,.

1.2.5 GASX~XCATXON - UNIT 21

The Texaco Coal G a s i f i c a t i o n Process (TCGP), chara~terized as an

e n t r a i n e d s l a g g i n g downflow g a s i f i e r , is utilized i u the ~ e s i ~ n of t h e
G a s o l i n e P l a n t . The u t i l i z a t i o n of t h i s t e c h n o l o g y was s p e c i f i e d i n the
Cooperative Agreement Statement of L~ork~ith e n g i n e e r i n g d e s i g n i n f o r m a t i o n
obtained through Texaco Development Corporation.

A. Basis of Design

The q u a n t i t y of synthesis gas generation capacity required by

the size of the Gasoline Plant ue,-.essitated th~ incorporation of 20 opeza~ing
coal gaslfler trains and two spares luto the design. The total of 22 trains
are arranged in four modules wit,h two modules containing six trains (five
operating plus one spare) and :he remaining two ~odules contain five each.
The feed a~d product streams shown on the followlng two pages depict the
design basis utilized in the d".siE~ of this unit.

B. _Process Selection Rat,io.al_~e

The design of the Gaeollne Plant centers around the TCGP for
combustion of Kentucky No. 9 high-sulfur, agglomerating coal specified in the
C o o p e r a t i v e Agreement. This commercially a v a i l a b l e t e c h n o l o g y has been
demonstrated as capable of efficiently gasifying hlgh-sulfur content, high
swelling index coals; operatln8 at hlgh-pressure and affordin E an excellent
heat recovery scheme to reduce o p e r a t i n g cost; and producing an
environmentally acceptable synEas and nonhazardous slag.

In the ensuing years, a commercially sized 8Qmonstration

plant has been built and £s operating at the RuhrcheeL%e Chemlc~1 Complex in
mm.e~i----, °

O'~erhausen-Holten, West Germany. The Ruhrchemle gaslfler has been running

successfully since early 1978. For these reason.s, Texaco has llcensed this
process foe other co~nercisl installations and considers this process to be
~ m

commercial. w ~

~-1.2.5-1

°.
-- A d
 P

GaslfJ.er Feed S t r e a m s
t
i inl

Total Coal Slurry Total Oxygen

to C a~iflcation to Gasification
Component (Ib mol/hr) (lb ~ol/hr)

CH 2
co
CO2 i

02 54,968.76
N2 i

276.28
H2S
COS m

Total. Dry, "Ib mo.~/hr Proprietary 55,245.04

I{20 m

T o t a l Wet, l b mol/hr 55,245.04

Coal, lb/hr
Ash, Ib/l~
Carbon

Total, lb/hr Proprle~ary 1,770~040

~ l m m m m m m m w m u e

PEe~suEe, p s l a 1~200 1,015

Temperature, °F 200 200

( ,

I~-1.2.5-2

,.

p P
...., ,.., ~`~`~`~d~.~.~p~.~y~..~:~¢~Z~2.~*;J~`~.~J4~.~Z~. . ~ ~ ` ~ ~!~:~;~,~.~ :.'~'.;~.~=:~,~.~,~,~.:~,~.~t~..~...~.i~;~,~.~,~2,~'.~.~e.~'_,~Z.,~..~.~,,,v:..,.~.:.,.
:,'~ ,.~,,~...,:,~.~,;..~_..~.
. . ~
 i

Product Streams

m i ii

Total Raw Syngas

Component (ib mol/hr) (molZ)
i . i i m-, • ~ J i m

62~580.97 36.19
CH4 343.44 0.20
C0 75,760.77 43.81
CO2 30,788.72 17.81
02 m m

N2 823.02 0.48
Ar 276.24 0.16
H2S 2,201.17 1.27
COS 135.71 m 0.08
Total Dry, lb mol/tn" 172,910.04 100.00
H20 123.170.76
Total Wet, ib mol/hr 296,080.80

Total., 1b/he 5,945,560.00

Pressure, psia 874

Temperature, °F 435
m

II-1.2.5-3
I ,
 r

C. Process Description

The e q u i p m e n t a r r a n g e m e n t and m a t e r i a l b a l a n c e f o r . t h i s unit

are shown on Process Plow and Control Diagram D-21-MP-INP. mm

The c o a l - w a t e r slurry i s . pumped a t h i g h p r e s s u r e t h r o u g h t h e

slurry preheater into the gaslfler. Zn the gaslfler, the slurry is partially
oxidized with oxygen at 900 pslg and at high temperature. The hot synthesis
Eas and molten slag generated flows downward from the gaslfier into the
radiant boiler, where much of the heat of reaction is recovered by generating
hlgh-pressure saturated steam. The slag falls into the w a t e r sump and
solldifles and s h a t t e r 8 to glass-llke granules. The synthesis gas is
withdrawn from the radiant boiler for further processing,

The g a s e x i t i n g the radiant waste heat boiler undergoes a

succession of scrubbing stages to remove particulate material. At the final
step, the gas is w~shed with condensate before it flows t o the CO Shift Unit.

A substantial portion of the ash and recycle slag in the

gaslfier feed agglomerates into coarse molten slag droplets. The slag is
solidified and quenched in the radiant boiler. This slag settles through the
water bath and is collected in a lock hopper. The contents of the lock hopper
a r e discharged p e r i o d i c a l l y ,

The c o a r s e s l a g i s s e n t t o s l a g d i s p o s a l w h i l e w a t e r and s l a g
f i n e s p a s s i n g t h r o u g h a s c r e e n are pumped t o t h e c l a r i f i c a t i o n system.

Water s t r e a m s from t h e r a d i a n t boiler, s l a g d i s c h a r g e , and

the scrubber system contain suspended ash and char particles, which are
routed to a clarification s y s t e m . The f i n e slag and u n c o n v e r t e d c o a l a r e
formed i n a c o n c e n t r a t e d u u d e r f l o w t h a t i s r e t u r n e d t o t h e C o a l G r i n d i n g and
Slurry Preparation Unit, The c l a r i f i ~ d w a t e r o v e r f l o w s i n t o a w a t e r h o l d i n g
-..
,,• tank for reuse in the gasification system,
t

i . II-1.2.5-4

p ......~ - ,-.,, ~ , ~ i ~ ¥ ~ ~ ~ ~ ~ .~L~C~'I

'-~ - ~ , ' ~ ' ~ . ~ ~ ~ d~~ ~ ~.,:~ P
 q

v.'.o,, , , , ...... ~ - .j II II I

~'------- I

C ',,

D. Risk Assessment

The c o m m e r c i a l l y a v a i l a b l e Texaco Coal G a s i f i c a t i o n P r o c e s s

o f f e r e d through Texaco Development Corporation (TDC) i s an e x p a n s i o n o f ~he
w e l l - p r o v e n Texaco S y n t h e s i s Cas G e n e r a t i o n P r o c e s s . TDC, a wholly owned
s u b s i d i a r y of Texaco I n c . , has been engaged in the development and l i c e n s i n g
o f the Texaco S y n e h e s i s Gas Generation Process s~nce 1945. The s y n t h e s i s gas
generated by this technology l e a mixture predominantly of hydrogen end
carbon moaoxide~ which is used as a feedstock for the production of ammonia,
methanol, hydrogen; oxo products, reducing gas, fuel gas, and Ylscher-Tropsch
l~quid hydrocarbons.

Over 80 Texaco synthesis gas generation plants have been

llcensed since the early 19508 ~nvolvln E some 150 gasiflers, Early units were
natural gas-flred. Later, liquid fuels such as naphtha and hesvy fuel oil
were Introduced. The majority of plants now in operaelon utilize heavy
residual oils,

Generator s i z e has i n c r e a s e d steadily, with present units

p r o d u c i n g 20 times t h e o u t p u t o f t h e e a r l y commercial u n i t s . Operating
pressure has ~ s e n from 350 psi~ in i n i t i a l p l a n t s to 1,200 ps~g in one p l a n t
iu o p e r a t i o n since 1968. Commercial o p e r a t i o n as low as 30 psi~ has a l s o b e e n
demonstrated. Pilot unit commercial o p e r a t i o u on r e s i d u a l f u e l s has been
c o n d u c t e d a t 2,500 p s i E , SynEas c o o l e r s have b e e n u s e d in 20 c o m m e r c i a l
p l a n t s , ~ h i l e the remainder have used d i r e c t quench.

