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.