ORNL,/ TM-86 1 1

Dist. C a t e g o r y UC-90d

C o n t r a c t No. W-7405-eng-6
CHKMICAL TECHNOLOGY D I V I S I O N

F o s s i l Enemv Proerarn

ASPEN MODELING OF THE TKI-STATE

I N D I R E C T L I Q U E F A C T I O N PROCESS

Ray E. B a r k e r *
John M. R e g O V ~ C h
James H. Clinton**
P h i l i p J. Johnson

* P r e s e n t a d d r e s s : T n t e r n a t i o n a l X i n e r a l s and Chemicals
C o r p o r a t i o n , T e r m H a u t e , Indiana.
**UCC-ND

Engineering.

Date P u b l i s h e d :

October 1983

Research s u p p o r t e d by Morgantown Energy Teciiinolngy C e n t e r ,

U.S. Department of Energy.

OAK RX N E NATIONAL T,AROMTOR.Y

Oak Ridge, Tennessee 37830
o p e r a t e d by
U N I O N CARBIDE CORPORATION

f o r the
DEPARTMXNT OF ENERGY

CONTENTS

ACKNOWLEDGMENTS

.
2.

.........................

........................
D E S C R I P T I O N OF MODELS . . . . . . . . . . . . . . . . . . .
2 . 1 L U R G I GASIFIER . . . . . . . . . . . . . . . . . . . .
2.2 ENTRAINED G A S I F I E R . . . . . . . . . . . . . . . . . .
2 . 3 RAW-GAS COOLING . . . . . . . . . . . . . . . . . . . .
2.4 IiECTLSOL MODEL . . . . . . . . . . . . . . . . . . . .
2 . 5 METHANOL SYNTHESIS . . . . . . . . . . . . . . . . . .
2.6 MTG XODEL . . . . . . . . . . . . . . . . . . . . . . .
2 . 7 SHIFT/METHANATION S E C T I O N . . . . . . . . . . . . . . .
2.8 NAPHTHA HYDROTREATER . . . . . . . . . . . . . . . . .
2.9 FORTRAN SUBROUTINES . . . . . . . . . . . . . . . . . .
3.
INTEGRATION OF MODELS . . . . . . . . . . . . . . . . . . .
4 . RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . .
4 . 1 B A S E L I N E T R I - S T A T E CASE. . . . . . . . . . . . . . . .
4.2 F u u - S L z E TRX-STATE CASE . . . . . . . . . . . . . . .

INTRODUCTION

4.3

T.LL1NOI.S NO

6 FEED

..................

........................
6.
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . .
7.
APPENDIX:
SASOL COAL T E S T DATA . . . . . . . . . . . . . .
5

CONCLUSIONS

iii

Page

6
6
10
14
1.7
219
26
38

39
43

45
47
47
55
57

59
62

65

ACKNOWLEDGMENTS
The a u t h o r s gratefully acknowledge t h e s u p p o r t of Morgantown

Energy Technology Center f o r t h i s work.

The t e c h n i c a l guidance and

review comments provided by Leonard E. Grahatnn, Chief of t h e Process

Simulation and Analysis S e c t i o n , and by h i s s t a f f were h i g h l y con-

s t r u c t i v e and added measurably t o t h e final results.

Yrogrammatic

guidance by Ralph E. Schafer, Deputy Director of Coal P r o j e c t s ,

Management D i v i s i o n , was i n v a l u a b l e a s t h e T r i - S t a t e P r o j e c t

evolved d u r i n g t h e c o u r s e of t h i s work.

MODELING OF THE TRT-STATE

-INDIRECT LI@~EEACTION
PRBCESF

ASPEN
-

Ray E. Barker
John M. Regovich

James 11, C l i n t o n
P h i l i p 9 . J01msc;an

ABSTRACT
The ASPEN process s i m u l a t o r has been used t o model an
t n d i r e c t l i q u e f a c t i o n f l o w s h e e t p a t t e r n e d a f t e r t h a t of the
T r i - S t a t e p r o j e c t . T h i s f l o w s h e e t u s e s Lurgi mving-bed g a s i f i c a t i o n w i t h s y n t h e s i s g a s c o n v e r s i o n to methanol followed by
f u r t h e r p r o c e s s i n g t o g a s o l i n e using t h e Mobil MTG process.
Nodels developed i n t h i s s t u d y i n c l u d e the following: LurgI
g a s i f i e r , Texaco g a s i f i e r , s y n t h e s i s g a s c.ooPing Rectisol.,
me thano 1 s y n t h e s i s m e thano 1-r o-ga s o l i ne 1o CO-s h i f t , m e thanaEion, and naphtha h y d r o t r e a t i n g . Therje models have keen
successfully developed In modular f o r m s o t h a t t h e y can be
used t o simulate a number of d i f f e r e n t f l a w s h e e t s DT p r o c e s s
alternatives.
.i

S i m u l a t i o n s of t h e T r i - S t a t e flowsheet have been made

u s i n g two d i f f e r e n t coal feed rates and ~ W Qt y p e s o f f e e d
c o a l . The o v e r a l l s i m u l a t i o n m ~ k l e lWAS a d j u s t e d t o match t h e
Tri-State f l o w s h e e t v a l u e s for methanol, LBG, fsolautane, and
g a s o l i n e . As a r e s u l t o f t h i s a d j u s t m e n t , t h e MTC r e a c t o r
y i e l d structure n e c e s s a r y t o match the f l o w s h e e t product rates
w a s determined, Tfae models were e x e r c i s e d a t dffferent flow
rates and were u n a f f e c t e d by such changes, demonstrating t h e i r
range of o p e r a b i l i t y . The u s e of Lllinois Ma. ti c o a l , w i t h
i t s lower ash c o n t e n t , resulted i n s l i g h t l y h i g h e r p r o d u c t i o n
r a t e s of each of t h e p r o d u c t s a s compared t o u s e of t h e
Kentucky c o a l

1.

INTKODUCTION

The T r i - S t a t e P r o j e c t was o r i g i n a l l y conceived as an i n d i r e c t

Fischer-Tropsch l i q u e f a c t i o n p l a n t producing approximately 56,000 b a r r e l s

of f u e l o i l e q u i v a l e n t p e r day of t r a n s p o r t a t i o n f u e l s and chemicals from

Kentucky c o a l .

The p r e l i m i n a r y d e s i g n of t h i s plant was co-funded

Department o f Energy (DOE) and t h e i n d u s t r i a l p a r t i c i p a n t s .

by the

Within DOE,

t h e &rgantown Energy Technology Centt?r (METC) has t h e r o l e of t e c h n i c a l

l e a d f o r g a s i f i c a t i o n systems t o ME-firnded p r o j e c t s .
t h e r o l e on ' h i - S t a t e

I n consonance wit11

of p r o v i d i n g Lechnological review and a d v i c e on

g a s i f i c a t i o n a d r e l a t e d systems

a p r o c e s s model of t h e o v e r a l l p l a n t

would (1) enhance t h e c a p a b i l i t i e s f o r i n v e s t i g a t i n g and e v a l u a t i n g

t c c h n i c a l u n c e r z a i n t i e s aid a l t e r n a t i v e s a and ( 2 ) p r o v i d e a permanent

r e c o r d f o r f u t u r e r e f e r e n c e and use.
Accurate p r o c e s s c a l c u l a t i o n s are n e c e s s a r y f o r r a t i o n a l d e s i g n and
These c a l c u l a t i o n s can range from very

o p e r a t i o n of p r o c e s s equipment,

s i m p l e ( r e q u i r i n g o n l y a pocket c a l c u l a t o r ) t o very complex ( r e q u i r i n g a

l a r g e computer).

I n t h e l a t t e r case, a primary t o o l i n u s e a t ORlvL i s

t h e ASPEN (Advanced System o r Process Engineering) process simulator.

I

ASPLN i s a modern, s t a t e - a f - t h e - a r t

f u r DOE

ar

a c o s t of $6 i n i l l i o n .

process s i m u l a t o r r e c e n t l y developed
This r e p o r t d e t a i l s t h e modeling of an

i n d i r e c t l i q u e f a c t i o n 1 owsheet u s i n g t h e ASPEN s i m u l a t o r .

These pro-

cess models have been developed i n modular form s o t h a t they can be used

t o m 4 c l a :urnmbP?sr of d i f f e r e n t p r o c e s s a l t e r n a t i v e s .
T h i s work has c o n s i s t e d of developing models of t h e v a r i o u s systems
comprising t h e T r i - S t a t e p r o j e c z and i n t e g r a t i n g t h e models i n a cons i s t e n t f a s h i o n w i t h recycle streams t o produce an o v e r a l l p r o c e s s model
u s i n g t h e ASPEN computer code.

Adequate p r o p e r t y data of l i q u i d s have

been obLainrd o r e s t i m a t e d and corre'laeed t o y i e l d t e c h n i c a l l y cons i s t e n t medels of t h e c r i t i c a l areas of t h e p l a n t .

Although t h e

T r f - S t a t e p r o j e c t has been t e r m i n a t e d , t h e ASPEN models and s p e c i a l purpose s u b r o u t i n e s developed for t h i s wcrk should be a p p l i c a b l e t o many
i n d i r e c t l i q u e f a c t i o n flowsheets.

S e v e r a l m o d i f i c a t i o n s t o t h e p r o j e c t and i t s flowsheet w e r e made

d u r i n g t h e d e s i g n phase.

uses Lurgi moving-bed

The f l o w s h e e t o f t h e T r i - S t a t e p r o j e c t modeled

g a s i f i c a t i o n and s y n t h e s i s gas conversion t o

methanol, which i s f u r t h e r processed t o g a s o l i n e u s i n g t h e Mobil MTG

(methanol-to-gasoline)

process.

S y n t h e s i s gas not converted t o methanol

i s methanated t o produce s u b s t i t u t e n a t u r a l gas.

A simplified overall

f l o w s h e e t of t h e Lurgi-methanol-MTG p r o c e s s i s shown i n Fig.

1.

The w e s t e r n Kentucky c o a l i s f e d t o t h e c o n v e n t i o n a l dry-ash Lurgi.

The Lurgi g a s i f i e r s are t o be modified f o r u s e w i t h caking coals by t h e
a d d i t i o n of a s t i r r e r t o m a i n t a i n good bed p o r o s f t y .

This arrangement

h a s been t e s t e d w i t h t h e proposed c o a l r e c e n t l y a t SAS0L.l

The L u r g i

g a s i f i c a t i o n model has been c a l i b r a t e d t o r e f l e c t t h o s e t e s t r e s u l t s .

The s y n t h e s i s gas from t h e Lurgi i s cooled t o condense water and t h e
condensable hydrocarbons.

The heat r e l e a s e d from t h i s c o o l i n g i s used

t o g e n e r a t e low- and medium-pressure

steam.

The cooled s y n t h e s i s gas i s then s e n t t o t h e R e c t i s o l p l a n t , where

i t i s cooled and t h e H2S i s removed by a b s o r p t i o n i n refrigerated metha-

nol.

The R e c t i s o l flowsheet i s a s t a n d a r d d e s i g n f o r gases c o n t a i n i n g

condensable hydrocarbons (i.e.

naphtha).

The s u l f u r - f r e e

compressed and p a s s e s t o t h e methanol s y n t h e s i s r e a c t o r .

gas i s then

The methanol

s y n t h e s i s process u s e s t h e Lurgi r e a c t o r , w i t h t h e h e a t of r e a c t i o n

being used t o g e n e r a t e steam i n t h e r e a c t o r j a c k e t .

The r e a c t o r product

i s cooled t o condense t h e methanol, and t h e u n r e a c t e d g a s e s are r e c y c l e d

t o the reactor.

I n o r d e r t o p r e v e n t buildup of i n e r t s i n t h e r e a c t o r

recycle, It i s necessary t o purge a p o r t i o n of t h a t stream, c a l l e d t h e

purge gas.

u3

"he purge gas i s t o be methanated t o produce p i p e l i n e - q u a l i t y gas.

However, s i n c e t h e r a t i o of H2 t o CO i n t h e purge gas i s t o o low for
f e e d t o a methanator, part. of t h e purge gas i s first s h i f t e d t o produce
more M2. The s h i f t e d gas i s remixed w i t h the remainder of t h e purge gas
and s e n t t o the methanator.