The Texaco Coal G a s i f i c a t i o n P r o c e s s £s a m o d i f i c a t i o n o f t h e

Texaco S y n t h e s i s Cas Generation P r o c e s s , producing g e n e r a l l y the same type o f
.... : ~:~...

syntheses gas for the same commercial a p p l i c a t i o n s . Developmeut work on c o a l

gasification, started in 1948, has involved l a r g e - s c a l e p i l o t unit o p e r a t i o n
on many s o l i d f u e l s i n c l u d i n g l i g u i t u s , bituminous c o a l s , anthracites, coal-
l i q u e f a c t i o n r e s i d u e s , and petroleum cokes.

11-1.2.5-5

p 5
 ~g ......... ~ . . . . . . ~ ptl ~ t~g0 p l~oJ e ~ n~eu ~ P I ~
p

A dumonstratlon plant was erected at the Morgantown Ordnance

Works in West Virginia in 1956. This unit charged I00 tons per day of an
eastern bituminous coal in water slurry and was in operation for 2 years.
This piant confirmed gaslfler scale-up cr~terla and demonstrated the ash-
handling system,

At t h e M o n t e b e l l o Research Laboratory, extensive facilities

~re availa~l~ fc~ the gasification of solid fuels. These include three 15- to
20-tpd coal gasification pilot units including one stand-alone pilot plant.
TestlnE has included ga¢ cooling, sulfur removal, and w a s t e w a t e r treatment. q
II
/
These pilot units have been operating on a wlde range of coals st pressures
ran~ing from 300 to 1,200 psi. Detailed environment data have been
accumulated on both eastern and western U.S. coal.

Ruhrchemie AO (RCH) and R u h r k o h l e AG (RAG) completed a

demonstration plant utilizing the Texace Coal Gasification Process in 1977 at
Oherhausen-Holten, Germany. The demonstration plant has been in ope~atlon
more than 4 years. Over I0,000 hours of operation, with a total throughput of
more than 50,000 tons of coal, have been achieved. Eleven different types of
coal have been tested. Three of the coal grades used were supplled from the
United States.

A number o f v a r i a b l e s that may a f f e c t the c o a l g a s i f i c a t i o n

L /

process i n t h e C a s o l i n e Plant a~e:

(I) Gasifier thermal performance

(2) Egfectiveuess o f ash removal and carbon r e c y c l e systems.

(3) Pumpabillty range o f h i g h s o l i d s c o n t e n t s l u r r i e s .

(4) Assessment of unexpected corrosion, erosion, and

refractory llfe.

II-I • 2.5-6
CI The temperatures mad pressures involved in the Gasoline Plant are
wlthi~ the range for which equlpmont has been eupplled for petrochemical and
process plants. Some key items in this process area are slurry charge pumps,
sluzTy p r e h e a t i n g , g a s i f i e r b u r n e r , and g a s l f l e r / w a s t e h e a t b o i l e r s y s t e m .

The removal and h a n d l i n g of s l a g from the gasifier are

p a r t i c u l a r l ~ a r d u o u s a p p l i c a t i o n s f o r v a l v i n g . Specie1 a t t e n t i o n was a p p l i e d
to the details of valve design. Safety interlocks on v a l v e s and
i n s t r u m e n t a t i o n f o r sequencing p r e v e n t m a l o p e r a t t o n of t h e l o c k b o p p e r s y s t e m
for slag collecting and d u m p i n g . The g a s i f i c a t i o n u n i t s a r e provided with
~'larmo to warn o f abnormal c o n d i t i o n s . The purpose of t h e a l a r m s y s t e m i s to
allow operators to take corrective action b e f o r e an a u t o m a t i c shutdown i s
initiated.

The efficiency of the process can be a f f e c t e d by t h r e e

signifiennt variables including slurry concentration, ash content of the
coal, and m e l t i n g p o i n t o£ the a s h . The g a s i f i c a t i o n facilities were designed
f o r a range of c o a l a n a l y s e s c e n t e r e d on the d e s i g n c o a l u s e d i n t h e n o r m a l
operating condlt£ono An i n c r e a s e in ash content, a decrease in slurry
c o n c e n t r a t i o n , or an i n c r e a s e i n c o m b u s t i o n zone t e m p e r a t u r e requires more
c o a l and o x y g e n f e e d per Btu o f h e a t i n g v a l u e of gas p r o d u c e d . This r e s u l t s
in h i g h e r o p e r a t i n g c o s t s than p r o v i d e d i n t h e Operating Cost Su~nary.

Technical risk is related mainly to equipment life and

maintenance r e q u i r e m e n t s , which i n c l u d e s t h e r a t e of wear o f t h e r e f r a c t o r y .
Life of at least a y e a r i s e x p e c t e d . Two s p a r e g a s i f i e r t r a i n s were i n c l u d e d
in the deslgn so that replacement of refractory can be scheduled
eequentiallyo The s p a r e g a s t f l e r trains a l s o allow an a g g r e s s i v e program of
recognlzlnE and s o l v l n ~ problems t o be e a r r l e d o u t by p e r i o d i c rotation of
units for inspection, p r e v e n t i v e m a i n t e n a n c e , and m a i n t e n a n c e .

The s l u r r y charge pump~ p r o v i d e d are c o m m m e r e l a l l y a v a i l a b l e

proven e q u i p m e n t , and r e q u i r e no s c a l e - u p or e x t r a p o l a t i o n o f d e s i g n . The

C pumps a r e d i s c u s s e d
Preparation.
In the s e c t i o n covering Coal Grinding and Slur~'y

II-1.2.5-7

I
 The g a s l f i e r design pressure o f 900 p s i and d e s l g n basis
( s l u r r y c o n c e n t r a t i o n co~, t y p e s , g a s l f i e r t e m p e r a t u r e s , e t c . ) a r e c o n s i d e r e d
well within c o m m e r c l a l u s e and c o n s e r v a t i v e l y s e t . Burner r e p l a c e m e n t i s a
s l m p l e m a t t e r and adequate s p a r e s a r e s t o c k e d . Casifler lock hopper valves
are c r i t i c a l i t e m s , b u t o p e r a e i n g u n i t s have c o n f i r m e d t e c h n i c a l a d e q u a c y ,

R e ~ c t l o n s w i t h h l g h - p u r i t y oxygen produce l a r g e q u a n t l t l e s of
heat and r e q u i r e careful monitoring and c o n t r o l . As d e s c r i b e d h e r e i n , the
gaslfler system i s h i g h l y i n s t r u m e n t e d to p r o v i d e o p e r a t o r s w i t h i n f o r m a t i o n
on t h e o p e r a t i n g conditions. This i n f o r m a t i o n is integrated into a trip
s y s t e m t h a t shuts down a t r a i n a u t o m a t i c a l l y i f u n s a f e c o n d i t i o n s a r i s e .

The waste heat boiler system is a very critical Item sir it

represents simultaneous gas cooling and recovery of a major portion of the
heat (steam) utilized in plant drivers. The design is based on the successful
operating experience in the Ruhrchem~e demonstration plant at Oberhausev.
Special soot blowin E equipment is utilized in maintaining heat transfer
surface coefficients and that source of technology is used for materlal
selection.

The m~ans by which slag is discharged from t h e gaslfier

requires speclal attention during operation to minimize the risk associated
with the scale-up from existing units.

A slguificant risk results from the uncertainty relatlng to

corrosion rates in the circulating water system, although information
available at present suggests that this corrosion may not be unusually high.

Uncertainties associated with the design and o p e r a t i o n of

c o a l s l u r r y h e a t e r s do n o t pose s e r i o u s r i s k s as the p l a n t can be o p e r a t e d
s a t l s f a c t o r i l y w i t h o u t them.

I r - I . 2.5-8
P

CIJ I
In general, the Kaaification section contains certain
equipmont mentioned above t h a t has r e l a t i v e l y severe operat£n8 cond£tJ.one;
however, commercial operation has proven the a d e q u a c y of the process. In
c o n j u n c t i o n with c o n s e r v a t i v e designs and a d e q u a t e sparing, the technical
r i s k i s considered minimal.

II-1.2.5-9
 'lmm,w,m.~,

E. p~ocssa ~low andConcro!.DiaKrnm (l,,~cludlns M a t e r i a l

Bslanco)

Tho Procaa8 Plow and Control D~agram f o : G a s i f i c a t i o n UniC 21

i s as f o l l o w s :

Drawing No. Titl.___~e

D-21-~P-INP PFCD G a s i f i c a t i o n - UniC 21

ZZ-2 .2 .5-10
 . los ,~,,m. e.

