the previous d i s c u s ion it can be s e e n that, if component i i s the m o r e permeable, i n c r e a s i n g P . f either by increasing the total p r e s s u r e o r the l re concentration of component i, &ls u l t in a higher m e m b r a n e permeability r rate. In addition, higher values f o r cyiIj e s u l t in g r e a t e r efficiency in g a s separation. If we define a p e r m s e l e c t i v i t y of the m e m b r a n e t o component i with r e s p e c t to component j by u .., 1J PjI PiI1 0.. = 5) 1J

J it c a n be shown f r o m Equations 4 and 5 that:

u.. =
1 J

9'

(Pi I

(Pt - P..II) J

PiI1)

255 It c a n be seen f r o m Equation 6 that as PI1& 0 o r P1/P1'+ the permselectivity

a,

of t h e m e m b r a n e approaches the ideal separation factor, i. e. : lim

cr..
i j

*i / j

7)

PI1+ 0 It i s evident then that by increasing the feed p r e s s u r e to product p r e s s u r e ratio, P1/PII, a n i n c r e a s e in the efficiency of t h e separation of the g a s mixture is obtained. Other s y s t e m vetriables that will have a n effect on t h e s e p a r a t i o n p r o c e s s a r e t e m p e r a t u r e and relative humidity of t h e gas. Usually a n i n c r e a s e in temp e r a t u r e i n c r e a s e s the permeability and d e c r e a s e s t h e s e p a r a t i o n factor. The e f f e c t of relative humidity is variable and has not been r e p o r t e d in the l i t e r a t u r e to a n y g r e a t extent. MEMBRANES AND MEMBRANE SYSTEMS The casting solutions f o r preparation of the m e m b r a n e s d i s c u s s e d h e r e i n contain cellulose diac etate, cellulose triacetate, acetone, d i o x w e , methanol and acetic acid o r maleic acid. The solution i s c a s t at a thickness . of 0 010 in. and i s gelled in i c e water. The resulting m e m b r a n e s a r e heat8C for s e v e r a l minutes and a r e then d r i e d by solvent t r e a t e d in water a t 85 to 9' exchanging the w a t e r with organic solvents followed by evaporation of the remaining solvent. Drying is n e c e s s a r y f o r application to g a s s e p a r a t i o n and this procedure s e r v e s t o prevent the m e m b r a n e f r o m shrinking and losing i t s a s y m m e t r i c c h a r a c t e r upon removal of water. The g a s permeability m e a s u r e m e n t s f o r the flat m e m b r a n e s w e r e made in c i r c u l a r (2.93 c m 2 membyane a r e a o r 0.0316 ft2) t e s t cells. Single d a s e s a t 23 to 25C w e r e brought into contact with the d e n s e active l a y e r side of the m e m b r a n e a t a regulated p r e s s u r e of 15 to 750 psig, causing a portion of the g a s t o p e r m e a t e through the membrane. The p e r m e a t e g a s was removed f r o m the opposite side of the m e m b r a n e a t a t m o s p h e r i c p r e s s u r e . The permeation r a t e s w e r e m e a s u r e d either by the displacement of a soap bubble in a 5 mP g a s b u r e t o r with a wet-test m e t e r . The m e a s u r e d permeation r a t e s and separation f a c t o r s for the single g a s e s with flat-sheet m e m b r a n e s a r e shown i n Table 1, m e a s u r e d a t 100 p s i p r e s s u r e differential, along with l i t e r a t u r e values f o r 0.001-in. cellulose acetate films. It can be s e e n t h t the p e r m e a t i o n r a t e s of the a s y m m e t r i c m e m b r a n e s range f r o m 600 to over 1000 t i m e s those of the films while essentially retaining the selectivity f o r g a s e s . The m e m b r a n e s exhibit a n exceptionally high permeation r a t e for hydrogen and helium a n d a r e p a r t i c u l a r l y permselective f o r hydrogen relative to c a r b o n monoxide and methane. T h i s evidence confirms the continuity of the thin active l a y e r and d e m o n s t r a t e s the improvement in m e m b r a n e separation technology. Cellulose a c e t a t e membrane modules have been manufactured in o u r f a c i l i t i e s f o r s e v e r a l y e a r s now for u s e i n w a t e r desalination. T h e s e modules have a s p i r a l wound configuration (6) that has the advantage of compactness and low cost. F o r example, the dimensions of such a module a r e 4-in. in d i a m e t e r by 3-ft i n length containing approximately 70 f t 2 of membrane. Development of s i m i l a r modules with d r y membrane f o r g a s separation will provide gas p e r m e a b i l i t y r a t e s of the o r d e r of 3200 9500 SCFH a t 750 psig f o r hydrogen.