The methanatlon flowsheet uses two r e a c t o r s

in series, w i t h r e c y c l e t o t h e f i r s t r e a c t o r and gas c o o l i n g by steam

The methanated gas 1s t r e a t e d t o

g e n e r a t i o n between t h e r e a c t o r s .

remove water and GO2 and i s t h e n ready f o r p i p e i i n e i n j e c t i o n .

The s y n t h e s i z e d methanol i s passed t o t h e NobI.1 MTG u n i t f o r conv e r s i o n t o hydrocarbons.

Most of t h e methanol i s converted t o l i q u i d

fuels, though some l i g h t gases are also produced.

The KCG product i s

s e n t t o a two-column f r a c t i o n a t i o n s e c t i o n t o separate l i g h t g a s e s ,
a l k y l a t i o n f e e d , and g a s o l i n e .

The a l k y l a t i o n f e e d i s sent. t o the

a l k y l a t i o n s e c t f o n f o r p r o d u c t i o n of a d d i t i o n a l l i q u i d fuels.
The condensate from t h e g a s i f i e r e f f l u e n t cooling i s phases e p a r a t e d i n t o hydrocarbon and water phases.

f r o m t h e Tri-State
Lurgi.

The o r i g i n a l flowsheet

p r o j e c t c a l l e d f o r r e c y c l e of t h e heavy t a r s t o t h e

This practice caused some operating problems a t t h e SASOL t e s t s ,

so t h e project: was modified t o use a Texaco p a r t i a l o x i d a t i o n u n i t t o

g a s i f y t h e tars.

The o r i g i n a l flowsheet also c a l l e d f o r a n upgradtng

( h y d r o t r e a t i n g ) of t h e naphtha f r a c t i o n from t h e g a s i f i e r t o produce a

s a t i s f a c t o r y g a s o l i n e blend stock.

Although t h e SASOL test r e p o r t

i n d i c a t e d t h a t no naphtha w a s formed i n t h e g a s i f i e r , i t i s s t i l l
i n c l u d e d i n t h i s s t u d y t o handle t h e s m a l l amount of naphtha l i k e l y to
b e formed f n l a r g e r - s e a l e processes.

The u n i t s ulodeled i n t h i s s t u d y I n c h d e :

Lurgi gasi.Cler, Texaco

( o r o t h e r e n t r a i n e d ) g a s i f i e r , s y n t h e s i s gas c o o l i n g , X e c t i s o l , methanol

s y n t h e s i s , methamol-to-gasoliznf,
hydrcit.reating.

CO-shift,

methanation, and naphtha

A d d i t i o n a l l y , two user FORTRAN subroul:tnnes have been.

w r t t t e n f o r t h e d e v o l a t i l i z a t i o n of coal t o form c h a r and v o l a t i l e p r o d u c t s and f o r t h e decompositioa of coal. t o i t s elements p l u s a s h and

char.

These r o u t i n e s are general. and very i i s e f e r P i n t h e rztcsde'ling of

many c o a l conversi.an p r o c e s s e s .

Orie user POKTW- u n i t a p c r a t i o n model

h a s been written to f a c i l i t a t e modeling of waste heat: b o i l e r s , wMch a i e

wl.dely used i n coal. conversion processes.

An enhancement t o t h e ASPEN

p h y s i c a l p r o p e r t y system has a l s o been made t o a l l o w f o r t h e d i r e c t

i11put: of h e a t of combustion v a l u e s f o r c o d .

T h e rernrairrder of t h i s r e p o r t p r e s e n t s (1) the de.ta.i.1~of t h e u n i t

o p e r a t i o n models, FORTRAN subroutj.nes

and ASPEN enhancement ; ( 2 1 how

t h e s e models were tiitegrated t o a l l o w o v e r a l l matertal halances t o be

made; and ( 3 ) t h e r e s u l t s u s i n g d i f f e r e n t types of feed c o a l and

The ASPEN computer i n p u t and r e p o r t

v a r i a t i o n s i n c o a l throughput.

f i l e s f o r t h e m 0 d e l s and FBB'IH.AN s u b r o u t i n e s developed i n t h i s s t u d y are

belng i s s u e d as a Suppleslent t o t h i s r e p o r t .

a r e a v a i l a b l e by c o n t a c t i n g ORNL.

A l i m i t e d number of c o p i e s

M i c r o f i c h e c o p i e s are available from

the N a t i o n a l T e c h n i c a l I n f o r m a t i o n S e r v i c e (NTIS
2.

2.1

>.

DESCRIPTION OF MODELS

LURGI GASIFIER
The information n e c e s s a r y t o f o r m 1 a t e the L u r g i g a a f f i e r model w a s

t a k e n from t h e SASOL c o a l t e s t

and a r e l a t e d p u b l i c a t i o n .

The model

has e s s e n t i a l l y f o u r s t e p s :

(1) dryingldevolatilization; ( 2 ) conversion

of d e v o l a t i l i z e d coal t o i t s elements, p l u s a s h and char; ( 3 ) conversion

of t h e elements t o produce gas-phase
of t h e gas-phase

components.

components; and ( 4 ) e q u i l i b r a t i o n

The e q u i l i b r a t e d gas-phase

components

a r e t h e n remixed w i t h t h e v o l a t i l e s t o form t h e raw s y n t h e s i s gas.

s o l i d s from t h e g a s i f i e r are removed i n a n o t h e r stream.
flow diagram for t h i s model i s shown i n Fig.

The

The ASPEN block

2.

The c o a l d e v o l a t i l i z a t i o n i s done i n block PROD u s i n g t h e ASPEN

r e a c t o r model KYIELD w i t h u s e r y i e l d s u b r o u t i n e DEVOL.

S u b r o u t h e DEVOL

c o n v e r t s h a l f of t h e v o l a t i l e matter from t h e proximate a n a l y s i s component a t t r i b u t e t o v o l a t l l e products.

H2, CH4, R 20 , CO, C,+,

CO

The p r o d u c t s are assumed t o be

phenol, and tar.

Their respective y i e l d s

are passed through t h e f i r s t e i g h t l o c a t i o n s of t h e RFCAL vector i n t h e

ASPEN i n p u t language.

These y i e l d s must be o b t a i n e d from e m p i r i c a l

d e v o l a t i l i z a t i o n d a t a o r from some o t h e r source.

DEVOL updates t h e

proximate and u l t i m a t e a n a l y s l s of t h e c o a l t o reElect t h e changes due

t o d e v o l a t i l i z a t i o n ; i n t h i s manner t h e element balance i s maintained.
A f t e r t h e v o l a t i l e s are removed i n t h e s e p a r a t i o n block. LBEVOL, t h e
d e v o l a t i l l z e d c o a l i s decomposed t o I t s elements f n block C O W .

Block

C O W also u s e s t h e ASPEN RYIELD r o u t i n e and a user y i e l d r o u t i n e ,

DECOMP.

Subroutine DECOMP merely decomposes t h e c o a l t o i t s elements

p l u s c h a r and ash based on t h e u l t l m a t e a n a l y s i s .

Ilhis scheme p l a c e s

t h e c o a l ( o r c h a r ) undergoing g a s i f i c a t i o n i n t o c o n v e n t i o n a l components
w h i l e s t i l l maintaining t h e e l e m e n t a l balance.
The e l e m e n t a l coal c o n s t i t u e n t s are t h e n mixed w i t h t h e g a s i f i e r
oxygen and steam f e e d s .

I n block GAS1, t h e ASPEN RSTOIC model i s used

ORNL DWG 82-1011R

COAL-FD

_q

PRUDGAS
COALPROD
OFFGAS

JACKTSTM

RGAS

I
Q1

REACTD

Fig. 2 ,

ASPEN b l a c k diagram of L u r g i gasifier model.

9
t o react carbon and oxygen t o form carbon diox.f.de, w h i l e i n block GAS2
carbon and steam are r e a c t e d t o form carbon monoxide and hydrogen.
A t h i r d RSTOIC model I s t h e n used (block GAS3) t o convert t h e s o l i d

s u l f u r and remaining oxygen a c c o r d i n g t o t h e f o l l o w i n g r e a c t i o n s : :

S
02

+ M2

H2S

2C0 f 2CQ2

Block ASWOUT removes 96% of t h e remaining a s h and 25% of t h e c h a r

i n stream HOTASH.

The gas-phase

components are t h e n e q u i l i b r a t e d i n
The p e r t i n e n t r e a c t i o n s are

block KEACT u s i n g t h e ASPEN REQUIL model.

assumed t o be t h e following:
CO

+ 820

CO

-+-

82s

N2

3: 8 2

-9- GO2

3112 2 CHI+ -I-H2O

+ CO

+ 3H2

I H2

+ COS

* 2m3

The e q u i l i b r a t e d gases are t h e n remixed with t h e v o l a t i l e s ts produce

t h e raw s y n t h e s i s gas.

Care i s t a k e n t o conserve h e a t

1.11

t h e model by

c o l l e c t i n g a l l h e a t r e l e a s e d i n r e a c t f o n s i n t o block REACT.

SASOL coal test'

In t h e

( s e e Appendix), t h e L u r g i s y n t h e s i s gas e x i t e d a t a

t e m p e r a t u r e o f 1030OF.

Thus, t h e e x p e r i m e n t a l t e m p e r a t u r e of 1030F has

been used t o determine t h e amount of steam g e n e r a t e d I n t h e BOILER block

STEAMER,

Ttre physical p r o p e r t i e s f o r tar and naphtha were obta-ined

u s i n g t h e Wilson3 c o r r e l a t i o n .

F P t t c d b i n a r y i n t e r a c t i o n parameters

w e r e used for a l l i n t e r a c t i n g s p e c i e s
e q u a t i o n of state.

with t h e Redlich-Kwong-Soave

These d a t a were e n t e r e d i n t o t h e ASPEN i n p u t f i l e

u s i n g t h e i n s e r t RKSKIJ.

10
2.2

EN'I'KAIINED GASIFIER

The Texaco eiztrainetl g a s i f i e r model i s sirnil.ar t o t h e TAurgi model.

e x c e p t t h a t t h e e n t r a i - n e d g a s i f i e r assumes t h a t d e v o l a t i l i z a t i o n i s
unimportant

'phis

model has g i w n e x c e l l e n t r e s u l t s f o r modeling

entrained g a s i f i e r s ; T a h l e S shows a comparison between our model pred i c t i o n s arnd d a t a from Koppers5 f o r t h r e e widely d i f f e r e n t c o a l s :

westerii, I l l i n o i s , and e a s t e r n c o a l s -

FOP each c o a l , t h e agreement

between t h e ASPEN p r e d i c t i o n s and t h e Koppers data i s q u i t e goad,

An ASPEN block f l o w diagram of t h e e n t r a i n e d g a s i f i e r model. for a
3.

s o l i d coal f e e d i s shown i n Fig.

The model begins by f i r s t decom-

p o s i n g a l l components having a n ul.tiinate a n a l y s i s a t t r t b u t e t o t h e i r

e l e m e n t s , p l u s ash and char.

T h i s d e c o ~ ~ ~ p o si is t done
f ~ ~ ~i n block CONV

u s i n g tlrcs user y i e l d s u b r o u t i n e , DECBMP, as d e s c r i b e d i n t h e p r e v i o u s

d i s c u s s i o n of t h e Lurgi model.

IF not o t h e r w i s e s p e c i f i e d , t h e carbon

burnup i.s assumed t o be 100%.

It s h o u l d be noted t h a t DECOMP will a l s o

decompose a t t r i b u t e c o n v e n t i o n a l components, such as tar.

When a s o l i d

coal. f e e d i s not used, as i n the T r i - S t a t e case, t h e ASPEN flow diagram

shown i n Fig. 4 i s used.

The c o n v e r t e d elements are t h e n mfxed w i t h t h e

~ adiaoxygen and t h e s o l i d phases r e a c t e d t o gas-phasi? c o m p ~ n e n tand

b a t i c a l l y e q u i l i b r a t e d as in t h e L u r g i model.