.... :, ,t" , ~ , I ~ I, 4~

A
F
I

F
MAK( UP IATI~
1'0 XOOUL(
.....v.. TO IIO~UL(It

~
i
I
m

1' 0_,2:,,5 im)O~(;( '

~ 10 KOOULr4
10 UO6ULI:3
TO~[ Z
[~ (~ ,, ,
I
: In,

TO MOOUL(]
TO~[ It II
e
I O-t;~,-ue-t "";)rE(o COAL
SLURRYPI~ARATIOi(
I
I
I
([

1
r
I
c

l
m

I
I

D
¢CI~T F[ ,) C6AL ~YG~ [
CARBON 3211TTI 67,00 -- I

I
HYOPlOGS'N 2 ~ 05;.p 4, O0
OXYGEN 31 r ~ I 7 &. SO 43~ TSO
N~Ii 5? TS) l , 20
AIt'GOla ~ ~ 2 t ?Stl
I
m SULFL~,, I0. 250 3. llO I

r
CHLORINE 480 (1. IO
AS~SI.AC ~s. ~zz oleo
: ~ T TOTAL 49G, 255 ~ 442, SlO ~ T / I I A T E R REC1fCL(
! IfAT[R 46, ~jl$ ~ I
lET TOTAL S~Tr 114 I00,00 i
stPp, OnT s,~] s,3to
Sl,rO ~ 6.]zi --
E OT~LO XXY DRY 12, 352

r ~'-'-" ' ' ' ' ' 1 I

~,FI I, I
Kf~alWTIQN

3
~1
i
I I
ii~
n I~-0~.11~1.~<~'~ .~P'I'~I";'I" F. . . . . .
C ~ . , ~ pml .~,1 ,.~' ~ I
, I,,,,,'3 ~d Jr~i I ~1
& ¢,,~nI I .rt I ,tAd ~ I
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i F ._
. . . ..
It-.--.

2 I

P
D
 ~.,,~,;~I.~;~,',.~.T~'I~.~'~..,:~ ,, ,.,, ,,e. . . . .

, ,
6 I 7
m

SCRUBBER SYSTI~U
14OTF2~
h Tile RASIF|CAT[OI~UUIT COHSt~TSOF 111ENTY-
TWO Tg~]NS (~'4).|0 OPSNkliNO AND i rd;AR~S~
|H FOUR (4) UCOULESa
~ n ~ ~ ~ ~ ~ ~ ~ ~
MOOULE I CONSISTSOF TRAIHS ! TXRUE-
IS OPERATING, / ~#ARi~I
MI~IULE 2 CON$1575Of TRAINS T TXRU I I - A
15 OPERATING)
MODULE 3 C0~|$1$ OF TRA~H$ 12 7XRU I?"
(S OPf~ATZH6, I SPARE)
XOt)ULE 4 COHSISTSOF TRA~N I! THRLI2=-
(50PER/~,T]I(GI
2, KA]ERLAL OALAflC( S~EAIIS AI~ STEAMRATE
ARE SIl~ilH AT HOR3ALOPERATXNOCOHO]T]ONS
FOA ONE MOI)UL[ OF 5 GUZF]ER TTLAZNSOF k
HOil]NAL 50.000 8PD CASOL[H( PLANT.

PROCESScOarl£1tSATr-',~O-S$-UP"I XP J

s ~ I ,,-BZ..W-ll n~

s o ~ Fe~MT(n C 0-23-~-e ~ 1 RAW GAS

CO~OKERT GA$ZFICAT]Olt

~oL.m. LB MOIJHR um.Z

e ~ m ~ i o-sz.-w-nn ~e) 2.02 15. 645. 2T ~,~19
_C_C_C_C_C_C_C_C
__C
~~ 16.04 B5. OG 0.20
CO 20.0I tot 9,40o21 4~e1
co| 44. Ol T~ GgT~ to IT, BI
@ [~ (~, ~s ,o co ~,zrr I o"'"~"' 'e> E| 20.O2 2O5.TS O.48
Ju" 39. 94 69. 07 O. IG
HIS ~1,06 550, 2~1 I.Z'/
COS ~o, OT o. o8
TOTAL olaf 43. 2ZT. 46 I00. O0
: HIO 152-65
TOTAL T4~OZO. 17
LB~I~ I~,406, 240
~ECULI~ II1'. :'0. OB
I~SCFDa,, 674, I
FS~k 874
°F 4)5

70 EASTe~T(e T e ~ G t o-z'/-Le-t m.> EFFLUENT SlAG TO

COld'RENT UT£R DISPOSAL
D
I.ZVH~ UYHR
I SLABTO ozseos~. I o-i~.-o .~> 3~)5
HYDROGEN

I'
OXYGEN ~

SULFUR" ~
CHLO(~(( i
ASH/9.,AG 114~1 76574 '6
DRY TOTAL [[]
kATi~ 572971 317'/I
TOTAL 574020 110740

D2ll~l NP.DO,4
U.S. DEPARTHI:HT OF ENERGY
VJ~GR~C:E & CO. ~DmJc~
59,E~B B.P.O.
COAl.. - TO - HE-I'HANOL - TO - GASOL]I~E PLANT
~ m r ~ m
'~ P P F , OVAL II¢ .,I.,, I I I
PROCESSFLOW Ik COW~,ROLD~GR~I ~ A
GA$~F'JL~ATZOR- ~ 21
t

4@ o
 F. P,lot,,,Plan/General, Arrangement Drawings

Plot P l a n / G e n e r a l Arrangement Drawings for Gasification

U n i t ~1 are as follows:

D,ra~n~ No. Titl...__~e

D-21-PD-INP Plot Plan - Unit 21 Gasification

D-21-PD-2NP Plot Plan - Unit 21 G a s i f i c a t i o n

D-21-MH-1RP General Arrangement - Gasification - Unlt 21

Caslfler Area - Plan and Elevation

am

(
II-1.2.5-11
 .... ..... ~`~`~i=~a~i~È`~im~mn~ri~<~-zt~`~`~`~[£J~y.~"~- ..... ~ ............... , . . ~ . t . . . . . ~,?t~,.,l . . . . . i, . . . . . . . , , • .. . . . . . . . .~ , P

1 I 2 I ~ I 4t .
N MATCH LIN~N, IO 025'-0'

A
0 SLAGCONVEYOR
AND P ~ AREA
!
]
I
SLAGCONVEYOR
AND P ~ A R E A

l'Illiillliillliliil~
I

GASIFIERS GASIFIERS
I AND HEAT AND HEAT
,q, RECOVERY RECOVERY
I',-
SYSTEM SYSTEM
,,I
B hi

.J
I i
!
i
DRLV; DRUMS i DRUMS ] DRUMS
n~
AND
HEAT '- - , . - , AND i AND ! AND
HEAT ! HEAT
.J
EXCHANGERS [XCHANGERS i EXCHANGERS . _ _ - - IEXC~I~ERS
i
i
; I
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n i

,t, ,."1 r'-... I I ~.-'7-'4..

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/ I -->'q.- / !/ ><:~ " "';:> '"" | ...,.."1"" I'TI~I ~I~ECTIR
"'d u.-º" I / •-'-._L.~ . . . . --IL.. " " " "- "l" / I--

iu
i BURNERCOOLING
CARBONAND ASH WATERCOOLING
RECOVERYFACILITIES FACILITIES

mu ,,i i
C/L ROADI!l MATCHLINE N.96:]0'-0'

.>
F~

I
O~ICN
@
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g. Si~Line Dlasram

Single-Line Diagram f o r G a s i f i c a t i o n Unit 21 i s as follows:

,Drawing No. Titl._~e

D-51-EE-3NP One-Line D i a g r a m - Uuitu 21 and 24

II-1.2.5-12
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NOTESa
416ov..cc _ _ j.e~ . . . . l, PROVI~£All, Alh't, IRTF..~ AT ALL LOCATIOn3liARKEO

NOTE I

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 1.2.6 OXYGEN - UNIT 22

The partial oxidation process assoclatod with the Texaco

Gaslflcatlon Process (TCCP) r e q u i r e s an o x i d i z e r to nustaln the partial
combustion of the coal feedstock. T b l s o x i d i z e r i n the form of h l g h - p u r l t y
gaseous oxygen Is s u p p l i e d from an a i r s e p a r a t i o n plant which cryogenically
separates air into its ~aJor composer, i s o x y g e n and n i t r o g e n . All of the
oxygen i s r e q u i r e d f o r the g a s i f i c a t i o n process while the nitrogen produced
is used for process, purge, catalyst regeneratlon, and blanketing
requirements in the process and offs~te units.