256

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APPLICATION O F MEMBRANE SYSTEM TO COAL UTILIZATION PROCESSES The feasibility of adapting p e r m s e l e c t i v e m e m b r a n e s t o coal utilization p r o c e s s e s i s described in the following paragraphs. Two p r o c e s s e s w e r e chosen f r o m contract r e p o r t s t o the U. S. Department of I n t e r i o r (7, 8). In the two p r o c e s s e s , the m e m b r a n e separation units d e s c r i b e d a r e a s s u m e d to have the permeability and separation p r o p e r t i e s of the a s y m m e t r i c cellulose a c e t a t e s described previously in Table 1. It is a l s o a s s u m e d throughout that all g a s s t r e a m s will have been p r e t r e a t e d f o r removal of a c i d gases. The resulting feed g a s e s may then be considered to be a two-component s y s t e m of hydrogen and methane-carbon monoxide (carbon monoxide and methane have s i m i l a r p e r m e a b i l i t i e s ) and a computer p r o g r a m c a n be used t o p r e d i c t t h e p e r m e a t e stream compositions. Hydrogasification of Lignite F i g u r e 1 is a schematic d i a g r a m showing how m e m b r a n e g a s s e p a r a t o r s could be y e d t o advantage in p r o c e s s i n g t h e g a s f r o m t h e hydrogasification of lignite. In this c a s e t h e d e s i r e d product i s high Btu pipeline g a s and t h e m e m b r a n e separations a r e incorporated into the Institute of C a s Technology o v e r a l l P r o c e s s Block Flow Diagram (7) in o r d e r to reduce the s i z e of s e v e r a l pieces of equipment and to produce 470 m o r e methane with a higher Btu value. The Prepurification Unit I effluent g a s is cooled t o l O O ' F to r e m o v e w a t e r and is then fed ( F i g u r e 1) into a s p i r a l wound m e m b r a n e s e p a r a t i o n unit which s e p a r a t e s a l m o s t all of the hydrogen f r o m the c a r b o n monoxide a n d methane. The c a r b o n monoxide and methane s t r e a m then h a s about 65% of the volume of the original s t r e a m and c a n be fed to a c a r b o n monoxide shift r e a c t o r w h e r e the low concentration of hydrogen enables t h e reaction to be shifted f u r t h e r t o the right (GO t HZO e CO t HZ), t h e r e f o r e consuming considerably l e s s s t e a m then otherw i s e required. '%he o v e r a l l r e s u l t is that the c a r b o n monoxide shift r e a c t o r s i z e is reduced and the heat load of the waste heat r e c o v e r y unit is reduced. The hydrogen-bearing p e r m e a t e s t r e a m c o m e s f r o m the m e m b r a n e unit at low p r e s s u r e and m u s t be c o m p r e s s e d and cooled before it is sent t o the Prepurification Unit 11. After r e m o v a l of carbon dioxide and the t r a c e of hydrogen sulfide, the hydrogen s t r e a m is fed t o the methanation unit w h e r e c a r b o n monoxide is converted into methane. The second m e m b r a n e separation unit p r o c e s s e s the effluent g a s a f t e r waste heat r e c o v e r y by removing m o s t of the 4.4% hydrogen and recycling it back t o the methanation unit. The r e c o v e r e d hydrogen allows about a 470 i n c r e a s e in the volume of methane produced and a n i n c r e a s e in the Btu value of t h e pipeline gas. The c o s t of the m e m b r a n e units is believed t o be s m a l l in c o m p a r i s o n with t h e savings to be gained by reducing the s i z e of the carbon monoxide shift r e a c t o r and waste heat r e c o v e r y unit and reducing t h e amount of s t e a m consumed so that t h e overall plant should be l e s s costly. In addition, the incorporation of t h e m e m b r a n e s e p a r a t o r s should allow g r e a t e r variation in operating conditions and compositions of intermediate g a s s t r e a m s .