The h o t , e q u i l i b r a t e d

gases are t h e n quenched w i t h water t o a temperature of 1800'F;

a design

s p e c i f i c a t i o n i s i n c l u d e d t o vary the quench water flow r a t e t o o b t a i n

t h e s p e c i f i e d o u t l e t temperature.

11

Table 1.

Comparison of ASPEN entrained g a s i f i e r model and published reports of KoppersTotzek g a s i f i e r p e r f o m n e e (basfs: 1 t o n / h )

INPUT

Coal
Western

Eastern
-___.

Illinois

Analysis, w t X

56,76
4.24
1.01
0.67
13.18
22.14
2.00

C
H
N

Ash
Moisture

69.88
4.90
1.37
1.08
7.05
13.72

61.94
4.36
0.97
4.88
6.73
19.12

2.

2.00

Gross heating value

(Btu/lb)

9,888

11,388

12,696

Oxygen (98% 0 2 >

(lblh)

1,298

1,408

1,634

Steam (250"F, 14.7 p s i )

272.9

(Iblh)

oa

587.4

541.3

RE sULT s
ASPEN

Gas production (SCFH)

5 1 665

Koppers

51,783

ASPEN

57,752

Koppers
-~

59,489

ASPEN

64,473

Koppers

65,376

Gas compositfon, m o l X
(dry)

33,3
59.5
5-81
1.07
0.27
0.02
Carbon burnup, w t X
(assumed 1

99.5

32.86
58.68

7.04
1.12
0.28
0.02

35.0
55.4
6.7
0.98
1.80
a. 09

97. 0

34.62
55.38
7.04
1.01
1.83
0.12

35.7
56.0
6.88
1.11
0.36
0.02

97.0

35.39
55. Y O
7. 18
1.14
0.35
0.04

12

1.

I
I
I

I
I
I
I

I
I
I
I

w-

GAS

COOLASH

BFWl

Fig. 3 . ASPEN block diagram of e n t r a i n e d g a s i f i e r model w i t h

a solid coal f eed.

13

ORNL DWG 82-1451R

TSTEAM

TOXYGEN

TLIQ5UT

WATER

TSTEAM

PROPUCT
Fig. 4 . ASPEN block diagram of e n t r a i n e d gasifier w d e l w i t h
l i q u i d feeds.

2.3

RAW-GAS

COOLING

The Tr-t-State flowsheet c a l l s f o r t h e r a w synthesjis gas t o he

cooled and s e n t t o R e c t i s o l , not u s i n g a r a w s h i f t as i n some o t h e r
proposed processes.

lhe s e n s i b l e h e a t i n hot raw s y n t h e s i s gas i s a

s i g n i f i c a n t f r a c t i o n of t h e h e a t i n g v a l u e of t h e f e e d c o a l and, t h e r e f o r e , must be recovered e f f i c i e n t l y .

t i o n of t h e raw-gas

This recovery p r o c e s s ts the func-

cooling section.

The process flow diagram used f o r our gas cooking model i s shown i n
Fig.

5.

The d e t a i l s o f t h i s flowsheet w e r e t a k e n from Wham e t a:.

The gas c o o l i n g s e c t f o n c o o l s t h e raw synthesis gas t o t h e lowest pract i c a l temperature u s i n g water and a i r cooling,

This maximum p r a c t i c a l

c o o l i n g reduces t h e r e f r i g e r a t i o n requirements i n t h e R e c t i s o l u n i t
which follows.
The ASPEN block flow diagram f o r t h e gas-cooling model i s shown i n
Fig.

The h o t s y n t h e s i s gas i s first scrubbed wPth r e c y c l e condensate,

6.

block M1.

The two-phase d x t u r e from t h e s c r u b b e r i s cooled i n t h e f i r s t

h e a t exchanger, block E301E3, g e n e r a t i n g medium-pressure

steam.

The gas

from t h e f i r s t h e a t exchanger i s f e d t o a knockout drum, w i t h t h e cond e n s a t e recycled t o t h e scrubber.

The gas from t h e knockout drum i s

cooled f u r t h e r i n t h e second h e a t exchanger, block E303AE1, producing

more medium-pressure

steam and d i r t y condensate.

t h e t h i r d h e a t exchanger t o produce low-pressure

h e gas i s t h e n f e d t o

steam.

At t h i s point,

t h e gas stream i s a i r - c o o l e d and water-cooled and s e n t 6 0 t h e R e c t i s o l

unit.

This model assumes a c l e a n tar/water separation i n block S W P L I T ,

w i t h t h e t a r being f e d t o t h e Texaco gasifier.

R e Redlich-bong-Soave

(SYSOP3) e q u a t i o n , which i s e x c e l l e n t f o r l i g h t gases and hydrocarbons,

15

16

:I

eti

il

i s used f o r t h e c a l c u l a t i o n of p h y s i c a l p r o p e r t i e s f o r p r o c e s s streams;
t h e ASME steam t a b l e c o r r e l a t i o n s (SYSOP12)
c o o l i n g water.

are used for steam and

Tbe p h y s i c a l p r o p e r t i e s for t h e condensable hydrocarbons

w e r e o b t a i n e d u s i n g t h e Wilson

correlation.

When a r f g o r o u s ASPEN

sour-water f l a s h mdel has been developed, I t should r e p f a c e the p r e s e n t

FLASH2 blocks.
2.4

RECTISOL ESODEL
The c a t a l y s t s used f o r methanol s y n t h e s i s and methanation are sen-

s i t i v e t o poisoning by s u l f u r

C O I U ~ Q U ~ ~ S The
,

R e e t i s o l p r o c e s s i s one of

t h e more w f d e k y used p r o c e s s e s f o r removing H2 S from s y n t h e s i s gas.

R e c t i s o l p r o c e s s uses methanol as a s o l v e n t f o r the H , S a
2

t u r e s used (-70"F),

"he

A t the tempera-

H, S i s more scslub1.e i n methanol than are t h e o t h e r

2

major components of s y n t h e s i s gaso

The flowsheet used h e r e I s t h e s t a n -

d a r d five-column process designed f o r t r e a t i n g g a s e s c o n t a i n i n g a s i g n i f i c a n t c o n c e n t r a t i o n of naphtha,

The presence of naphtha complicates t h e

p r o c e s s i n g because an a z e o t r o p e i s f~rmedlbetween naphtha and methanol

and two l i q u i d phases can be formed i n t h e naphtha/methanol/water

system.

To provide f o r t h e s e h i g h l y n o n i d e a l v a p o r - l i q u i d equilibria,

t h e v e r s i o n of t h e Soave-Redlich-Kwong

e q u a t i o n of s t a t e t h a t has been

modified for p o l a r components (Redlich-bong-ASPEN)

was used.

Fitted

b i n a r y i n t e r a c t i o n parameters are used f o r a l l i n t e r a c t i n g s p e c i e s .

The data shown i n the ASPEN i n p u t file are i d e n t i c a l t o t h e RKSKIJ

i n s e r t used i n the gasifier s e c t i o n .

The p r o c e s s flow diagram f o r the Rectisol model i s shown i n Fig.
The corresponding ASPEN block diagram i s shown i n Fig, 8,

"he r a w gas

7.

---.-

18

___I__

RECMXG

HXDL'TP3
RECVAP 13

RECDESC.2

RREFRIGl
HEATER

REC.WG3

RECGLIQ

RECAZEO

RECLiQi7

! RECNAPEF
I

FLASri3

REiGbI92

REC SAP 15

SC 1

L,
PI7

HECH

RHZOWASH

PADFRC

RECOFFG

Fig. 8.

u
RHZOWCV

RADFRC

RECHZOEF

ASPEN block diagram of Rectissl section.

kECMStiR3

20
from gas c o a l i n g is exchanged a g a i n s t the purified gas and w P t h makeup
r e f r l g e r a t i o n and f e d t o t h e prewash s e c t i o n of t h e absorber.
prewash i s o p e r a t e d

SQ

The

t h a t t h e naphtha i s absorbed whlbe allowing t h e

l i g h t e r components t o pass t o t b e u p p e r s e c t i o n s E the absorber.

The

loaded soPvent i s s e n t t o t h e a z e o t r o p e column t o separate a clean

naphtha product and a methanol-rich stream.

The loaded s o l v e n t from t ~ s

u p p e r s e c t i o n of the a b s o r b e r i s f l a s h e d t o release absorbed s y n t h e s i s

g a s (w:iich

i s r e c y c l e d t o t h e absorber i n l e t ) and t h e n f e d t o t h e

s t r i p p e r a l o n g w i t h the methanol-rlch stream from t h e a z e ~ t r o p ecolumn.

In t h e stripper t h e H r S is s t ~ i p p e d .f n m the solvent- forming a H S-rich

7

vapor stream.
meehanol.

The 3 , s - r i c h stream i s washcd w i t h water t o rzcover t h e

E

The water-methanol mixture i s t h e n d i s t i l l e d t o o b t a i i l a l e a n

methanol stream for r e c y e l c to the absorber.

R e bottom s t r e m from t h e

H ~ ~
S t r i p p ~i sr a l s o recycleel t o t h e absorber,
2. S

P I E T W Q L SYNTHESIS

The methanol s y n t h e s i s model i s based on t h e 14urgh tubular reactor

concept.

6,8--11

In that scheme, t h e h e a t s f r e a c t i o n i s used t o wake

steam I n t h e r e a c t o r shell, w h i c h i s t h e n available f o r use elsewhere i n

t h e process.

rtao methanol s y n t h e s i s r e a c t i o n s are assumed t o occur and

t o be a t e q u i l i b r i u m a t the reactor exit:

CO
CO,

2R2 8 (11-I OH

4-

3s2

C H p

1120

The flowsheet d e t a i l s have been t a k e n from Wham e t a1.6

compressed and d x e d w i t h the r e c y c l e .

The f l o w s h e e t

The mbxtrsre of fresh f e e d and

(r
Q,

c-

N
0

z:
rr:
ea

LL
(H3

21.

22
recyc1.e i s t h e n compressed t o t h e d e s i r e d r e a c t i o n p r e s s u r e .

TE-IPS

stream i s heated by h e a t exchange w i t h r e a c t o r e f f l u e n t b e f o r e e n t e r i n g

t h e reactor.

A f t e r heat exchange w i t h the r e a c t o r f e e d , t h e r e a c t o r

e f f l u e n t i s cooled. f u r t h e r i n air- and water-cooled

dense the prod1xc.t methanol.

exchangers t o con-

The noncondensalzles are s p l i t > part

r e c y c l e d , and the rest purged t o p r e v e n t hi.l.&ap of i n e r t s such as

methane and h i g h e r hydrocarbons i n t h e r e a c t o r l o o p ,

The p u r g e gas i s

s e n t t o the s h i f t / m e t h a n a t i ~ o nt i n i t f o r f u r t h e r processing.
pi:odiict

is f u r t h e r depressurized

The methanol

v a p o r i z i n g a d d i t i o n a l l i g h t gas

c a n be w e d as f u e l . o r s e n t t o methanation.

which

Part of the steam g e n e r a t e d

i n the r e a c t o r j a c k e t i s expanded through a t u r b i n e t o g e n e r a t e the

p m m r n e c e s s a r y t o w n t h e f e e d and r e c y c l e compressors.
T h e ASPEN block diagram f o r t h e methanol s y n t h e s i s simulacj.on -Is

shown io. Fig.

10.

"he si.mul.ation u s e s t h e ASPEN COMPR block t o sim-

l a t e t h e two compressors and thtt: t u r b i n e ,

ASPEN BEATER b l o c k s have been

u s e d t o s i m r r l a t e t h e h e a t exchangers, w i t h the two s i d e s of t h e

f e e d / e f f i u e n t exchanger connected by a beat i n f o r m a t i o n stream, Q1.

The

r e a c t o r i s modeled by a n ASPEN REQUXL block and i s assumed t o o p e r a t e

isothermally.

The heat of reactf-on f r o m the reactor i s passed t o the

b o i l . e r u s e r model v i a heat: stream 42.

'The steam. produced i n t h e b o i l e r

i s s p l i t , w i t h p a r t o f t h e steam sent t o t h e t u r b i n e .