A. ,Basis of Design

The d e s i g n o f t h e a i r s e p a r a t l o n ( o x y g e n ) p l e a t i s based upon

the u t l l l t y s u p p l y of 25,000 s t p d o f o x y g e n a t 9 9 . 5 X p u r i t y . The o x y g e n i s
compressed to i,I00 pslg to feed t h e TCGP. Due to the l a r g e requlrement o f
oxygen, t e n p a r a l l e l 2,500-stpd air separation plants (trains), whlch a r e
b a s e d on t h e l a r g e s t commercially available, are Included in t h e d e s i g n .
Total ~Itrogen produced from these plants is about 8,500 stpd and a v a i l a b l e
at 7 pBig with s maximum I0 ppmv oxygen c o n t e n t . The f e e d and product s t r e a m s
for this unit are shown on the next page.

B. i
Process Selection Rationale
I J

A summary o f t h e p r o c e s s s e l e c t i o n r a t l o n a l e dlsc~ssed below

is b a s e d upon t h e e n g i n e e r i n g t r a d e - o f f s t u d y performed f o r t b l s u n i t .

I. Oxygen P l a n t Vendor C o m p a r i s o n . Investigations were

made o f t h e prlnclpal slr sepsratlon plant suppliers i n orde~ to e s t a b l i s h a
source of information for the prellmlnary design. These investigations
included Air Liqulae, Lotepro, Union C a r b i d e , A l t o n , and Air P r o d u c t s . The
approach dictated for this unit was t h a t the air separation plant is a
process u t i l l t y wbich i s r e q u i r e d to supply the specific a~ount o f p u r i t y
oxygen n o t e d above f o r p r o c e s s r e q u l r e m e n t s . Therefore, the selection o f an
a i r s e p a r a t l o u p l a n t vendor was n o t n e c e s s a r y and was n o t made.

II-1.2.6-1
 Baaed p r l m a r l l y on the extensive experience by ~ l r
Liqutde in i t s s u p p l y ot l a r g e - s c a l e oxygen p l a n t s f o r the SASOL f a c i l i t y and
lower capital cost, It usa determined that data for the prellmlnary design
would be obtained from Air Liqulde.

2, Gaseous Oxygen Compression vs Liquid Oxygen Pumpl.ng,

Two alternative oxygen pressurization process schemes were considered:
8aseous oxygen compression and liquid oxygen pumping. Of the £1ve oxY8en
plar, t ~ e n d o r s contacted, none had c o n s i d e r a b l e experience i n l i q u i d oxygen
pumping. A i r c o , Air Produces, Lotepro, and Union C a r b i d e f a v o r e d gaseous
oxygen c o m p e a s l o n . A i r L l q u l d e was o p e n , however; its very extensive
experience r e c e n t l y i n the SASOL p l a n t s is with c e n t r i f u g a l compression So
500 pstg,

From the oxygen plane vendors' comments, it was concluded

t h a t the c u r r e n t i n d u s t r y consensus is that gaseous oxygen compression In
preferred to liquid oxygen pumping, and g a s e o u s oxygen compression was
researched further.

3. G a s e o u s Oxygen C o m p r e s s i o n , Based on c u r r e n t commercial

experience, the selected scheme was centrlfugal compression to 610 pslg
followed by reciprocating compression So 1,100 pslg. Sulzer and Demag
confirmed that is 1982 there were centrifugal oxygen compressors operating at
1,500 pslg and that commercial experience is being developed for all-
centrifugal oxygen compressors.

C. Process Description

The e u u l p m e n t a r r a n g e m e n t and m a t e r i a l b a l a n c e f o r t h i s u n i t
are shown on Process Flow and Control Dlagrams D-22-HP-1NP, -2NP, -3NP, -4NP,
-SNP, and -6NP.

II-1.2,6-2
w

( :
Feed 8treamo i ,J _ ,,,

i i , n , j lllll

~J.r to Cold Box

Cemponent (lb mol/hr) (molX)
J . .

N2 210,733 78.11
br 2,509 0.93
02 56,548 20.96
Total dry, lb mol/hr 269,790 100.00
H20 m

To~al wet, lb mol/hr 269,790

TotalD lb/hr 7,813,640
Pressure, psia 84
Temperature, oF 95

Product Streams

Oxygen to
GasLfication Nitrogen
Component (ib mollhr) (molX) ( I b mol/hr) (mol~)
wu

N2 m
- 23,470.6 100.00
02 54,968.8 99.50 0.2 Max. 10 ppmv
Ar 276.2
i u,
0.50 1.2 50 ppmv
Total dry, lb mol/br 55,245.0 100.00 23,472.0 100.00
H20 m

Total wet, ib mol/hr 55,245.0 23,472.0

Total, Ib/hr 1,770,030 657,600
Pressure, psia 1,115 22
Temperature, °F 201 90

C
IT-1.2.6-3

-- r

m
I I H i
s I 4v
I
p P

Atmospheric alr, after passing t h r o u g h an i n l e t alr f11ter,

is compressed in t h e alr compressor. Followlng compression, the air is
cooled In dlrect-contact W a t e r Wash Tower 22-01-1203. The c o o l e d compressed
air then enters the cold box, an e n c l o s e d steel structure containing
cryogenic equipment f i l l e d w,tth i n s u l a t i n g m a t e r i a l . The a i r e n t e r ~ t h r o u g h a
set of automatic switching valves that controls the flow to Reversing
Exchangvr 22-0|-1306, The r e v e r s i n g exchanger Is an a s s e m b l y o£ b r a z e d
aluminum, e x t e n d e d s u r f a c e heat exchangers that have the dual function of
coollng the air and r e m o v i n g w a t e r and c a r b o n d l o x l d e from i t at the same
t i m e . The a l r tu c o o l e d by h e a t exchange w l t h out£1owlng gaseous p r o d u c t s and
waste nltrogcv. The p a s s a g e s a r e a r r a n g e d so t h a t s t p r e d e t e r m i n e d i n t e r v a l s
t h e a i r and waste n i t r o g e n s t r e a m s a r e s w l t c h e d by o p e r a t i o n of t h e v a l v e s at
t h e warm e n d , with the check valves controlling the f l o w s sc t h e c o l d end.
When t h e a i r i s c o o l e d , t h e c o n t a i n e d m o i s t u r e i s condensed as w a t e r and i c e ,
and t h e c a r b o n d i o x i d e is deposited as s s o l i d a t l o ~ e r t e m p e r a t u r e s . When
the air and w a s t e n t t r o g e n passages are switched over, the deposits ere
evaporated i n t o t h e v e n t s t r e a m in one s e t o f p a s s a g e s and c a r r i e d out o f t h e
system w h i l e t h e impurities from the air are deposited in the other set.
Since ell the passages are in thermal c o n t a c t w i t h each o t h e r and ~rlth the
products, there is continuous heat exchange.

The cooled alr, nov at a b o u t - 2 8 0 ° F and c l o s e to Its dew

point, i s s e n t to t h e bottom of H i g h - P r e s s u r e Column 2 2 - 0 1 - 1 2 0 2 a s feed. The
prlnclpal function of this column i s t o p r o v l d e pure n i t r o g e n a t t h e t o p as
p r o d u c t , impure l i q u i d n i t r o g e n as r e f l u x f o r L o w - P r e s s u r e Column 2 2 - 0 1 - 1 2 0 1 ,
and a liquid rlch in oxygen at t h e b o t t o m as f e e d for the low-pressure
column. Re£1ux £or ~he h i g h - p r e s s u r e column i s provided by H a t h V a p o r i z e r
22-01-1310, which by v a p o r i z i n g l i q u i d oxygen In the sump o f the l o w - p r e s s u r e
column, condenses n i t r o g e n r i s i n g from below.

Rich liquid f r o m t h e sump o£ t h e h l g h - p r e s s u r e column Is

w i t h d r a w n and p a s s e d through either Rich L1quld Filter 22-01-2203 or
22-01-2204. These £ 1 l t e r s , fllled ~rlth a d s o r b e n t , s e r v e t o remove t h e b u l k o f
°

any hydrocarbons that enter wlth the alr and a r e not deposited In the
i
reversing exchanger. Followlng the fllters, t h e r l c h l l q u l d i s s u h c o o l e d In

II-I.2.6-4

P
P
p

C Auxiliary V a p o r i z e r 22-01-1308 by v a p o r i z i n g lSquid oxygen and then expanded

i n t o t h e l o w - p r e s s u r e column as f e e d . The l o w - p r e s s u r e column o p e r a t e s at
about 19 p a l a , w i t h b o i l - u p from the main v a p o r i z e r and r i c h l i q u i d f e e d and
impure l i q u i d n i t r o g e n r e f l u x f r o ~ t h e h ~ g h - p r e s s u r e column.