i Coal O l Hydrogenation
Membrane g a s separation may a l s o be applied to c o a l o i l hydrogenation such a s the Coal Oil Energy Development (C. 0. E. D. ) p r o c e s s (8). The hydrogenation unit i s fed C. 0. E. D. oil f r o m the pyrolysis unit along with a m i x t u r e of f r e s h and recycle hydrogen. The m e m b r a n e s e p a r a t o r r e m o v e s most of the methane

258
and heavier hydrocarbons f r o m the recycle hydrogen s t r e a m a t high p r e s s u r e , T h e one-pass m e m b r a n e unit operating a t 1050 psig i n c r e a s e s the r e c y c l e hydrog e n concentration f r o m 4370 to over 90%, with the accompanying improvement in t h e hydrogenation efficiency and reduction in s i z e of the hydrogenation unit. The methane and hydrocarbon g a s s t r e a m contains l e s s than 270 hydrogen and a f t e r extraction of the h i g h e r hydrocarbons would be ideal f o r pipeline gas. REFERENCES
1.

J V. Mitchell, J. Roy. Inst., .

4,

101, 307 (1831). 21, 279 (1950). 46, 585 (1950).

2. 3. 4. 5. 6. 7.

Sol Weller and W. A. Steiner, J. Appl. Phys., -

Sol Weller and W. A. Steiner, Chem. Eng. Prog.,

P. K. Gantzel and U. Merten, Ind. Eng. Chem. P r o c e s s Des. Develop., 331 (1970).
Modern P l a s t i c s Encyclopedia, Oct. (1969).

2,

U. S. Patent #3,417,870 by D. T. Bray, Assignment t o S e c r e t a r y of t h e Interior.

Institute of G a s Technology, Chicago, Ill., "Cost E s t i m a t e of a 500 Billion Btu/Day Pipeline G a s P l a n t via Hydrogasification and E l e c t r o t h e r m a l Gasification of Lignite, 'I Office of Coal Research, R&D Report No. 22, I n t e r i m No. 4, pgs, 6-7, Contract No. 14-01-0001-381.

8 .

FMC Corporation, Princeton, New J e r s e y , 'tChar O l Energy Development, i Appendice I, T a b l e XV, RSISZ, Office of Coal Research, Washington, D. C. Contract No. 14- 01 - 001 235.

It

259

T'LT Prcpu~ 11'1cetion I Effluent Can (7) 240F 1080 P S l g

H2

CO

31.11% C2+ 24.9% C02

3.3%

2.G
Trace

Membrane Separation Unit I

CH4
I

3.) 61:

3s

CO Shift Reactor
(smaller)

W?.stc Heat Recovery (smaller)

\

+120F,

lo50 psig

f
R e p u r i f i c a t i o n U n i t I1 (m &e s i z e )

Metlanation Unit (%me s i z e )

Waste Heat Hecovery (Samr: size)

t o Dryer

(49

more CHI,)

Fjgure

1 SCHENA'J'JC - APPJJCATJOII OF MF3llBANE G A S SEPAMTIONS . IN A LIGNI'JX IM)HCCA5IPICATION PROCESS

260 COMBINED POWER CYCLE USING L W O

BTU GAS PRODUCED FROM THE KELLOGG MOLTEN SALT COAL GASIFICATION PROCESS C. A. KUMAR, L. D. FRALEY, S . E. HANDMAN RESEARCH & ENGINEERING DEVELOPMENT THE M. W. KELLOGG COMPANY HOUSTON, TEXAS INTROOUCTION