Tlie t u r b i n e block

accepts t h e work i t ~ f o r r n a t i o nstreams from t h e @ompj:&SsoTS, W1 and W2,

and c a l c u l a t e s a n "excess" work i n f o r m a t i o n stream, W3.

An ASPEN

DESIGN-

SPEC v a r i e s t h e s p l i t uf t h e steam stream so that t h e e x c e s s work from

t h e t u r b i n e i s zero.

The p r o d u c t condensation and l e t d o w n o p e r a t i o n s arc

s i m u l a t e d w i t h the ASPEN FLASH2 bl0c.k.

The f i t t e d b l n a r y i n t e r a c t - i o n

23

PUREGAS

w2
-I--?

METNIXER
MIXER

HETCOOLR
HEATER

Fig. 20.

METRECYC

ME'TcDND

I
JJ
I

?'iLTKECYA
HiAl I

MLIKtI

wrw
FLASH2

ASPEN block diagram of the methanal synt.hesis s e c t i o n .

24

c o n s t a n t s disci.issed i n rhe R e c t i s o l model are u s e d Tor the v a p o r - l i q u i d

equi l l b r i u m c a l c u l a t i o n s .

T h e methanol synthesis model has Four primary independent v a r i a b l e s :

(1)

feed composition and s t a t e , ( 2 ) reactor t e m p e r a t u r e , (3) r e a c t o r

p r e s s u r e , and ( 4 ) r e c y c l e ratio.
constant ( e . g .

Other v a r i a b l e s , u s u a l l y c o n s i d e r e d

pressure d r o p s through the equipment, temperature and

p r e s s u r e of the product s e p a r a t o r s , steam p r e s s u r e , e r e . ) , can a l s o be

varied.
Table 2 shows t h e r e s u l t s of varying t h e reactor p r e s s u r e and
recycle r a t i o , h o l d i n g the s y n t h e s i s temperature constant (500F) and
u s i n g t h e f e e d eonposition. from t h e T r f - S t a t e design r e p o r t . l 2

cornposittoen and c o n d i t i o n s are shown i n Table 3.

me

The r e s u l t s i n T a b l e 2

i n d i c a t e t h a t u s i n g recycle r a z i o s g r e a t e r t h a n about 1.0 i n c r e a s e s t h e

equipment s i z e and comprt:..ssor horsepower, with l i t G I e increase i n methan o l production.

I n t h e case of T r i - S t a t e ,

where t h e purge gas i s t o be

s h i f t e d and m t h a n a t e d t o produce SNG (assuming t h a t t h e SNG can be s o l d ) ,

there i s 1it:tIe i n c e n t v e t o use a recycle ratio g r e a t e r than 1.0.

Table 3 , Synthcs-bs gas f e e d t o

methanol s y n t h e s i s model
Cornpocent
H
C6
c02

CH
C B
C

"4.;

N
H20

Ci30K

Feed temperature
Feed p r e s s u r e

Plow rate
(1b-mol/h 1
57,241
28,630
1,528
13,594
388

92
541

0
0
100F
508 p s i a

25

26
2,4

MTG MODEJ.,
The b a s i s f o r producing g a s o l i n e from synthesis gas v i a methanol i s

t h e Mobil methanol-to-gasoline

(MTG) p r o c e s s -

T n i s proprletary process

u s e s a z e o l i t e c a t a l y s t t o convert m.tljPai101 to l i g h t 1.iqui.d f u e l s

( l i g h t e r t h a n about C

10

) and some l i g h t , gases.

p r o p r i e t a r y n a t u r e of Che

~ P O C ~ R R very
,

syathesis reactor i t s e l f .

taken from Schreitner.

Lee

13

and from S d o v e r .

Because of t h e

1ittl.e i s known about the MTG

A product yPe1.d s t r u c t u r e f o r t h e r e a c t o r was

Other process d e t a i l s were t a k e n from b m and

11

The process f l o w diagram used f o r t h e s i m u l a t i o n of t h e MTG,

t i o n a t l o n , and a.lkylacfon s e c t i o n i s showr, i n P i g .

11.

frac-

The f e e d t o

t h e u n i t i s h e a t e d a g a i n s t t h e reactor e f f l u e n t , mixed w i t h Light,-gas

r e c y c l e , and f e d t o t h e r e a c t o r .

The r e a c t o r i s assunzed t o be t h e

Luxgi.-tubular t y p e p and t h e h e a t of r e a c t i o n i s used t o g e n e r a t e steam.

T h e r e a c t o r e f f l u e n t i s cooled t o produce a three.-p'taase mixtinre of gaso-

l i n e , w2ter, and l i g h t gases:

(1) t h e gases are recycled t o t h e r e a c t o r ;

( 2 ) the water i s s e n t t o wastewater t r e a t m e n t ; and ( 3 ) the g a s o l i n e i s

sent t o t h e g a s o l i n e f r a c t i o n a t i o n sectdon.
T h e f r a c t i o n a t i o n s e c t i o n I s of t h e s t a n d a r d two-column d e s i g n ,
producing l i g h t gases ( C 2 - j ,

t i o n feed

(e3<, 5 >. Il"r\e

a stabillzed gasc,l.ine

( C 5 - t - ) , and an a l k p l a -

g a s o l i n e can be s e n t t o gaso?.ine b l e n d i n g

w t t h o u t f u r t h e r treatment.

'l"ne a l k y l a t i o n f e e d i s m i x e d w i t h t h e isobu-

t a n g r e c y c l e stream and f e d t o t h e alkg7latPon reactor.

'The alkylat:i.on

s t e p reacts u n s a t u r a t e s w i t h Lsoalkanes t o produce high-octane g a s o l i n e

by t h e r e a c t i o n s :

cn

27

ch

28

c 3 B6 +

i-B:

4 10

C7H1 s

i-c c II 1 0 +. c 81%1 8
I- i-c 1-7
3 c K
4 1 0
9 20

C,,H8 -f0

Tt i s cornon p r a c t i c e

1. 1.:

t o r e c y c l e l a r g e amounts of i s s b s l t a n e t o p r e v e n t

p o l y m e r i z a t i o n and t o e n s u r e complete c o n v e r s i o n of t h e u n s a t u r a t e s .
The a l k y l a t i o n product 9s s e n t t o a two-column f r a c t i o n a t i o n system t o

recover t h e unreacted isobutasie f o r r e c y c l e , t h c a l k y l a t e f o r g a s o l i n e

b l e n d i n g , as well as C 3 and (21, product sL;r%ams.
The ASPEN block diagram f a r t h i s s i r n i l a t i o n i s shown i n Ffg. 12.
The o v e r a l l s e c t i o n cont-aim r e a c t o r s , h e a t exchangers, and d i s t i l l a t i o n

columns.

The Grayson-Streed

c o r r e l a t i o n (SPSOPZ) i s used f o r vapor-

l i q u i d eqiillihria calculatlons.

Gragson-Streed

i s adequate f o r t h i s

unit: since t h e compounds haadlied are p r t m r i l y l i g h t l i q u i d hydrocarbons.

The ASPEN r e a c t o r model RYIELD i s used t o s i m u l a t e the MTG s y n t h e s i s

r e a c t o r , based on y i e l d d a t a froisn Schreiner.

e q u i l i b r i u m reactor

model could n o t be used because t h e a c t u a l r e a c t i o n s have not been

p u b l i s h e d ; i n addition, a s h a p e - s e l e c t i v e z e o l i t e catalyst which skews
t h e product slate has been used i n t h e process.

The RYIELD model quan-

t i t a t i v e l y c o n v e r t s t h e feed methanol t o g a s o l i n e and l i g h t e r p r o d u c t s

u s i n g the f i n a l product d i s t r i b u t i o n as published by Hobil.

A serious

l i m i t a t i o n of t h i s model i s that t h e reactor is based on a s i n g l e

p ruduct d i s t r i b u t i o n , obtlalned a t Mobils p r e f e r r e d o p e r a t i n g

conditions.

Therefore, varying r e a c t o r tempesattnre and p r e s s u r e may

g i v e e r r ~ n e o u f iresults.
dutles

The modcl is adequate f o r e a l c u l a t i n g heat

product r e c o v e r i e s , etc.

z.

29

30
The d i s t i l l a t i o n columns i n the f r a c t i o n a t i o n s e c t i o n a r e s i m u l a t e d
u s i n g the ASPEN r i g o r o u s d i s t i l l a t i o n model, U D F R C , 2s shown i n Fig.

13.

The a l k y l a t i o n r e a c t o r i s modeled u s i n g t h e ASPEN s t o i c h i o m e t r i c r e a c t o r

R S T O I C , as i l l u s t r a t e d i n Fig.

14.

Tfne h e a t exchangers are modeled

u s i n g t h e ASPEN s i n g l e - s t d e d h e a t exchanger model, HEATER.

For heat

t r a n s f e r between p r o c e s s streams, t h e HEATER blocks are connected by an

i n f o r m a t i o n h e a t stream.

2.7

SHIFT/M:ETHANATION

SECTION

T h e purge gas from methanol s y n t h e s i s and various o t h e r mal-ler gas

streams i n t h e process c o n t a i n a s c g n i f i e a n t f r a c t i o n of t h e energy v a l u e

of t h e f e e d coal.

For that reason t h e s e streams m s t h e p r o p e r l y used t o

m a i n t a i n an a c c e p t a b l c p r o c e s s e f f i c i e n c y .

I f a market f o r SNG i s a v a i l -

a b l e , t h e most e f f i c i e n t use of t h e s e g a s e s i s t o produce p i p e l f n e q u a l i t y gas.

This o p t i o n was t h e one chosen in t h e T z f - S t a t e design.

Details f o r t h e f l o w s h e e t s used i n t h i s s i m u l a t i o n were o b t a i n e d

from J e l a m ,

Selover,

11

and I r v i n e .

15

The p r o c e s s f l o w s h e e t s used f o r

t h i s s i m u l a t i o n are shown i n F i g s , 15 and 16.

Most of t h e gas sent

t o t h e s h i t / m e t h a n a t i o n u n i t i s purge gas from t h e methanol s y n t h e s i s

The amount of gas s e n t t o t h e s h i f t u n i t , which i n c r e a s e s the

area.

hydrogen c o n t e n t , i s deterwined by the amaunt o f hydrogen needed by t h e

methanation p r o c e s s e s o r o t h e r processes.
a r e r e a c t e d t o form C 0 2 arid H

for U

2.

In t h e s h i f t area, H2Q and CO

Some of t h e H -rl.ch stream i s t r e a t e d

2

recovery f o r subsequent use i n the h y d r o t r e a t e r .

The remaining

gas i s remixed w i t h t h e r e s t of t h e purge gas and f e d t o t h e methanation

31

MTGGASBL

Fig.

13.

ASPEN block flow diagram of fractionation s e c t i o n .

32

O N , DWG 82-l452R

M G C3

IBUTRECL

LPGPRBD
GASPROD

KTGGASBL

MIXER

HIXER

---l--

GAS

Pig.

14.

ASPEN bl.ock diagram of alkylation s e c t i o n .

OANL DWG 82-12898

PRESSOR

w
w

NmnTnA
HYDROTREATER

60 NDENSATE

METHANOL OFF-GAS

Fig.

'15.

Process f l a w diagram of methanatton s e c t i o n .

4
w
m

34

35
In t h e methanation u n i t , 6 8 , C82, CII30H, and C~RPJ are r e a c t e d

unit.

w i t h hydrogen t o form CH4 and water i n two r e a c t o r s as follows:

eo

-t- 3112 f Clt4 f B20

C2Rg

+ H2

CH30W f

coz

8 26H,

H2

+ 4a,!

CMq

-4- H2Q

f CBq -4- 2H20

The f i r s t r e a c t o r reacts most of the 6 0 , CR301-2, and C2Rg w i t h hydrogen,

and t h e second r e a c t o r e s s e n t f a l l y completes t h e s e r e a c t i o n s and r e a c t s
CO2

w i t h the remaining hydrogen,

sections

I n both t h e s h i E t and t h e methanation

condensers remove water f r o m the r e a c t o r e f f l u e n t e

The ASPEN block flow diagram f o r t h e s h i f t u n i t s i m u l a t i o n 1s shown

i n Fig.

17.