Pure o x y g e n Ls p r o d u c e d a t the bottom of the low-pressure

c o l u m n . As a s a f e t y precaution, part of the l!quld is circulated via
thermoslphon action in the auxiliary v a p o r i z e r t h r o u g h L i q u i d Oxygen F i l t e r
22-01-.2202, which i o similar to the rich liquid filters. Another part of the
llquld oxygen will be withdrawn to Oxygen Vaporizer 22-01-1311, where it is
partially e v a p o r a t e d to g i v e a gaseous oxygen p r o d u c t . The gaseous p r o d u c t is
withdrawn overhead from Separator 22-01-1204, while excess liquid is returned
to the sump of the low-pressure column by either Oxygen Pump 22-01-1503 or
22-01-1504. In order to evaporate the liquid oxygen, a stream of gas having
essentially the same composition as air' is taken from the high-pressure
c o l u m n , c o n d e n s e d , and t h e n f e d back t o the column. Par~ c£ t h i s condensed

( a i r i s withdrawn again from t h e column and used as a d d i t i o n a l

l o w - p r e s s u r e column.
reflux in the

|
Gaseous waste nitrogen is produced at the top of the
low-pressure column. This is used in Subcooler 22-01-1309 to subcool the
liquid nitrogen p r o d u c t and r e f l u x s t r e a m s ~nd ~he l i q u i d a i r r e f l u x . The
4

waste i s be warmed f u r t h e r by c o n d e n s i n g a s m a l l a i r e t r e a m and by t h e p u r e

gaseous nitrogen product before it p~sses out through the reversing
e x c h a n g e r , removing the d e p o s i t e d w a t e r and c a r b o n d i o x i d e a s St i s finally
warmed t o a m b i e n t t e m p e r a t u r e and e x h a u s t e d t h r o u g h a s i l e n c e r . The gaseous
oxygen and n i t r o g e n p r o d u c t s ~lso flow out t h r o u g h t h e r e v e r s i n g ezehanger,
l e a v i n g a t ambient t e m p e r a t u r e , r e a d y f o r c o m p r e s s i o n .

In o r d e r to m a i n t a i n the c o r r e c t t e m p e r a t u r e s t h r o u g h o u t the
cold box, it is necessary to produce refrigeration at a low-temperature
l e v e l . This i s achieved by t a k i n g some pure gaseous n i t r o g e n from the top of
the high-pressure column, reheating it partially in the cold-reversing
exchanger and then expanding i t i n Turbine 22-01-1803. The t u r b i n e i s coupled

11-i,2.6-5

I I
i
 t

to on electric generator, and the gas temperature wlll be lowered by about

70°F while producing power. It is be sent back through the subcooler and the
r e v e z a l n g exchanger as gaseous nitrogen p r o d u c t .

The plant is provided with the means to dispose of purged

llqulds by evaporation, using warm compressed alr In Purge Stack 22-01-1401.
For derlmlng and reactivation of filters, Derlme System 22-01-2803 wlth
Regeneration Heater 22-01-1321 is provided, and the dry alr heated i n
D e f r o s t i n ~ Heater 22-01-1312.

D. Risk Assessment

The gasification unit requires a maximum o f 24,600 stpd of

oxygen at 1,100 pslg. Ten oxygen plants provide thls~ High-pressure oxygen
gas is provided by compressing the gaseous oxygen from the cold box in two
stages. The centrlfugal compressor compresses oxygen to about 610 psig and
tbe reciprocating compressor uo 1,100 pslg. The nitrogen gas required by the
process units is provided by compressing t h e low-pressure nitrogen produced
In the cold box Using this approach, most of the equipment remains within
the limits of commercially proven technology. The recently commissioned
3 x 1,000 stpd oxygen facillty near Houston employs this combination to
compress the oxygen output to 1,250 pslg, the only difference being the
capacity of the oxygen cnmpressors: 2,500 stpd vs 1,000 stpd.

The oxygen s u p p l y i s o f c r l t l c a l importance to the gaslflers

to maintain plant output, Fortunately, in recent years there has been
excellent expsrlence wlth large oxygen plants. The design selected is similar
to the system operated successfully at SASOL. A i r compressor and oxygen
compressor selections have been influenced strongly by commercial experience.
The ozygen plants at SASOL and this plant produce 2,500 stpd of oxygen st 500
pslg and I,I00 pslg, respectlvely. The oxygen compression facilities are now
designed and operated with a very high level of safety and rellablli~y.

II-1.2.6-6

........ . , . . . . . . . .. . . . . . . . . . . . . . . . .

4~__ s ] 8 I z i_
 J

P .r:

i!r',

The c o l d box, with f e w m o v £ n g p a r e s and 100% i n s t a l l e d

s p a r e s , contributed very l i t t l e Co s h u t d o v n t i m e o f t h e p l a n t . With normal
air quality, t h e r e are no problems o f c o r r o s i o n using the s p e c i f i e d ataadard
m a t e r i a l s o f c o n s t r u c t i o n . Adequate oxygen c a p a c i t y i s i n c l u d e d t o a l l o w f o r
flexible operation o f the g a s i f i e r s and maintenance, dertm~ag, e t c .

C
XI-1.2o6-7

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~l~t f l m ~ l ~ s ~ rV~F ~ IIIIII ~rJ 4 j ~11~ I i~ ~ II~l 14 ~l~rlll~tf~l~lql~ ~ ~1~ ,

Z. Process,Flow and C o n t r o l Diagram-, ( I n c l u d i n g Haterial Balance)

Process Flow and C o n C r o l D i a g r a m s f o r Oxygen Plant Unit 22 a r e

as f o l l o w s :

Drawin~ No, ~
Title
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D-22-MP-INP PFCD OxyEen P l a n t - U n i t 22 A i r C o m p r e s s i o n

D-22-MP-2NP PFCD Oxygen P l a n t - U n i t 22 Cold Box
D-22-MP-3NP P¥CD Oxygen P l a n t - U n i t 22 Cold Box
D-22-MP-4NP PFCD Oxygen P l a n t - O n i t 22 Oxygen C o m p r e s s i o n
D-22-MP-SNP PFCD Oxygen P ! a n t - U n i t 22 Common E q u i p m e n t
D-22-MP-'6NP PFCD Oxygen P l a n t - U n i t 22 M a t e r i a l Balance

~ r

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HOL ~IGHT L6 HOUI'.R uOL X tB uOL/HR MOL LO UOL/HR I~)l. ll LO,MOOJH~,i UOL~' LO MOL./lai MOL1(
.H 2 2O.OZ 2It I)25.I't ?l, I I 820, 20 78. I I ~4,)T TII. I I 2 Ii,Opt. :SO T8, I l o.0 0.01
k" 39,14 Z61,05 0o9,~ 9. 6G O.9'1 O. 29 0.9) 250.00 0.93 37.GZ 0.50:
. o2 :~.oo ISr 893. SO 20, 9G 222. 24 20, 96 G.54 20.96 5~6';4. Ors - 2,(1.9~, o.IZl ::'-.",""
S, 49G. 08 99. 50 o.0~I tOr~
.,~GTALFLOW 29~0T0,50 I00, O0 I, 05(~.30 IO0,O0 11.20 100.00 26, 979_1 I01£O0 8,524.50 I00. 09
~ L IIIFJr~III ~'O,96 28. 96 28. 96 28. 96
z,~.~Ol t~..oo! .
32.04 28,0~' I
LB/HR el2, 9'1'0 30, 708' so~ ,JJq~ 177,004
4,

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P~.~,"RE PSIA
....TFJdP[RATURE"F
255, G6
14.3
80
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60
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I, IHE MATERIAL BALANCE5H0111O~ lllIS 5P,A ~
INO IS FOR ONE OF TEll IIIAIH5 A.~DFOR
floRUAt. OPERAT][OR.
2, THEREAt4ETHREEI~AIHS IN HOUE5 el AHD
=:ll AND ~ TRAINSIN MOD~.ES=2 AHO m4.
A

3, AIR LOSSES.~/se~. OCCURBEllEEH ^lit

IHTAKE AND COLD OOX, (STREAM%'/Z`%
) IS HOT
INDICATEDON THE PFCI~).