I n recent years, i t has become i n c r e a s i n g l y important t o look f o r a l t e r n a t e sources o f energy on a commercially f e a s i b l e basis. I n t h e m i d s t o f t h e present energy c r i s i s , coal remains t h e most abundant source o f energy i n t h i s country. However, t h e time honored techniques used t o convert coal i n t o e l e c t r i c a l power no longer s a t i s f y t h e needs o f t h e power i n d u s t r y . Also, t h e p u b l i c and t h e i n d u s t r y a l i k e have grown t o be ecology conscious; t h e r e i s an ever i n c r e a s i n g emphasis on burning "clean" f u e l . A d i r e c t i o n now established f o r i n c r e a s i n g t h e economics o f power generation i s t o e x p l o i t t h e use o f a combined gas turbine-steam t u r b i n e power c y c l e . The r e l a t i v e l y inexpensive gas t u r b i n e extends o p e r a t i o n i n t o t h e higher temperature range ( p r e s e n t l y 195OOF) and t h e temperature l i m i t on gas t u r b i n e development has y e t t o be established. However, t h e gas t u r b i n e r e q u i r e s a clean f u e l , n a t u r a l gas o r c l e a n l i q u i d s . Low Btu f u e l obtained from The M.W. Kellogg Molten S a l t Coal G a s i f i c a t i o n Process, c u r r e n t l y under development, when used i n c o n j u n c t i o n w i t h a gas turbine-steam t u r b i n e combined power c y c l e system provides f o r an e f f i c i e n t method o f generating e l e c t r i c a l power from h i g h s u l f u r , h i g h ash coal w h i l e minimizing environmental p o l l u t i o n .
DISCUSSION
G a s i f i c a t i o n o f coal using K e l l o g g ' s Molten S a l t Process has been described i n d e t a i l elsewhere (1, 2, 3 ) . The o v e r a l l process converts t h e heating value o f high s u l f u r c o a l t o f u e l gas w i t h a lower heating value o f 100 t o 150 Btu/SCF a t a conversion e f f i c i e n c y o f around 90% w i t h most o f the s u l f u r r e t a i n e d by the melt. The g a s i f i e r i s s e t t o operate a t 260 p s i a and 170OOF and compressed a i r i s used t o p a r t i a l l y burn coal t o produce t h e f u e l gas a t these c o n d i t i o n s . The work t o develop t h e Kellogg Molten S a l t Coal G a s i f i c a t i o n Process f o r SNG ( S u b s t i t u t e Natural Gas) has been modified t o develop a process t h a t i s compatible with the combined c y c l e concept. (See Figure 1.) There are f o u r systems i n t h e process: 1. G a s i f i e r - - a s i n g l e pressure vessel where molten sodium carbonate catalyzes the p a r t i a l o x i d a t i o n o f coal by a i r t o produce a raw f u e l gas. A t y p i c a l composition i s shown i n Table 1. Coal and Carbonate Feed --supply coal and make-up sodium carbonate a t pressure t o the gasifier. Gas Conditioning - - a s e r i e s o f heat exchanges and gas washes make t h e raw gas compatible w i t h a gas t u r b i n e .

2.

3.