The purge gas from t h e methanol s y n t h e s i s ks s p l i t between

t h e s h i f t a r e a and t h e m t h a n a t i o n area,

A s p l i t of 35% t~ t h e shift

u n i t has been assumed f o r t h i s s t a g e of development of t h e d e t a i l e d

models.

The amount of gas s e n t t o t h e s h i f t area w i l l depend on how

much hydrogen i s needed and will be determined concurrent w i t h t h e

o v e r a l l p l a n t mass balance.

The gas t o t h e s h i f t u n i t i s h e a t exchanged

w i t h r e a c t o r e f f l u e n t u s t n g ASPEN h e a t streams.

The gas i s t h e n mixed

w i t h steam v i a a FORTRAN d e s i g n s t a t e m e n t t o achieve a WpO-to-CO

of 3:1.

ratio

The steam-gas mixture i s r e a c t e d i n an a d i a b a t i c REQUIL r e a c t o r

t o a c h i e v e t h e CO and H 2 0 conversion t o H2 and C 0 2 .

The r e a c t o r e f f l u e n t 1s h e a t exchanged w i t h t h e reactor f e e d I n

HEATER block.

The r e a c t o r e f f l u e n t i s cooled f u r t h e r by h e a t exchange

w i t h b o i l e r f e e d w a t e r t o produce steam.

The u s e r s u b r o u t i n e BOILER

d e t e r m i n e s how much b o i l e r f e e d water i s r e q u i r e d t o produce s a t u r a t e d

steam a t a given p r e s s u r e .

The gas i s cooled f u r t h e r i n a series of

36

The naphtha produced from L u r g i g a s i f j c a t i o n i s a p o t e n t i a l l y

v a l u a b l e product,

Before t h e naphtha can be used, however, i t m i s t

f i r s t be t r e a t e d t o reduce k t s s u l f u r and n i t r o g e n content.

The comer-

c i a l l y available technolo,gy f o r t h i s f u n c t i o n i s catalytic h y d r o t r e a t i n g .

Details of the h y d r o t r e a t i n g Elowsheet used f o r this s i m k a t . 4 o n w e r e

obtained from Schreiner.

The process flow diagram f o r t h e h y d r e t r e a t e r model 5s shown i n

Fig.

39.

The g a s i f i e r naphtha i s pumped t o r e a c t i o n p r e s s u r e , mixed w i t h

hydrogen, heat exchanged w i t h the reactor e f f l u e n t , and heated f u r t h e r t o

Conditions i n the e s t a l y ' t l c

r e a c t i o n temperature by a f i r e d h e a t e r .

r e a c t o r are chosen t o s a t u r a t e t h e double bonds with as little carboribond cracktng as p o s s i b l e and l i t t l e aromatic-ring

hydrogenatfan.

After

t h e reaction, t h e e f f l u e n t i s cooled, and three phases are formed.

The

gas phase i s s e p a r a t e d a d amine-washed to remove hydrogen e i i l f i d e and

then 5 s s p l i t i n t o r e c y c l e - and purge-gas streams.

The aqueous phase Ps

sent t o w a t e r treatment, and t h e o r g a n i c phase 1s s t a b i l i z e d hy removing

water, P-Eght hdyrocarbons, and d i s s o l v e d gases i n a d i s t h l l . a t i a n untt,

The ASPEN b l o c k diagram f o r t h i s model is shown in Fig. 20.

equipment names i n t h e ASPEN diagram shown in P i g .
o r correspond w i t h t h e equi.pment names

20 are a j t h e r mnemonic

S c h r e i n e r ' s flowsheet.

OR

and product seream v a l u e s f o r temperature,

The

~ K P S S U T ~ and
,

Input

f l o w rates of

components are given by Schreiner, but a l l i n t e r n a l vnlsiea w e r e developed

f o r t h i s study.
I n the ASPEN sirmulation, ASPEN HEATER blocks are used t o simu'hate
h e a t i n g or cooling processes.

"Kp.

ASPE

PiJMP bl.ock i s used f o r t h e

I^- 1

d
H

4 1.

-1

42

lhrn ASPEN compressor

g a s i f i e r naplitha feed and t h e w a t e r f e e d pumps.

(COMPR) i s use9 t-o compress t h e r e c y c l e hydrugera stream t o r e a c t i o n

pressure.

Three-pliasr

f l a s h o p t i o n s are u s e d f o r t h e streams a f t e r tlie

i n j e c t i o n of water i n t o the r e a c t o r e f f l u e n l - and art: used u n t i l t h e

thrrc-ph;nse

f l a s h scpaiator i s rearhsd i n L l i t stream.

S i n c e no specific

d e t a i l s are known about t h e r e a c t o r , a n e q u t l i b r i u m model cannot be

u t i l i z e d ; hence, t h e ASPEN RSTOLC r e a c t o r i s u s e d .

The r e a c t i o n

s t o i c h i o m e t r y i s deduced ram t h e i n p u t s am1 p r o d u c t s of the g a s i f i e r

The tm r e a c t i o n s used i n RSTOlC

h y d r o t r e a t i n g sect-ion I n S c h r e i n e r .

are g i v e n as f o l l o w s :

56.66 H 2 i- 157.b4 naphtha (gasifier)

i3.25

II2S -6 2.16 E20 4 4.18 CHI,

0.2

+-

C 3 H 8 3 2.81

C4pI10

-+

$ NH3 -I-0.29

CO2

1.1 C2Hb

0.21 C5I-112

158.43 naphtha ( s t a b i l i z e d )
CH30W

+ Hz

@Mq 4- H70

The s e p a a t i o n o f t h e three-phase mixture c o n t a i n i n g t l i c rea

LLOf

p r o d u c t and t h e cool-ing w s t e r i s simulatpd w i t h ASPEN'S FLASH? block,

T h p s p l i t of Che hydrogcn-containing

gas strcam t o recycle or to purge

gas i s a r b i t r a r y and may be changed i f f u r t h e r I n f o r m a t i o n brcornes

a v a i l a b l e on t - h r e c y c l e stream or

011

t h e dependency of t h e hydrogena-

t i o n reaction(s) in .the r e a c t o r on the c o n c e n t r a t i o n of hydrogen,

The

s p l i t i s p r e s e n t l y s e t t o r e c y r l e 702 of t h e gas stream.

The naphtha s t a b i l i z e r t h a t t r e a t s the o r g a n i c phase from the
FLASH3 block i s modeled as a 30-lray d i s t i l l a t i o n r o u t i w u s i n g the
RADFRC block of ASPEN,

The colurnii i s k e p t hot rnough so t h a t there i s

o n l y one l i q u i d phase ( o r g a n i c ) .

No condenser i s used i n t h e RADFRC

b l o c k ; a FLASH3 ASPEN block i s used as a condenser, and o n l y the o r g a n i c

phase i s r e f l u x e d a f t e r being h e a t e d by a HEATER block.

The h y d r o t r e a t e d naphtha w a s given a m o l e c u l a r weigh!:

of

S c h r e i n e r , but no molecular welght w a s a s s i g n e d t o t h e g a s i f i e r naphtha,

I n t h i s s t u d y , a molecular weight of 100 was a s s i g n e d t o the gasifier

naphtha and mzy bc a d j u s t e d i f more informatfon i s obtained.

The

g a s i f i e r naphtha and h y d r o t r e a t e d napbtha are e n t e r e d as user-def-ined

components.

Except f o r t h e molecular weight, t h e p h y s i c a l p r o p e r t i e s

a r e t h o s e of t o l u e n e but may be a d j u s t e d as f u r t h e r information dfc-.

tntes,

e q u a t i o n of s t a t e w a s used f o r vapor:

The b.dlfeh-)i(wong-Soave

l i q u i d e q u l l i b r i u m and e n t h a l p y calcul at ions

I n t h e course of developing t h e ASPEN s i m u l a t i o n s , %t was found

n e c e s s a r y (or conveniiE.nt 1 to w r i t e . some

~~~~~~

subroutines to perform

some simple, r e p e t i t i v e tasks and to enhance the f l e x i b i l i t y and utility

of t h e models.

Two of these subroutines

i.zser--yiel.d r o u t i n e s DE'UOJ, and

IDECOMP, were d e s c r i b e d in t h e L u r g l gasj-fier section,

The gasifiers

also call three oth-er user S U ~ ~ O U ~ Z (developed

R ~ S
hy a p r e v f o u s s t u d y

1:

(1) ENYHLU, Salrnic,h c a l c u l a t e s the e n t h a l p y of ash a t any t e m p e r a t u r e ;

( 2 ) ASH.Il, which c a l c u l a t e s the e n t h a l p y of ash s o l i d s a t a g i v e n ternp e r a t u r e , and (3) S

of a stream.

which c a l c u l a t e s the average mohecular weighl:

User u n i t o p e r a t i o n s u b r o u t i n e BOILER a n

t o the coal enthalpy model ~

the enhancements

O are
~ dXi s c u~ s s e~d in
~ this
~
section.

M a i n t a i n i n g an a c c u r a t e steam b a l a n c e I s very important if usefiml.

s i m u l a t i o n s are to be produced,

User u n i t o p e r a t i o n model BOILER was

m - h t t e n f o r t h i s purpose.
waste he&

In many places i n t h e Tri-State proeess,

i s used t o make stea81~ The ~nechanism f o r t h i s i n ASPEN is

f o r Che HKA'IER or FLASH2 block chat is s i m u l a t i n g t h e c o o l i n g of the

p r o c e s s stream to r a l c u l a t e t h e h e a t duty and store &he r e s u l t in a heat
i n f o r m a t i o n stream.

ln o r d e r t o model the wasLe heat. b o i l e r , it i s

n e c e s s a r y t o a d j u s t t h e flow of feed water t o t h e b o l l e s s o that

saturated steam Is produced ~ i t h

no h e a t o r water "left over."
f u n c t i o n can be accompl-islaed w i t h an ASPEN DESIGN-SPEC;

This

however, t h e

i n p u t language i s clumsy, and i t s u s e r e q u i r e s i t e r a t i v e e a l c u l a t l o n s .

User u n i t o p e r a t i o n model BOILER performs t h i s f u n c t l o n rapi.dly.

S i m p l y p u t , BGTLER accepts an input h e a t stream and calculates the

water flow r a t e n e c e s s a r y t o o b c a i n t h e desired s t r a m c o n d i t i o n s .

d e s i r e d steam p r e s s u r e and degrees s u p e r h e a t ( d e f a u l t = 0.0)
v i a the HEAL v e c t o r in t h e ASPEN i n p u t language.

The

are passed

HOILEW performs t h e

n e c e s s a r y u n i t s conversion.
The ASPEN p h y s i c a l p r o p e r t y system p r o v i d e s several methods f o r
e s t i m a t i n g the heat of eornbustian o f a coal.

Provts-l.on w a s n o t made,

however, f o r the d i r e c t i n p u t of a known value of a c o a l ' s h e a t of cow-

bustion.

The model HCOALGEN has b ~ e nm o d i f i e d to allow t h i s option.

u s e t h e d i r e c t i n p u t o p t i o n , two s t e p s are necessary:

To

(1) t o s p e c i f y

o p t i o n six for t h e h e a t O E combustion (first o p t i o n code) i n RCOALGEN,

and (2) t o p u t t h e deslred h e a t of combiistion ( B t u / l b , d r y ) in t h e firsr-,
loeation o f the component a t t r i b u t e COALE?ISC.
Thc m o d i f i c a t l o n s t o IICOALGEN are q u i t e simple.

"he heat-of-

combustloii monitor s u b r o u t i n e ENEICC w a s modified t o accept an o p t i o n

code of 6.

F3hcn an o p t i o n eode o f 6 i s encountered, ENTBCC w j l l c a l l

45
S u b r o u t i n e ENT445 merely obtains the heat of

t h e new s u b r o u t i n e ENT445.

combustion from t h e component a t t r i b u t e v e c t o r , c o n v e r t s t h e u n i t s t o

S I , and r e t u r n s the v a l u e t o ENTBCC.

3.

INTEGRATION OF MODELS

A s can be s e e n i n Fig.

I , most of the uni% o p e r a t i o n s present i n

t h e T r l - S t a t e p r o j e c t f l o w s h e e t have been rmdeled u s f n g ASPEN.

[Unit

o p e r a t i o n s not modelea i n c l u d e head-end p r o c e s s i n g steps; (such as coal

p r e p a r a t i o n and the oxygen and steam p l a n t s ) and cleanup p r o c e s s e s (such

as ammonia and s i l l f u r r e c o v e r y . ) ?

In o r d e r t o perform o v e r a l l plant

m a t e r i a l and energy b a l a n c e s , i t would now be des-irable t o couple

a p p r o p r i a t e l y a11 of t h e developed models i n t o a s d n g l e simi-ilation,
P l a n t o u t p u t streams could t h e n be checked f o r v a r i o u s input f e e d and
i n t e r n a l process conditions e

I n t h i s way

t h e process eff i c i e n c y and/or

product s l a t e d e s i r e d could be optimized f o r a particular c o a l and

o v e r a l l Elclwslieet e

The c o u p l i n g of a l l of these ASPEN models i n t o a s h a l e s3mulation

program y i e l d s , however, a computer program chat is q u i t e ccmplcx and
one t h a t requfres a c o n s l d e r a b l e amount of care.

T h l s problem has been

circumvented by d i v i d i n g t h e o v e r a l l flowsheet dnto suhsets,

i n Fig.
groups:

21, the v a r i o u s ASPEN m o d e l s have been combinied i n t o flvc mjor

(1) h r g i gasifter, gas cooling, g a s - l i q u o r s e p a r a t i o n , arid

Texaco g a s i f i e r ; ( 2 ) k c t i s o l ;
nation, and SNG p u r i f i c a t l o n ;
MTG,

*9s shown

( 3 ) raetlianol s y n t h e s i s

W - s k l f t , metha-

( 4 ) naphtha h y d r o t r e a t e r ; and ( 5 ) 'I.lohPE

f r a c t i o n a t i o n , a l k y l a t i o n , and gasoline blending.

S e q u e n t g a l ex@-

c u t i o n of these major groups s h o u l d a l l o w a v e r a l l p l a n t balances t o he

achieved i n e s s e n t i a l l y a s i n g l e p a s s .

47
4.
The f i n a l Tri-Stace

**case13

S y n f u e l s P r o j e c t block f l o w diagram, e n t i t l e d

coal t o Gasoline

baseline Tri-State

SULTS

% a r t c r Size P l a n t , ' " 1 2 w a s used as t h e

case f o r checkfng t h e developed ASPEN models I n an

o v e r a l l s h n i l a t i o n p e r f o m e d by s e q u e n t i a l e x e c u t i o n of t h e major
groups.

To demonstrate t h e range of o p e r a b i l i t y of t h e s e models,

overall s i m u l a t i o n s were also performed u s i n g feed of I l l i n o i s No. 6

c o a l and t h e o r i g i n a l f u l l - s c a l e f e e d r a t e rsf Kentucky No. 9 c o a l to the

I:, l a n t

4.1

BASELlNE TRI-STATE CASE

I n the b a s e l i n e Tri-State

case,

240 trans/h of Kentucky No.

would be converted t o t r a n s p o r t a t i o n f u e l s and chemicals e

9 coal

The chemical

and p h y s i c a l c h a r a c t e r i s t i c s of t h i s coal are g i v e n in Table 4.

It

s h o u l d be noted t h a t t h e hydrogen and oxygen v a l u e s l i s t e d i n Table 4

i n c l u d e c o n t r i b u t i o n s from t h e m o i s t u r e i n t h e coal., so t h a t t h e u l t i m a t e
a n a l y s i s I s on an "as-received"

basis.

s i s i s r e q u i r e d by the ASPEN model.

T h i s form of t h e u l t i m a t e analy-

Before a s i m u l a t i o n could be

performed, i t was n e c e s s a r y t o match t h e ASPEN p r e d i c t e d Lurgi g a s i f i e r

o u t p u t r e s u l t s w i t h t h e e x p e r i m e n t a l l y determined o u t p u t of t h e L u r g i
g a s i f i e r used i n the SASOL t e s t of Kentucky No.

This was accomplished i n two s t e p s :

9 coal'

(see Appendix).

( 1 ) by v a r y i n g t h e REAL v e c t o r

s p e c i f i e d i n the ASPEN i n p u t f i l e and used by t h e s u b r o u t i n e DEVOL t o

form the v o l a t i l e p r o d u c t s , and ( 2 ) by v a r y i n g t h e temperature a t which

t h e f o l l o w i n g f i r s t two r e a c t i o n s of t h e REQUIL block took p l a c e :

48
Table 4.

C h c a i c a l and p h y s i c a l c h a r a c t e r i s t i c s
of Kentucky No. 9 coal.

UI timare a n a l y s i s (as r e c e i v e d coal)

15.4

Ash
Carbon
Bydrogerf
Nttrogen
Sulfur
oxygen

59.6
5.3
1.2
3.5

15.0
100.0

P r oxima t s ana ly 8 i s

Mois t u r c
F i x e d carbon
V o l a t i l e matter
Ash

8.2
43.4
33.0
15.4
100.0

S e n t of combustton = 1 ? , 4 7 5 B t u / l b ( d r y e o a l )

CO

+ H2Q

co

4- 3H2

-$ H2 -b CO2

* CHq

4- H26)

A comparisorz of t h e experimental and p r e d i c t e d g a s t f i e r r e s u l t s (using

1620 and 141OoP, respectfveiy, f o r thc two r e a c t i o n s above) i s shown in

Table 5.

lma agreement is q u i t e good; f u r t h e r refinement of the REAL

v e c t o r and/or t h e r e a c t i o n temperatures could make i t even b e t t e r .

t h e SASOL c o a l tesr,

known,

t h e amount of tar, C2+,

S l n c e these c o ~ p o n e ~ at sr e only

t h e i r Vector values

rt3ere

and phenol formed were

formed i n t h e s u b r o u t i n e

e a s l l y deter1114
ned.

Prom

DEVOL,

L-I a d d l t i o n , t h e water vec-

tor v a l u e was s e t t o account f o r the amount of w a t e r i n d i c a t e d by the

c o a l proxjmate analysis.

remalning v e c t o r v a l u e s ( f o r N2, @Hq, CO,

49

Table 5.

Lurgi g a s i f i e r o u t p u t u s i n g Kentucky No.

--

Mode 1

Clean tar produced

as X W c o a l fed:

9 coal

SASOZ c o a l test

5.6

5.6

41.4
15.4
30,8
9. P
0.9
1.0
1,4

40.8
15*9

Dry gas composition, X

Wy d r oge n

Carbon monoxide
Carbon d i o x i d e
Methane
C2 +
Nitrogen
Hydrogen s u l f i d e

30.6
.4

0*9
8,9
1.5

100.0

100.0

and CO,)

w e r e set t o make t h e t o t a l v e c t o r sum t o u n i t y w h i l e s l m u l t a -

n e o u s l y they w e r e manipulated, a l o n g w i t h t h e r e a c t i o n t e m p e r a t u r e s , t o
match t h e coal test d a t a .

0.2863,

0.340Q, 0.0131,

mation of H,,

c=Hq, H,O,

The f i n a l v e c t o r s o b t a i n e d were 0.0072,

0.0849,
6 0 , C2+,

0.0915,

0.0036,

and 8.1734 f o r t h e f o r -

60 2 phenol, and t a r , r e s p e c t i v e l y .

I n t e r m e d i a t e r e s u l t s of s e q u e n t i a l e x e c u t i o n o f the major groups

shown i n Fig. 21. are given i n Table 6.

The o u t p u t of t h e f i r s t major

group c o n s i s t s of t h e cooled g a s e s from t h e Lurgi and Texaco g a s i f i e r s

and i s t h e i n p u t t o t h e R e e t i s o l model.

The C O S , NTl[3, and C2-C4

output

streams w e r e not i n p u t t e d t o t h e R e c t i s a l model because they have not

y e t been i n c o r p o r a t e d i n t o t h a t model ($.e.,

for t h e s e s p e c i e s were not a v a i l a b l e ) .

b i n a r y i n t e r a c t i o n parameters

The C6H6 e n t r y r e p r e s e n t s t h e

amount of naphtha e n t e r i n g rthe second major group.

Since ( 1 ) t h e SASOL

c o a l tests d i d not i n d i c a t e t h e f o r m a t i o n of any naphtha, and (2) t h e

50
ZaZ11-. 6.

Coiiiponcnr

Interme3iate simulat. i o n r e s u l t s f o r base1 i n e T r i - S t a t e

G a s i f i e r and
cooling o u t p u t ,
Rectisol i n p u t
( 1b-mo 1/h 1

case

synthesis
o u t p u t , MTG
j. np u t
(lb-mol/h )r

&OH

Kertisol output,
MeOH s y n t h e s i s i n p u t
(Ib-moP/h)

16,583

7,660

11,823
3,460,
333b
100
418
jii
6a
173
41"

0.4
0.7
120
13

14,532
7,551
1,441
3,306
..-

4L2
0. y a

0.2

O u t p u t stream component, b a t not used i n i n p u t stream.

h s e d as an i n p u t strean only.
e
MeOH s y n t h e s i s = ( 5 3 4 4 lb--mol/h)(32,042 l.b/lb-mol) ( 2 4 h/d3/(2000
1 b / t o n ) = 2670 t m s / d ; MeOh s y n t h e s i s from CasP 13 Flowsheet = 2670
t 0 1 7 s /d

Case 13 flawsheet

Tewaco g a s i f i r : r ,

shows naphtha rota t h e k c t i s o l . u n i t b e i n g fed t o t h e

the f o u r t h major group, naphtha hydrotreat-ing, has been

o m i t t e d i n t h i s o v e r a l l sirraillation.
The s i x L4DPRC blocks i n the ASPEN B e e t i s o l modal are shown in

Fig.

8.

The first two of t h e s e d i s t l l l a t i o n u n i t s are used t o remove

t h e II S i m p u r i t y , w h t l e t h e remaining u n i t s are used p r i m a s f l y t o

2

r e c o v e r naphtha frvlln t h s s y n t h e s i s gas stream.

10 actual ASPEN simula-

t i o n s , a l l of t h e s e RADF'RC blocks converged i n d i v i d u a l l y , but o v e r a l l

convergence of t h e e n t i r e f l o ~ h e e t :was very d i f f i c u l t t o o b t a i n .

NUDE~GUS

a t t e m p t s were made t o a c h i e v e convergence of t h e right h a l f of

t h e flowsheet (Fig. 8) by (1) b r e a k i n g the t i e s between t h e t w o h a l v e s

51

of t h e f l o w s h e e t (elg. streams R E C W 1

RECLIQ2, and

and

~~~~~~~~~~

( 2 ) r e p l a c i n g he RADFRC blocks by sLmple SEP blocks, i n d i v i d u a l l y and

in varying combinations e

Unfortunately

a i d e d t h e convergence p ~ o b l e mes

ere

n e i t h e r o f these approaches

were some f n d i c a t i o n s

that t h e convergence d i f f i c u l t i e s could be trace

$WO

i n n e r loops in

T h s e inner loops are d e f i n e d by the

t h e r i g h t half of the flowsheet*

following:

to

however,

( I ) streams RECACIDG, ~~~A~~~~

REGVAPPT, E C L I Q 1 9 , and

~ and
A ~ (2)1 streams
8 ~
RECLEQl7, R.ECLTQ18,

and

~ Tearing
~ ~

stream REcVM-as -might e o n f t r m .if t h e s e l o o p s are indeed the souT(le o f

t h e convergence p r o b l e
The number of i t e r a t i o n s was cot i n c r e a s e d above the default v a l u e s

because the hPstory f i l e d i d nor i n d i c a t e that t h e maximum number of

However, more it r r a t l o i a s and/or t h e use

i t e r a t i o n s was being approached.

of d i f f e r e n t convergence schemes could be t r i e d t o see i f any inprovement

c o u l d be made.

were used.

For t h i s s i m u l a t i o n , only the f i r s t two W F R C blocks

T h i s w a s r e a s o n a b l e s i n c e all. of the H2S i s removed from t h e

gas stream by t h e s e f i r s t two blocks, while t h e remaining blocks are

p r i m a r i l y used to r e c o v e r naphtha.