• .,... ~,a~ru ~CE, To a~x~s W,STr mTeO,~

L--~" IlOL Y LD UOL/HR UOL Z
0,0= 0,0 IBr 72-'i. IS 90.00
21,69 0.50 2Z3. 5G I. IT
5e495.09 ! _99.55 159.59 0,83
I00.00 51524,50 IOR,OR 19r lOT,]tO iO0,O0
32.04 . 28. 19
I TTr004 536~SOl
50. 39' IT4.02
2Z h 115 ,, 14.?
9O 201 gO

6
m

D2~II4~RP,OCA
t U.S. DEPP.RTMENT OF ENERGY
e,~sxe'rr W,R,I~AACE & CO, 'KEmUCKV
5B.BM B.P.D.
COAL - TO - HETHANOL - TO - GASOLINE PLPJTi"
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P. Plot Plan/General Arrangement Drawings

Plot Plan/General Arrangement Drawings for Oxygen Plant Unit 22

are as follows:

Drawln~ No. Tltl__._.ee

D-22-PD-INP Plot Plan - Unit 22 Oxygen Plant

D-~2-PD-2NP Plot Plan -. Unit 22 Oxygen Plant

D-22-PD-3NP Plot Plan - Units 22 and 51 Oxygen and N i t r o g e n

Compression

D-22-PD-4~P ~tion - Unit 22 O x y g e n P l a n t

C
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= , ,
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~Err W.R. G R A C E & C O . ~u~r
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COAL - TO - METHANOL - TO - GASOLINE PLANT
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 i G. Single-Line D,£agram

S i n g l e - L i n e Diagram for Oxygen Plane Un4C 22 io ~ £ollo~m:

D r g ~ n g No. Title

D-$1-EE-4NP One-L&ue Diagram - Units 22 and 23

m
m - -

.1,
II-1.2.6-10
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1 ,1
NOTESI
I. PRBItI~,4Mw~ ~'TER$AT ALL LOC4TI~ ~ •
2, ~OVIDE$0~ RElY TO,41.Lar)rORSJC/~D ~.

J_

- ' I- U.$. DEPARTMENT OF F.NERGY ' ~

• ~ I-e~sK~'r w.q. GRACE & CO. KENTUCKY
- I ~ • ~ / 5o.ooo..Ro.
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13
 Ill I __ Ill

C, 1.2.7 CO SHIFT - UNIT 23

The CO S h i f t Unit processes about 62~ o f the raw s y n t h e s i s gas

from the c o a l g a s i f i c a t i o n unit over a cobalt-molybdenum catalyst bed t o
obtain the required H2:CO r a t i o for the methanol synthesis unit and
r e c o v e r s heat as the gas i f cooled for £urther downstream processlng. The
balance o f t h e raw g a s i s diverted t o a s e p a r a t e gas c o o l l n ~ system, which
r e c o v e r s heat to produce steam.

A large amount of heat is available from cooling shift reactor

effluent and unohlfted gas. An integrated heat recovery scheme is designed to
recover useful energy for heating shift feed gas, hlgh-pressure boiler
f e e d w a t e r , p r o c e s s condensate~ and vacuum c o n d e n s a t e . P r o c e s s c o n d e n s a t e from
cooled shift effluent and u n s h i f t e d gas are reheated and returned to the
gasiflc~tion unit.

A. B a s i s o f Design

The l a r g e quantity of syngas from t h e g a s l f l c a t l o n unit

r e q u i r e s that four p a r a l l e l modules, e a c h c o n t a i n i n g one s h l f t e d train and
one u n s h i f t e d train, be i n s t a l l e d . The s p l i t of syngas into shifted and
unshifted train results in lower capital and o p e r a t i n g costs for the
d o w n s t r e a m Acid Gas Removal U n i t . The Basis o f Design ±ncludes Feed Streams
aud Product Streams (shown on the g o l l o w l u g two p ~ E e s ) .

B. Process, S e l e c t i o n R a t i o n a l e

The raw syngas r e c e i v e d from the g a s i f i c a t i o n ualt consists

mainly of CO, H2, and C02, wlt~i sulfur present as H2S and COS. The
water/gas shift reactS-on c o n v e r t s CO and H20 t o CO2 and H2 s o that the
desired H2:CO r a t i o is obtained to f e e d t h e ~ownstream Methanol S y n t h e s i s
Unl t .

I I - I , 2.7-1

_1 t I I 3 I
I
 i

I t m , I i ,v e i ~ q @ ~#1~ ~*'t ~ Hm I ¸

Feed Streams i i i ,

Raw Shift Feed Gas Makeup Steam Unshlfted Gas

Component (Ib mol/hr) (mol%) (Ib mol/hr) (ib mol/hr) (molZ)

H2 39,069.34 36.19 23,511,64 36.19

CH 4 214.41 0.20 129.O3 0.20
co 47,297.49 43.81 28,463.28 43.81
CC2 19,221.42 17.81 11,567.31 17.81
N2 513.81 0.48 m
309.21 0.48
Ar 172.46 0.16 103.78 q.16
H2S 1,374.19 1.27 m
826.98 1.27
COS 84.72 0.08 50.99 0.08

Total Dry, 107,947.84 100.00 - 64,962.21 100.00

lb ~ol/hr
H20 76,895.59 31,073.04 46,275.17
Total Wet, 184,843.43 31,073.04 111,237.38
lb mol/hr
Total, lb/hr 3,711,910.00 559,800.00 2,233,650.00
Pressure, psla 850 900 85O
Temporature, °F 435 640 435

Product Streams

Shifted Efflueut Unshlfted Gas Combined

to AGR to kGR Condensate
Component (lb mollhr) (molZ) (ib mol/hr) (molZ) ( l b mol/hr)

H2 73,546.72 51.61 23,511.64 36.19

CH4 214.41 0.15 129.03 0.20
CO 12,820.12 9.00 28,463.28 43.81
CO2 53,771.42 37.73 11,567.31 17.81
N2 513.81 0.36 309.21 0.48
Ar 172.46 0.12 103.78 0.16
H2S 1,446.82 1.02 826.98 1.27 m

COS 12.10 0.01 50.99i

0.08

Total Dry, 142,497.86 100.00 6~,962.22 100.00

lb mol/hr
H20 171.42 75.28 119,416.08
Total Wet, 142,669.28 65,037.48 119,416.08
lb mol/hr

C Total, l b / h r
Pressure, psia
Temperature, °F
2,951,690.00
795
100
1,4OI,320.00
820
100
2,151,400.00
790
223

ll-I, 2.7-2

. . . . . . . . . . . . •. ~. o.,..w~w

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",'7-'- ""

, t ,,,,i i,, i, _ ,,

E. The w a t e r / g a s shift r e a c t i o n has been used Xn many chemlcal

process plants; however, i n most a p p l i c a t i o n s , a nonsulfur-tolerant catalyst
is used to t r e a t a sulfur-free gas. The s u l f u r content o f t h e raw syngas
requires a sulfur-tolerant shift catalys~ (e.g., a cobalt-molybdenum type).
The catalyst manufacturer w-lth the most experience in sour gas shift Is BASF
wi~h Its KS-If catalyst. The reactor is sized according to the BASF catalyst
requirement. The r e s u l t i n g shift section is capable of operating wlth
catalyst from any of the other three vendors solicited for recommendations.

The s y s t e m i s d e s i g n e d f o r maximum u s e f u l r e c o v e r y o f ~ a s t e
heat from the s h i f t e d t r a i n and u n s h i f t e d train. The u s e o f w a s t e h e a t for
generating steam and heating condensate and b o i l e r feedwater reduces the c o s t
o f providing g a s o l i n e .

The feed gas is split into shlfted and unshlfted streams to

individual acid gas absorbers to give the most economical deslgn. The H2:C0
ratio in the feed to the Methanol Synthesis Unit Is adjusted by varying the
f]~ of syngas to the shifted train.

Direct sour shlft following gasification i s s e l e c t e d over a

scheme u s i n g s,~lfur removal, convent!oual hot shift followed by CO2
removal- Posl~ioning the conventional hot shift between s u l f u r removal and
CO 2 removal involves coollng and reheating the raw gas from gaslfleatlon
and thus will reduce the overall thermal eff.lclency of the Gasollne Plant.