4. Carbonate Recycle - - t h e stream which purges ash from t h e g a s i f i e r i s approxi-

26 1
mately 70% sodium carbonate and 8% sodium s u l f i d e . sodium f o r r e c y c l i n g t o t h e g a s i f i e r . COMBINED P W R CYCLE O E The o v e r a l l e f f i c i e n c y o f a combined c y c l e power p l a n t b u r i n g low Btu gas produced from the Kellogg process i s dependent on the coal g a s i f i c a t i o n efficiency-i n c l u d i n g the s a l t cleanup and regeneration--and the temperature-pressure c o n d i t i o n s i n the steam generation system. S a l t recovery technique thus i s one o f t h e key features i n the performance o f t h i s cycle. The s e n s i b l e heat from t h e m e l t purge (See (@ 1700F) i s used t o preheat the a i r supply t o t h e g a s i f i e r ( t o 990F). Figure 2.) Most o f t h e s a l t i s recovered by evaporation as carbonate f o r r e c y c l e rm and the heat f o r evaporation i s provided f o t h e gas t u r b i n e exhaust. S u l f u r r e t a i n e d by the m e l t i s converted t o hydrogen s u l f i d e by carbonation and then recovered as elemental s u l f u r i n a nearby Claus p l a n t . The f u e l gas l e a v i n g the g a s i f i e r i s cooled i n a s e r i e s o f heat exchangers t o a temperature o f around 175F before being sent t o a scrubber. The major p a r t of t h i s heat i s u t i l i z e d f o r the production o f steam and B W heat f o r t h e steam system F (2400 psia/lOOOF/lOOOOF) as w e l l as f o r r e h e a t i n g t h e scrubbed f u e l gas back t o 500F before being sent i n t o t h e gas t u r b i n e . The scrubbing o p e r a t i o n provides the CO2 needed f o r carbonation o f t h e s a l t , w h i l e scrubbing w i t h water e l i m i n a t e s sodium. The o n l y f i x e d n i t r o g e n i n the f u e l i s a t r a c e o f NH and thus t h e f u e l gas produced i s q u i t e clean. Also, sodium carbonate being a c a t a f y s t g a s i f i e s coal completely w i t h o u t t h e production o f associated coal d i s t i l l a t e s . For example, using Ohio C l a r i o n High S u l f u r (4.65%) Coal i n t h e Kellogg process, i t has been determined t h a t more than 90% o f s u l f u r i s r e t a i n e d by m e l t f o r recovery l a t e r . T h i s r e s u l t s i n 0.78 l b SOz/MMBtu i n t h e f l u e gas w i t h o u t any scrubbing t o remove SO2. The g a s i f i c a t i o n system d i s t r i b u t e s the heating value o f t h e coal i n t o f o u r p a r t s . (See Table 2.) The sensible heat i n the f u e l gas i s a v a i l a b l e a t various temperature l e v e l s . This requires a c l o s e i n t e g r a t i o n w i t h t h e steam system o f t h e combined c y c l e so t h a t i t i s used i n the most e f f i c i e n t manner. The number and type o f i n t e r f a c e s j u s t described mean t h a t t h e g a s i f i e r and combined c y c l e must be t i g h t l y i n t e g r a t e d ift h e o v e r a l l system i s t o be v e r y efficient . Figure 2 shows t h e r e s u l t o f j u s t such an i n t e g r a t i o n . A commercially a v a i l a b l e gas t u r b i n e w i t h 1950F i n l e t temperature and a 2400 psia/1000"F/1000"F steam c y c l e were used. The match up between the steam cycle.and s e n s i b l e heat, b o t h i n t h e f u e l gas and f l u e gas, i s shown i n Figure 3. These curves show t h a t t h e heat interchanges are arranged i n such a fashion t h a t minimum temperature d i f f e r e n t i a l s o f around 40F a r e observed a t the pinch p o i n t s . This, along w i t h the f a c t t h a t heat a v a i l a b l e a t t h e g a s i f i e r l e v e l i s l i m i t e d t o steam generation, has r e q u i r e d t h a t B W heating and steam generation be done i n more F ,W than one step. The d i s t r i b u t i o n o f power among various components f o r a 120 M n e t p l a n t i s shown i n Table 3.
It i s estimated t h a t i n t e g r a t i o n o f a gas t u r b i n e combined power c y c l e ( w i t h f u l l y loading t h e gas t u r b i n e i n conjunction w i t h a 2400 psia/1000"F/1000"F steam system) w i t h t h e Kellogg Molten S a l t Coal G a s i f i c a t i o n process generates power a t a n e t heat r a t e of around 9500 Btu/kw-hr o r lower u s i n g a v a i l a b l e equipment (HHV).

The system recovers the

262 UTILIZATION OF L W ASH COAL O

(e.g.,

P i t t s b u r g h Seam Coal w i t h 5.2% ash-l.3IS)

I n c o r p o r a t i n g minor changes

i n t h e purge r e c y c l e and t h e power c y c l e discussed above, the molten s a l t process

can be v e r y e f f e c t i v e l y used w i t h low ash coal. I t i s estimated t h a t such a process would have a g a s i f i e r e f f i c i e n c y o f over 95% w i t h a 0.45 lb/MMBtu o f SO2 i n the f l u e gas w i t h o u t any scrubbing. The o v e r a l l e f f i c i e n c y o f such a combined c y c l e power p l a n t u t i l i z i n g t h e low ash coal i s estimated around 40% (8500 Btu/kwh based on HHV).