Sfmce t h e SASOL coal t e s t d i d not

I n d i c a t e t h e formation of any naphtha, t h e use of t h e remaining W P R C

blocks w a s not considered essential.

"he entire ASPEN language I s

i n c l u d e d i n t h e i n p u t f i l e , but t h e r i g h t half of t h e flowsheet shown Pn

F i g . 8 has been commented o u t .

These could be used by anyone d e s i r i n g

to check t h e recovery of t h e naphtha i n t h e s y n t h e s i s gas stream.

The output front t h e Rectisal u n i t , w i t h i t a mch reduced c o n t e n t of

H25 and COz, is f e d i n t o t h e t h i r d major group: methanol s y n t h e s i s ,

s h i f t , and methanation.

The p r e d i c t e d amount of methanol produced,

52
2670 tons/d, was forced t o agree closcly with tlw 2670 tons/d shown on

the Case 13 flowsheet by varying t h e rt.,cyele r a t i o in t h e methanol

synthesis aodel-

To obtahn agreement, a recycle r a t i o o f 1.63 was used.

The predicted composition and pate of SNG prod;ic23ui-t are shown in

T a b l e 7 , d o n g w i t h the ~ u t p t sof the fifth najor groixp (MTG,

fractionation, and alkylation).

The ASPEN block diagrams shorn in Figs. 13 and 14 f o r t h e frattlonation and a l k y l a t - i o n sections, respecttvcly

use several RlhDPRC

Ac; was t h e case for t h e RectisoP model, these

distillation blocks.

RBDFRC blocks can be made t o converge indtvPdually, b u t are very d i f f i c u l t to converge when p a r t of t h e overall. f l o w s h e e t *

Table 7.

in these

Predicted o u t p u t s f o r baseline T r f - S t a t e case

------

product ton

_
I

Model

39.5

SNG, MNSCFI)

4,300

LPG, l b / h
I s o b u t a n e , lbJh

GasolPne

?%is,

lb/h

Component

Total

Case 13 Flowsheet
37-0

4,300

4,750
85,400

85,600

1b-mo I/"h.
30.7
205.7
1.2
4,104.2

0.71
4- 7 3
0.03
94.53

4,341.8

100.00

53
s i m u l a t i o n s t h e KmFRC blocks have been r e p l a c e d by simple SEP blocks
which requfre no i t e r a t i v e c a l c u l a t i o n s *

"I'laese blocks were c a l i b r a t e d

u s i n g t h e r e s u l t s o b t a i n e d when t h e a p p r o p r i a t e i n d i v i d u a l

w a s used.

The ASPEN input f % l e developed i n thBs work, however, c o n t a i n s

b o t h t h e SEP b l a c k s and t h e original RADFRC b l o c k s , wfth t h e l a t t e r

being commented out.

If d e s i r e d , a u s e r could remove t h e comments and

use a l l or p a r t o f t h e RADPRC blocks, along w i t h two specaal FOR

b l o c k s (ETSPEG and GSSPEC) u s e f u l f o r s e t t l n g t h e product f l o w s a t e s from

b l o c k s PIDEETHAN and MGASST

(see Pig.

13).

The s i m u l a t i o n p r e d i c t s that: 39.5 MPI SCFD af SNG, contaitihng 94.5%

methane, w i l l be produced.

T h i s v a l u e compares f a v o r a b l y w i t h t h e 37 MM

SCFD shown on t h e Case 13 flowsheet.

The models p r e d i c t t h a t 4760 Ib/h

o f i s o b u t a n e i s formed (stream XSIBUT on F4.g. 1 4 ) , which is 0,2X higher

t h a n t h e flowskeet v a l u e of 4750 l b / h .

(stream GAS on Fjg. 1 4 ) o f 85,40

v a l u e o f 85,600 l b f h .

The p r e d i c t e d g a s o l i n e v a l u e

l b / h i s 0.2X less t h a n t h e flowsheet

The p r e d i c t e d LPG p r o d u c t i o n i s f d e n t i c a l to the

f l o w s h e e t v a l u e of 4300 l b f h .

These predicted produet rates w e r e

o b t a h e d by modifying t h e y i e l d s t r u c t u r e used f o r the MTG r e a c t o r so

t h a t t h e LPG, isobutane, and g a s o l i n e product rates would match t h e
T r i - S t a t e flowsheet.

This T r i - S t a t e y k l d s t r u c t u r e i s shown In Table 8.

When t h e y i e l d s t r u c t u r e given by Schreiner9 and shown i n Table 9 w a s

u s e d , t h e p r o d u c t i o n rates p r e d i c t e d by t h e models were changed cons i d e r a b l y , as Shawn in Table 10.

It should be noted t h a t a s l i g h t e r r o r

w i l l occur i n t h e atom b a l a n c e around t h e r e a c t o r when e i t h e r of t h e s e

y i e l d s t r u c t u r e s are used.

This e r r o r i s caused by lumping a l l of t h e

p r o d u c t s beyond Cg i n t o a s i n g l e - t e r m l a b e l e d g a s o l i n e and t h e n

om

-l If--0

1%
\g

.-I

03

LQ

- -.

&,

Af

rn

o0

I
n o o e rn m rn e
e m m
a N uz a 0 P. 9-l m

N u2 03

vl

03.3
O r 0 0 N 0 0 0 4 0 N a 0 4
0 1%~ h
0-l00000080000000N

omoooooooooooooo8

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

ddddddddddddddddd

Prcrdlact:ican

Schreiner y i e l d
S p:TU ctu re

T r i - S t a t e ytelnz
seructure

assigning this pseudocomponent the p r o p e r t i e s of n-heptane

If these

higher moleanlar weight products were not combined, however, an additional 31 components would have t0 be alsed i n t h e r P t d n d e r of tile
simulati@ln. u s i n g Schreiner s yfeld s t n x t u r e 9 the p r e d f e t e d aaollint of

gasoline produced is eonsfderably reduced, w h i l e the p r e d i c t e d m o u n t of

isobutane and LPG produced are larger,

Thus the basic d:EEfererzce between

t h e two y h l d s t r u c t u r e s has been to shift produet f o r m a t i o n toward the

higher carbon ( $ . e . * gasalFne) end of t h e groc3uc.t slate.

4.2

FULL-SIZE TRP-STATE CASE

I n t h e f u l l - s i z e T r l - S t a c e case9 960 t o n s of coal. per 11oer1- would

b e f e d to tbe L u r g i gastfier.

the

This case was sIwul.ated to ensure that

developed could operate over a range of flow rates.

intermediate s i m u l a t f s n results are shown in Table 11.

~o~~~~~~~~

with

Table 6 shows that each component of t h e gasifier o u t p u t streams have

been increased by a factor of 4 , the same factor t h a t t h e coal f e e d rate
h a s been increased,

Similarly, t h e Kectisol o u t p u t streams have been

Increased by a f a c t o r of 4 as cornpared to Table 6 ,

Tne R

c o n t e ~ ~oft

56

6h9131

66,334
30,641

1.6
2.8
481
54

30,204
5,764

47,292

13,222

1,647 a
2.8

1,571
2,044
2 5u

593,

1,138

245

27,

me

the gas stream has been reduced by 99.867: so that t h e t o t a l gas stream
c o n t a i n s orrly 24 ppm H S .
2

'%he amount of n e t h a n o 1 produced,

10,680 tnns/d,

i s a l s o a factor of i~ t.lmes ehe baseldne case? v a l u e of 2670 tons/d.

The p r e d i c t e d product r a t e s f o r t h f s case are shown I n Tab1.e 12.
As w o u l d be expected, since

ethanol i s being converted t o g a s o l i n e , the

p r e d d r t e i l g a s o l i n e p r s d u c t I o n r a t e of 341,6363 l b / h fs 4 t f w s the base-

l i n e val.ue cf 85,400 I b / h .

The estimzited i s o b u t a n e , SNG, and LFG rates

are a l s o 4 t i m e s the baseline v a l u e s .

Thus the change i n coal f e e d r a t e

p r o p a r t I o n a P l y changed a14 t h e o u t p u t p r o d u c t rates , showing tihe

rangeability of the ASPEN models developed i n Lhis s t u d y .

Demonstrating such v e r a a t - l l i t y and range of o p e r a b i l i t y i s very
I m p o r t a n t f o r any process simulation s i n c e it shows i f the wnsde.1~

5 '7
P r e d i c t e d o u t p u t s for f u l l - s i z e T r i - S t a t e case

Table 12.

Model

Production

158

SNG, MlMSCFD
LPG, l b / h
Isobutane, l b / h
Gasoline, lb/h

19,200

341,600
S WG

u
I

Component

lbVOl/h
_elm_

118

0.68

CO
CR4

5
16,376

0.03
94.55

Total

17,321

100" 80

H2
N2

822

4.74

Meat of combustion (HHV) = 956 Btu/SCF

I__

developed have been s u f f i c i e n t l y g e n e r a l i z e d .

In t h i s case, s p e c i f i c

values f o r c e r t a i n feeds, splits, and o u t p u t s w e r e r e p l a c e d w i t h r a t i o s ,

o f t e n u s i n g FORT

blocks t o set i n i t i a l estimates.

Similar tests of

any new models t h a t are developed should be made t o a s s u r e g e n e r a l i t y .

4.3

ILLINOIS No. 6 FEED

I n o r d e r t o demonstrate t h e v e r s a t i l i t y of the ASPEN models developed

i n t h i s s t u d y , t h e b a s e l i n e T r i - S t a t e case ( i r e . $ 240 tons of c o a l f e d

p e r hour) was s i m u l a t e d u s i n g I l l i n o i s N o * 6 coal as f e e d t o t h e Lurgd
gasifier.

'She chemical and p h y s i c a l c h a r a c t e r i s t i c s of t h i s c o a l , shown

i n Table 13, w e r e taken from t e s t data.

16

Table 14 shows that the composition of t h e d r y gas produced using the

Illinois N o . 6 c o a l , u s i n g the same R E f i vector a d reaction temperatures

58

T a b l e 13.

Chemical and physical characteristtcs

o f 11 1.j-noE.s Ma. 6 coal.

Ash
C a .a-?ro n
Hytl w g e i?
Nitrogen
Sulfur
Oxygen

9.0
64.3
5.5
1.2
2.8
17.2

100.0

P r o s im a t e ana 1y s i s

Mo i
s turn
Fixed carbon
V o l a t i l e natter
Ash

10.3
46.0
34. 7
9.0
--

100.0
Beat of combust-ion = 12,770 B t u / l b (dry c o a l )
----_-..I.....I

1
1
1
1

TabLe 14,

___.

1___

Lurgi g a s i f i e r o u t p u t u s i n g Illinois Nae 6 coal

as compared to Kentucky No. 9 coal
14.1.. No.
coal.

Clean &ar produerd, as

MAF coal f e d :

Ky. No. 9
coal

5.9

5.6

40,3
16.0
30. '7
10.0

41.4

Dry gas composition, %

Hydr ogeri
Carbon momxide
Carbori d i o x i d e
Methane

1.0

c 2 -1-

N i t rogen
Hydrogen sulfide?

1.0
1.0

..^..,..._._

100.0

15.4
30.8
9.1
8.9
1.0
1.4

100.0

59
as

previously, is v e r y sfrnllar r a t h a t p r e d i r t x d for the Kentucky No, 9

coal,

Higher percentages of carban mc~noxide and aaetha-tae a r p~r e d i c t e d for

the Tl.lincis c o a l , while a s l i g h t l y lower pereenmge

of

kydrogen is expected,

Because of its lower sulfur e m t e n t , the amoan: of BzS predicted i s

c o n s i d e r a b l y less ttiian that p r e d t c t e d u e b g the Kentucky

9 coal.

The i n t e r m e d i a t e simulation resulss are shewn in Table 15.

X cow

parison with Table 6 shows that the g a s i f i e r asintputs are very simflar
and t h a t the Rectisol u n i t again remooes over 99% of the B2S from t h e
gas stream.