C. P,ro,cess Des,cription
6 i

The e q u i p m e n t a r r a n g e m e n t and m a t e r i a l b a l a n c e f o r the CO

Shtgt - Unit 23 is presented on P r o c e s s F l o w and C o n t r o l Diagrams
D-23-MP-l'(~,', -2NP, aud -3NP.

C
' , I
1I-1.2.7-3

, I 2 I 3 I
_I
J~ i
 The p u r p o s e o f the CO S h i f t Unit is to s h i f t earbou mouoxide
and s t e a m t o c a r b o n d i o x i d e and h y d r o g e n i n o r d e r to obtain the ratio
required for methanol synthesis. A p p r o x i m a t e l y 62% o f the raw synga8 from
gasification passes through the shift section while the remainder of the raw
synga8 is routed through the gas cooling section of the CO Shift Unit.

The portion of the raw syngas going to the shift section

is mixed with superheated makeup steam to obtain a steam to dry gas ratio of
I:i. The shift feed gas is heated to 600°~ in Shift Effluent/ Feed Heat
Exchanger 23-01-1301 and then flows to Shift Reactor 23-01-2501. Approxi-
mately 73% of the CO entering the reactor Is shifted with H20 to C02 and
H 2. The shift reaction is exothermlc and the gas temperature rises from
600°F at the reactor inlet t o 8790F at t ~ o u t l e t .

The shift reactor effluent is cooled by exchange with

reactor Zeed in S'hlft Effluent/Feed Reat Exchanger 23-O1-1301. The shift
effluent gas is cooled to 2500F in a series of four exchangers: Shift
Effluent Boiler Feedwater Heater 23-01-1302, Shift Effluent 50-psig Steam
Generator 23-01-1303, HP Boiler Feedwater Preheater 23-01-1304, and HP Tur-
bine Condensate Exchanger 23-01-1305. The heat r e m o v e d from the s h i f t
effluent is used to heat HP boiler feedwater from 250°F to 500°F and turbine
condensate from 126°F to 220°F and to generate 50-pslg steam. The condensate
in the s'l,lft ef!.~.~,,.ent is r e m o v e d in Shift Effluent 1st Knockout Pot
23-0| -1202.

The Shift Effluent Ist Knockout Pot overhead is finally

cooled by flowlng through a series of two exchangers, Shift Effluent Air
Cooler 23-01-1306 and Shift Effluent Water Cooler 23-01-1307. These
exchangers cool the gas to 100°F~ The condenc:~te formed in the air cooler and
water ~ooler is separated from the gas in Shift Effluent 2nd Knockout Pot
23-01-1204, The overhead from the Shift Effluent 2nd Knockout Pot flows to
t h e Acid Gas Removal U n i t .

II-1.2.7-4
n~m

46 5 I 6

b
~
 I'[IP i ill • [ __-- ~ _jl [
B~

, ~, ~:', "'t "'.":i ....

C .
The raw syngss from gasification not destined for the
s h i f t e d s e c t i o n i s sent to the u n s h i f t e d gas cooling section. The d i v e r t e d
~'aw g a s ~s c o o l e d by a s e r i e s of six e x c h a n g e r s ~ Approx~,nately 94~ o f the
h e a t removed from t h e raw g a s i n t h e u u e h l f t e d sectlon is recovered by
generating s t e a m and heating c o n d e n s a t e , while the rema~nlnE 6% o f the waste
heat is lost to air and w a t e r coollng.

The raw diverted Eas from the gas£fieatlon section is cooled

in Shift Bypass 150-psi8 Steam Cenerator 23-01-1308 and then flows to Shift
Bypass 50-pslg Steam Generator 23-01-1309. The partlally condensed bypass
stream from the 50-pslg Steam Generator flows to Shift Condensate Heater
23-01-1311, where heat is recovered by heating condensate from 223°F Eo
300°F. The bypass stream ls cooled further ~n HP Turblue Condensate Heater
23-01-1312, where heat removed from the bypass stream is used to he~t turbine
condensate from 125°F to 220°F, The bypass stream flows from HP Turbine ,r
Condensate Rearer 23-01-1311 to Shlft Bypass Ist K n o c ~ u t Pot 23-01-1203,
where the eondensaEe is separated from the Ea~.
C
The overhead from Shift Bypass Ist Knockout PQt 23-01-1203
is cooled to 100°F by two exchangers in series: Shift Bypass Air Cooler
23-01-1312 and Shift Bypass Water Cooler 23-01-1313. The condensate ~ormed in
the two coolers is separated from the gas in Shift Bypass 2nd K~o=kout Pot
23-O1-1207. The u n s h l f t e d gas leavlng Shi~t Bypass 2nd Knockout Pot
23-01-1207 is sent to the Acid Gas Removal Unit.

The condensate from each knockout pot in the shifted section

and unshlfted section le sent to Knockout Pots Bottoms C o l l e c t l n g Drum
23-01-|205. Part of the condensate from the collectlng dr.-- is reheated to
300°F in Shift Condensate Heater 23-01-1310, then returned to the gasifi-
cation unit. The remalndez of the condensate is sent to the gaslflcatlon unit
as makeup water.

II-I •2.7-5

............. '.4.. °~" '. '~ .~'.~',' ~ ' . * . " ',~' ~ ".'.~

1 i__ I 2 I 3 t 4~

N
 . . . . . . . , .,~ . . . . . . .

D, Risk Assessment

The CO Shift Unit uses coz~entlonal cobalt-molybdenum (CoHo)

sour-shift catalysts backed by several years of commercial experience. The
catalyst is available from ' s e v e r a l reputable suppliers s u c h a s BASF and
United C a t a l y s t I n c . H o w e v e r , the shift uult designed for this project is
capable of using catalysts from ocher suppliers as well. The process
configuration of the CO Sh~.ft system is simple and process conditions do not
pose any f a b r i c a t i o n problems.

The BASF s u l f u r - t o l e r a n t shift conversion catalyst, with

more then 10 y e a r s o f s u c c e s s f u l o p e r a t i o n , was s e l e c t e d for this project.
Presently this catalyst is in operation in several plants. BASF s h i f t
catalysts meek tb~ following requirements:

(I) High activity in the presence of sulfur compounds In

the s y n t h e s i s g a s .

(2) High mechanical strength.

m
(3) R e s i s t a n c e to high stream p a r t i a l ptessu:e.

BASF catalyst K8-11 is used in a temperature range of

approximately 450°F Co 950°F. It is resistant to temperatures of up to
1,000°Fo Successful pilot tests have been made at pressures of up to 1,500
psla, and there is a plant in operation at 1,100 psla.

m
J Shift catalyst has a lifetime of about 2 years or more when
it Is directly exposed to raw gas from the gasiflers, such as in thls case
where there is only one shift reactor per train.

, j
T e c h n i c a l r i s k in t h i s s e c t i o n i s minimal.

II-I • 2.7-6

6
5 I ' I_

EQUIPMENTLIST
I , ~ l :=~ r II rll I

ii

E. Process Fl.ow.and C o n t r o l D i a g r a m s ( I n c l u d i n g Material

Balance)

Process Flow and Con~.rol Diagrams for CO Shift Unit 23 are

as follows :

Drawln~ No. Title

D-23-MP-INP PFCD CO S h i f t - Unit 23 Gas C o o l i n g

D-23-MP-RNP PFCD CO S h i f t - U n i t 23 S h i f t Section
D-23-MP-3NP M ~ t e r ~ a l B a l a n c e CO S h i f t - U n i t 23

C
.t .