ECONOMICS
Any attempt a t economic a n a l y s i s i n these days must be based more on underlying fundamentals o f a system r a t h e r than on numbers. However, i n Table 4 i s an attempt a t a c u r r e n t analysis. This compares the c o s t o f power generated by a conventional power p l a n t equipped w i t h a stack gas scrubber t o the g a s i f i e r combined c y c l e system. Both systems were considered t o have an e f f i c i e n c y o f 36%. Coal was assumed t o be 20$/ton, the conventional p l a n t t o c o s t 400$/kw p l u s 55$/kw f o r a scrubber. The g a s i f i e r - combined c y c l e system was estimated t o be 375$/kw. These parameters r e f l e c t t h e c o n d i t i o n s a t the end o f 1974. Table 4 shows an 11% advantage f o r t h e g a s i f i e r combined c y c l e system. T h i s can be considered marginal s i n c e i t i s a system c u r r e n t l y under development.

STATUS O THE PROCESS F Extensive work has been done i n t e s t i n g t h e containment o f t h e molten sodium carbonate bath for t h e prcductio:: o f high Btu p i p e l i n e q u a l i t y gas (SNG). Basic data on t h e g a s i f i c a t i o n process have been reported. Low Btu coal g a s i f i c a t i o n i s e s s e n t i a l l y an outcome o f t h e Kellogg Molten S a l t process f o r t h e production o f SNG and as such most o f t h e work done f o r t h e SNG process can e a s i l y be extended to t h e production o f low B t u gas. Thus, i n c o r p o r a t i n g a combined c y c l e i n conjunction w i t h t h e Kellogg Molten S a l t process, c u r r e n t l y under development, f o r t h e production of low BTu gas,,provides f o r a r e l a t i v e l y easy way o f o b t a i n i n g power w i t h t h e f o l l o w i n g advantsges: 1. The Molten S a l t g a s i f i e r w i l l handle any type o f coal i n c l u d i n g caking coals w i t h o u t pretreatment. The c a t a l y t i c a c t i o n of t h e molten sodium carbonate promotes complete g a s i f i c a t i o n o f coal w i t h o u t t h e production of associated coal d i s t i l l a t e s , thus e l i m i n a t i n g downstream f o u l i n g and some o f t h e p o l l u t i o n c o n t r o l f a c i l i t i e s t h a t would otherwise be required. The c a t a l y t i c e f f e c t of sodium carbonate allows g a s i f i c a t i o n a t lower temperatures p e r m i t t i n g higher g a s i f i c a t i o n e f f i c i e n c y . The system provides c l e a n f u e l gas f o r use i n a gas t u r b i n e . I n the next f i v e t o t e n years gas turbines p o s s i b l y w i l l be a v a i l a b l e w i t h i n l e t temperatures o f 2 5 O O O F and 3000F. The power c y c l e e f f i c i e n c y i n these cases a r e estimated t o be 46% and 49%, r e s p e c t i v e l y , based on HHV and low ash coal. And f i n a l l y , I t i s estimated t h a t power p l a n t s using 300OOF i n l e t t o gas t u r b i n e r e s u l t i n about 47% r e d u c t i o n i n power costs compared t o a conventional c y c l e (Table 4)

2.

3. 4. 5.

6.

263
REFERENCES 1. Cover, A.E., W.C. Schreiner, and G.T. Skaperdas, "The Kellogg Coal G a s i f i c a t i o n Process", paper presented a t American Chemical S o c i e t y Meeting, Washington, D.C., Sept. 1971. Cover, A.E., W.C. Schreiner, and G.T. Skaperdas, "Kellogg's Coal G a s i f i c a t i o n Process", Chemical Engineering Progress, March 1973. Cover, A.E., and W.C. Schreiner, "The Kellogg Molten S a l t Process", paper presented a t t h e 4 t h Conference on Synthetic Fuels from Coal, Oklahoma S t a t e U n i v e r s i t y , S t i l l w a t e r , Oklahoma, May 1974.

2.
i

3.