The fact that some HzS Ps p r e d i c t e d t o r e m k n gn the

synthesis gas stream for each of these sinnuPations Pndicates t h a t zinc

oxide p a r a

b.as

should probutaiy be

a v o i d pofsoning sf its c a t a l y s t ,

E IPBxPc31 syntbes is to

~ C L Xto

The pr-ed-lcted a m u : ~ t of metZ~ano2pro-

duced, 2772 tuns/d is 3.8% greater thzera ?:Ire baselhue m ~ <valueR

?

The estimated outputs; are given in T a b l e 16,

Table 7 shows t h a t more SNG2 LPG, lisobaitarae, a n

Bison w"el.1
g<3aourtcr. would be

produced u s i n g I k l i n i s i a Eoe 6 coal, as empared t o tile u w of Kentucky

No. 9 coal.

The SMG produced 1s again coqcsscd of 95% methane, with the

major kmpurity being mitrrpgen.

cf!

major

reasO3-i

f o r che Increased

p r o d u c t rates using the Illinois coal i s P t s Bower ash e m t e n t (9.0% as

opposed to 15.42 f o r t h e Kentucky coakg,

The ASPEN process; simulator has been used to m d e l t h e Tri-State

S-ndireet coal liquefaction process.

Individual eo

onenta of the

T r i - S t a t e flowsheet were developed Ln modular form so t h a t they w i l l

have a p p l i c a t i o n to a number of d l f f e r e n t . process alternatives,

developed i n this s t u d y i n c l u d e the following:

Models

Lurgi g a s i f i e r , Texmco

(Zomponent

Gasifier and
casling output,
Rectisal input
(1b-mol /h )

(lb-mol/h)
0.4

16,897

1
124

8,279
1,448

12,379

3 949

3,764

ma

1 oob

427

ga

189

15

0.2

42 1
0. 5a

407

MeOH s y n t h e s i s
o u t p u t , mG
Pnput

E b c t i s o l olatptlt,
Me08 synthesis i n p u t
(1b-asol / i k )

16,949
8,399

~~

196

63

7,211c

a O u t p u t stream component, but not u s e d i n input stream.

b e d as an i n p u t stream only.
%eOH synthesis = (7211 lbaro3/h)(32,042 1b/lb-erc,oE)(24 h/i1)/(2000
l b / t o n ) = 2772 tons/d
T a b l e 16.

Predicted o u t p u t s u s i n g I l l i n o i s N 9 . 6

Production

--.I

44.3

4,460
4,940
88$600

S NG
___I

H2
N2

I.-.--.

MDdE?l

SMG, MMSC'FD
LPG, l b / h
Is obutane , l b / b
G a s o l i n e lb/h

Component
_-.I

coal

lb-mol/h

13.0

co

CHI+

210.2
0.4
4,640.4

Total

4,864.0

Meat of combustion (HHV)

0.27

4,32

0.01
- 95.40
100.00
=:

964 Btu/SCF

61

g a s i f i e r , synthesis gas c o o l i n g , R e c t i s o l , methanol s y n t h e s i s ; , methanolto-gasoline,

@@-shift,

n e t h a n a t i o n , and naphtha h y d r o t r e a t i n g .

In a d d i -

t i o n , a n enhancement has been m d e t o ASPEN t o a l l o w for t h e d i r e c t

i n p u t of c o a l h e a t of combustion v a l u e s , and t h r e e FORT

programs were

developed t o h a n d l e t h e d e v o l a t i l i z a t i o n and decomposition of c o a l i n

dl

g a s i f i e r and t h e h a n d l i n g of bojller f e e d water.

S i m u l a t i o n s were made of t h r e e c a s e s : (1) t h e b a s e l i n e T r i - S t a t e
f l o w s h e e t w i t h Kentucky NoI 9 c o a l f e d i n a t 240 tons,%;
Tri-State

(2) a f u l l - s i z e

c a s e w i t h Kentucky No. 9 c o a l f e d i n at 960 t o n e / h ; and ( 3 ) t h e

baseline Tri-State

case w i t h I l l i n o i s k. 6 c o a l f e d at 240 tons/h,

P r e d i c t i o n of t h e s y n t h e s i s gas composition produced by the h r g i

g a s i f i e r was c a l i b r a t e d u s i n g t h e SASOL c o a l t e s t data.

For t h e first

case, t h e s i m u l a t i o n was f o r c e d t o match t h e p r o d u c t i o n rates of methan o l , LPG, i s o b u t a n e , and g a s o l i n e as i n d i c a t e d by t h e T r f - S t a t e Case 13

flowsheet.

This w a s accomplished hy (1) u s i n g a r e c y c l e ratio of 1 , 6 3

i n t h e methanol s y n t h e s i s model, and (2) modifying t h e EaTG r e a c t o r y i e l d

structure.

Cbadrupling t h e c o a l f e e d rate of t h e f i r s t case, t h e second

ease i n d i c a t e d t h a t e x a c t l y f o u r times as much SNG, LPG, i s a b u t a n e , and

g a s o l i n e would be produce&

The u s e of I l l i n o i s No. 6 coal i n the t h i r d

case r e s u l t e d Pn o u t p u t s s l i g h t l y h i g h e r t h a n t h o s e p r e d i c t e d by
Kentucky No. 9 coal.

The a n t i c i p a t e d i s o b u t a n e , LPG, and g a s o l i n e pro--

d u c t i o n rates are 3.8% h i g h e r f o r the I l l i n o i s coal, w h i l e t h e SNG prod u c t i o n would be expected t o be 12% h i g h e r .

6.

REFERENCES

Paul F. R. Kudol.ph, P. K. H z r b e s t , atid H. Vferrath, " G a s i f i c a t i o n

of US--NestF_j-n1 and Eastern Coals in the Jnrrgi Ery-Ash and t h e
B r i t i s h G a s j h r g i S1 aggiwg G a s i f i e r s , presen%sda t t h e 4 t h Annual
Coal U t P I i z a t i s n Conference9 i%oust.oii, Texas, NOY. 17-19, 1981.

3.

4.

5.

6.

7.

8.

R. Salmon, M. S.. E d w a r d s , and R. M. Whim, Pmduct-iorl of MethmpzoZ

a d Me-t'ruriol-Related F u e h from Coal, OWL-5664 (May 1980).

9.

10.

11.

.Je C. SePover, '"Coal Conversfon t o Methanol Gasoline and SNG,"

p r e s e n t e d at the 31st -Annual AIChE bkctirng, Defrrc~it,Michigan,
P*ejg, 16-19, 1981.

12.

T ~ i - S & a t oSynfuel6 P m j e c t Reviey Contract 835504, T r E - S t a t e

S y n f i . ~ I sCompany (June 1982).

13.

A b r i e f srimmary of the SP.SOL coal t e s t d a t a

is shown in Table 17.

These d a t a represent a vary small p a r ' s of t1-r~overall r e p o r t and s l ~ o u l d

not be i n t e r p r e t a d as r e p r e s e n t i n g the d e s i g n condf tloras of t h e

TrS-State

pro.jec&, Extensive data and di-scuesiicptrc of t h e coal test ate

i n c l u d e d i n the. DOE r e p o r t ,

;mad i r t @ r e s t e d r e a d e r s are r e f e r r e d t o

it,

The d a t a p r e s e n t e d in T a b l c 17 wem-r. usedl to tleterndne the flow

r a t e s of oxygen, steam, and water to the Lurgrh gasifier In thts

simulation.

1030'F

In a d d i t i o n , the average g a s i f i e r ouP:let t e m p e r a t u r e o f

w a s used in t h e s i m u l a t i o n .

Furt1-tc-c coal r e s t r e s u l t s (i.ea,

produet gas composition a n d acasunl: of clean t a r produced) wcrc p r c ~ s e i i t e d

e a r l i e r i n Table 5.

T a b l e 17.
Fec?d rates u s e d I n SASOZ c o a l t e s t and
L u r g i gasifier simulatlrsn of b a s e l i n e "b"ri-State case

Coal (MhI.')

15.9

T o t a l as received c o a l

20. E?

Oxygen
Steam
Wareer

8.6
34,6
7.7

Ash
Moisture

Gasifier outlet
t e m p e r a t u r e OF

0,764
0.154
(I*082

3.2
1.7

366,226
73,576
39,137
---.----

0.74i.
0,154
Oe082

479,039
0,413
1.663
0.370

1000- 1060

65

197,741
796,864
177,337

0.413
1.663
0.378

1030

Dist

ORNL / n.I-86 11
Category UC-9063

INTERPJAL DISTRIBUTION

1-5.
6,
7.
8-12.
13
(I

14-18

19.
20.
21

22.
23
24.
25.
26.
27-31.
a

32
33 *
34 *
35 *
36.
37.
e

J. M. Begovich

38

39

c.

H. Byers
K. 7%. Canon
J. H. C l i n t o n
S. D. C l i n t o n
B. D. Cochran
E. D. Collins
T. L. Donaldson
P. w. F i s h e r
C . W. Forsberg
R. K. Genung
H a W. Godbee
M. V. H e l f r i c h
J . R , Hightower
P. J . Johnson
R , F. Judksns
J. A. K l e i n
D. L . Lennon
K. 11, L i n
E. W. McDaniel.
C. P. iYIeCinni5

.
I

40.

41.
42.

43-45.
46
47.
48.
J

49-Sl.
52.
53.
54.
55.
56
57.
r

58-59

69.

41-62,

63
64.
D

L. E * Mc:Neese
J, J. Perona
A.
Rivera
S. M. Robtmcsn
R e Salmcn
c. H. Shappert
M. Sirnan-Tov

z.

c. EB.

W.

Smith.

6 . Ulrich

v. c.

A . Vaughen
J . IC, Walker

R, M.

mam

S. K. Whatkey
S . H. t J i l s o n

6. R. R E l P ( c o n s u l t a n t )
A , M. Squire!, ( c o n s u l t a n t )
C 6 S I t K a l Research Libr~3b-y
Docmen9: Referpnce Section
L a b o r a t o r y Records
Laboratory Records - RC
O k N L Patent Office

EXTERNAL DTSTRLBUTLON

Department of Energy, Oak R i d g e O p e r a t i o n s , P s O e Box E ,

O a k Ridge, TN 37838:
65. O f f i c e oLr A s s i s t a n t Managcr f o r Energy Research and DeveZapment
66, J. A . lieafsnyder
67. M. R. Rogers
U.S.

68-69.
70.

71.
72.

73-77.
78.

R. E. Barkilr, I n t e r n a t i o n a l X i n e r a l s and Ghcmisals Corp.

P . 0 . Box 2 0 1 , Terre Haute I N 47805
A . DYSOR, Tennessee V a l l e y h U t h G r i t y , 300 C o r o u n and Black 23.dga,
Chattanooga 'i'N 37401.
W, E , E a r l , U n i v e r s i t y of Canterbury, Dept. o f C h m i r d l E~zgineezi n g , C h r i s t church 4 , New Zealand
G , D. Girnson, I n t e r n a t i o n a l Coal R e f i n i n g Co., P . 0 . Mox 2 7 5 2 ,
Allentown PA l8OOl
I,. E. Graham, P r o c e s s Technology arid Engineering Branch,
Morgnntown Energy Technclogy C e n t e r , P.O. Box 8 8 8 ,
Elorgantown XJV 24505
J . M. Holmes, U n i v e r s i t y o f Tennessee, D e p t . of C h e m i c a l ,
M e t a l l u r e i c a l and Polymer Engl n e e r i n g , 41 9 ]Dougherty Engineer i ng
B u i l d i n g , Knoxvil1.e TN 37496

67

68

Neville H o l t , t X e = t L L c Powc'r Research Institute, 3412 HI i b v i e w

Ave. P a l o Alto CA '34303
80. M. C. Mil J i r i a u , Malcoa SD Groiip Inc
TWO P a r k Ave.,
NCZ~JYork NY 10016
81. U. Z i t z o w , I ' ~ n i l ~ r , s eV~1-lr-y
e
Awthnrity, 300 Coroorr and Black
H u i l d i n s , Chattanooga TN 37401
82-334.
Gives distr i b u i - i o n as s h o m in I'ID-450Q under Coal Coinversidjii
and Utilization - L i q u e f a c L l o n , UC--90d.
79.

U 5 GOVERNMENT P R l N l lNG OFFICE 1983 E16 955 151