264

TABLE 1 COAL AND FUEL GAS COMPOSITION

COAL PROXIMATE ANALYSIS

% ASH

16.87 39.44 43.69 100.00 4.65

% VOLATILE % FIXED CARBON

% SULFUR

% MOISTURE
HIGHER HEATING VALUE

3.43

1 1 2 7 3 BTU/LB

FUEL GAS ANALYSIS WGT. FRACTION N2 H20 co2 CH4 H2 0.614

.02
.04 .31 .006 .Ol .0002 1 .oo

co

HIGHER HEATING VALUE

BTU 1 3 7 ScF

265

TABLE 2 DISTRIBUTION OF HIGHER HEATING VALUE I N COAL AFTER GASIFICATION

. 1. FUEL GAS TO GAS TURBINE . HHV

72.5%

NET SENSIBLE HEAT GAIN

1.8
16.6

\
2 . STEAM GENERATED BY FUEL GAS
3. ASH PURGE LOSS
NET SENSIBLE HEAT LOSS COMBUSTIBLE ( C , S ) 1.9 6.7

4. SCRUBBER LOSS

0.5 100%

GASIFIER EFFICIENCY ( 1 )

+ (2)

= 90.9%

266

TABLE 3 DISTRIBUTION OF POWER FOR 120 M ,W (REFER TO F I G . 1.) GAS TURBINE STEAM TURBINE GROSS AUXILIARIES BOOSTER COMPRESSOR

PLANT

69.3

61.2
130.5 M ,W 6.5
4.0

10.5 M ,W POWER OUT (NET) = 120 eMW OVERALL EFFICIENCY = 36%

I

TABLE 4 COMPARISON OF POWER COST FOR 480 M CONVENTIONAL PLANT W WITH SCRUBBER VS. GASIFIER COMBINED CYCLE PLANT CONVENTIONAL WITH SCRUBBER MILLS 15.8 KWHR 0.3 10.6
26.7

GAS1 F I E R COMBINED CYCLE

13.0 0.3
10.7 -

CAPITAL LABOR OPERATING TOTAL

KWHR

MILLS

24.0

FUTURE PLANTS w/3O0O0F I n l e t t o Gas T u r b i n e

9.2 0.2 8.8

MILLS KWHR

1. 82

I
I

267

\
\

u 0

26 E

26 9

-0 0

'0 0

.O D

c ,
3
D I -

W Q

.O 0

'0 0

LL
0 0

0
0 0

(D

8 -

0 . D

0 0

270

INTERACTION O F MOLTEN SODIUM CARBONATE WITH COAL ASH COMPONENTS ALUMINUM OXIDE. A. J. Darnell, Atomics International Division of Rockwell International Corporation, 8900 DeSoto Avenue, Canoga P a r k , CA 91304

A fundamental study i s b e i n g m a d e of the c o a l a s h - m e l t i n t e r a c t i o n s i n relation to gasification of c o a l i n m o l t e n sodium carbonate. I n the p r e s e n t paper, the i n t e r a c t i o n of alumina with m o l t e n sodium carbonate is discussed. Alumina r e a c t s with m o l t e n sodium c a r b o n a t e to f o r m sodium aluminate (NaAlO,) and c a r b o n dioxide, i. e . , Alu,03 ) t Na,C03 (1) 2NaAIO,(s) t CO,(g). The sodium aluminate (s f o r m e d is v e r y r e f r s c t o r y (r.p > !?OOC) and is only s p a r i n g l y soluble (10-20 ppm) in m o l t e n sodium c a r b o n a t e , The sodium aluminate f o r m s a protective coating around the u n r e a c t e d a l u m i n a which slows down f u r t h e r r e a c t i o n with the m o l t e n sodium carbonate. The r a t e of the reaction between A1203 and Na,CO, h a s been examined o v e r the t e m p e r a t u r e r a n g e 900' to llOOC under a n atmosphere of CO, and with alumina p a r t i c l e s ranging i n s i z e f r o m 1 IJ. to 300 p. T e m p e r a t u r e cycling did not a f f e c t the p r o t e c t i v e n a t u r e of the coating of NaA10, on Al,O, even though sodium aluminate is known to undergo a solid phase t r a n s i t i o n a t 470C. This was d e m o n s t r a t e d i n t e s t s i n which the t e m p e r a t u r e w a s cycled f r o m ambient to 9 0 0 C and i n t e s t s i n which the t e m p e r a t u r e w a s held at 900C. Identical r a t e l o s s c u r v e s w e r e obtained i n the two s e t s of t e s t s , Supported b y U.S. E n e r g y R e s e a r c h and Development Administration.