II-1,2,7-7
A

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NOTES,
I. fNrmE All( k tOTAL OF FOURil0OULIt'! ID|NIICAL
lO Ym|mouLz.
', !:', i I~, XF.ATAm IdATI'RIAL~IIALANC[S~lOirll AflJ~ FOX
Ola MOOIJLKAT 1111(~ 1 , OP~TIJIQ ¢OXOITIOH$.
3, LIM! sr/lilo Is ~$i~ OI1 11~ OATAOF' I)(SI~
OPU~TI~ CO~1110i¢
4, START-UPH~1(R 1~O1-1401 IS |N il0OUL( A
1~41{Bur SF.h~S Ill00~r¢ ~ ( ANDWO. AL~O
5T~T-UP Hl~1(R 23-'03-1401 L~ Ill ii~UL[ ]i~E[
aUT $~VF.S MOOULI~lillE( AND F~I~

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5HLFIFJ) I~FfLQF.IT/ i.D'34"t'IP'!
23-OI-I307G $illf'T~ F(E0 GASCOOLERIA~I

13-'01-1L'04

po~-p, o2
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SET •
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23-O1-1205

$ EOUU~EI(T $H0111ON THIS ORAI~4Ga

23"01"1202 33-'0iol304k
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~E¥ IIAT£RTANK Z3-O1-1204 23-O1-13048

23"01-1S01 2301-1205 2,3-01-I ~5A
2POI'I3OIA PJ-OI- 13059
23..'01-13018 23-01-1306
23-'O1-1302A 2"q-Ol-13OfA m
23...01-1302B 23-01-13078
23-.01-1303A 23-01-1401
|3-01-1501 23-.01-1z'.')38 23-01-1501
|3-01-150! ~t}..'OI-I ~,.'~C 23,"O1-1SOZ
2}"01-13(,3D 23-01-2501
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U.S. DEPARTHENT OF ENERGY

B.PJ3.
IA~ II m 5e,eeB - T0,- C~SOLINE PLANT I
C0AL - TO,- HETXANGL
Fffi P l ~ REPORT I1""'" I !
_F~R~'Ll£1ff APpI~OYAL ~ l l " , . , , ~ . .
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SHIFT 1R~IH SIEAU FEED OAS Zm If.O, POT
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MMSCFD IIkOZ
420,14 "tO, 75 4g |, 5} 49l, 55 338, 95 324.85
850 900 046 830 805 BOIL T55 '795
TEMF eF 435 540 ~O0 079 ;~SO 250 tO0

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F. P10,t ,Plan/Caner,.1 Arrangement Drawl,ago

P l o t P l u n / O o n a r a l Arrangement Drawings f o r CO S h i f t Unit 23

are as follows:

Drawin~ No. Titl__..~e

D-23-PD-INP P l o t P l a n - U n i t 23 CO S h i f t
D-23-PD-2NP P l o t Plan - Unit 23 CO S h i f t
D-23-PD-3NP P l o t P l a n - Unit 23 CO S h i f t
D-23-PD-4NP P l o t Plan - Unit 23 CO S h i f t
D-23-PD-SNP E l e v a t i o n - Unit 23 CO S h i f t

memo--

II-!. 2.7-8
 [ I ill III " ................ ' i i mE,==. ~]~ W I~. ''I ' i 'I I I ..........

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. . . . I I II IIIII i llill i ilii i

EOUI~EHT LIST

13.Ol-IlOZ SHIFT (FFLUCNT l i t E,O.POT A

l).Ol-IlO] SHIFT I~Y'PASS l i t K.O,POT
2).Ol-IlOl IlIIFT ZFFLUDff INO I,O, POT
I).OI=IIOS lID, POTS OOIlOMSCOLL(CTIHODRUM
I3-OI-IIOT SHIFT IV.PAlS l ~ K,O,YOT
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EOUIPUENT LIST

I)-H-IIO2 SHIFT EFLtJ~T l i t LO, POT

23'-04-1tO~ SHIFT BY*PASS151 K.O,POT
23"04-1204 SHIFT EFTLUERT2NO K,O,POT
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US. 0EPARTHEt,iT OF ENERGY

5D,BBB 9.P.D.
COAL - 1"0 " HETHAHOL " TO " GASOLINE PLRNT
~-, Ee0~'r I: . . . . =,: "1 ! I/'Er~:t"
• --==~AL I,'-,,=,==.-. I I a PLOTPL,, l F,,a,
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III I

I".~FT

I U.S. DEPARTMENT OF ENERGY

- i m~SKSn" W.R. GRACE & CO. K~T'JCKY
,,,,, ~ 50,000 B.P.D.
. ~:~,.RR~ov:T I ~---= ,Mr. I ! j~7~ :Ip L.. COAL- TO - METHANOL- TO - GASOUNE PLANT
,L~n ~ ® , . o 'ritE RALPH M. PARSONS COMPANY
" -- . .... / '='~ ~'"'~" / °'~'~'''~°'~"~" /"~ ~"
q,w
C G. Single-Line Diagram

See Volume 11, 1.2.6(G) for CO Shift Unit 23 Single-Line

Diagram.

L.

II-I • 2.7-9
~.T=.

I. 2.8 COAL GRINDING AND SLURRY PREPARATION - UNIT 24

A. Basis o f Design

The Texaco slurry preparation technique utilizes wet grlndi~g

technology which does not require drying of the coal prior to slurrying.
Design of the coal s l u r r y u n i t was based on a summary o f the c r i t e r i a listed
below~

(1) Top s i z e of coal particles ccntrolled for compatibility

of downstream equipment.

(2) Provide a coal partlcle size distribution as s p e c i f i e d

for gaslfier f e e d .

(3) Concentration of solids controlled c l o s e to the slurry

concentration specified for the gasifier feed.

The selection of equipment provides a high degree of control

on particle size and water balance In the slurry. These were important design
features required to produce a pumpable slurry of the desired concentration.

The Coal Grinding and S l u r r y Preparation Unit has p a r a l l e l

g r i n d i n g t r a i n s and i s a r r a n g e d in modules c o m p a t i b l e w i t h t h o s e o f t h e TCGP.

Feed Stream
tl

Component Total Coal Feed (ib/hr)

Coal 1,921,021
Water 187~674
Total 2,108,695
Average Solids Density I. 444
Partlcle Size 2" x 0
T e m p e r a t u r e °F Ambient

lI-1 • 2.8-1
 B. Process S e l e c t i o n R a t i o n a l e ~
~ m
m

The process selection of the Texaco Coal Gasification Process 9mmmmRq

~ m
~mmmmmm~

(TCGP) was specified by W.R. Grace & Co. prior to the initial phase of the
preliminary design of the Coal-to-Methanol-to-Gasollne Plant. The slurry ~ m

pEeparaclon system is considered to be an integral part of the Texaco Coal

Gasification Process and contains proprietary data; specifically, t h e coal
grind distribution and slurry concentration. This c~nf~dentlallty e~tends to
equipment associated with producing this size distribution.

The Demonstration Plant (SGDPP c o n t r a c t batween W.R. Grace &

Co. and DOE) design incorporated wet grinding. However, at this stage of the
program in 1979, the impact of oversize material on the performance of the
Texaco gaslfier had not been demonstrated, partlcularly the impact of a
slurry on a steady flow through the hlgh-pressure positive displacement
pumps. Therefore, until this problem could be investigated in more detail,
the Demonstratlou Plant design I n c l ~ e d the necessary facilities to provide a
positive system for removal of oversize m a t e r i a l from the product grind.
Similar coal grinding for slurry transportation is a proven technology,
l a r g e l y developed i n the United S t a t e s .

Experience with Texaco gasifiers at Montebello and at

Obarhau~en-Holten continued during the time p e r i o d that elapsed between the
SGDPP work and the Gasoline Plant Project. D~.si~t of the coal slurry unit for
the Gasoline Plant was based on criteria established by Texaco.

C. Process Description

The a r r a n g e m e n t of equipment and m a t e r i a l balance f o r t h i s

u n i t i s shown on P r o c e s s F l o w and C o n t r o l Diagrams D-24-MP-1NP,
-3NP.

The d e s i g n of the coal slurry

-2NP,

u n i t i s based on c r i t e r i a
and

set
!
out by Texaco as i n d i c a t e d above in the B a s i s o f D e s i g n .

II-1.2.8-2

[
P

The Coal Grinding and Slurry Preparation Unit has parallel

grindinE trains. The grinding trains are arranged into modules for purposes
9mm~mm~lmm'..I
of constructlo~ sequence. Each group of grinding trains has a common header,
linking the trains to the slurry holdin E tanks.
~Sz~mmmmm

A 29,000-ton covered live day storage in silos is the source

of feed Co the coal grinding trains. Raw coal 2 inches and under is reclaimod
from a silo by a discharge feeder and transferred to a belt conveyor for
feedlnE to a grinding train. An indivldually controlled variable flow of coal
is used for each of the grinding trains. Provisions were made ~n the coal
surge storage for downtime of mill trains caused by maintenance.

Each train was designed to handle 2-1nch coal contalnin E 8.9%

moisture at normal operatinE rates ranglnE from I18 to 151 tons per hour, 24
hours per day, 7 days per week. Design coal feed rate was set at 200 tph.
This rate permits normal production of slurry from each group of grinding
trains for the normal operatln~ condition with design coal, even if the spare
grlndln E trains are out of service.

The 2-inch and under coal conveyed from each live storage
silo is fed to a first-stage reduction mill for reduction. Feed t o the impact
type crusher discharges from a 30-1nch belt conveyor operatln E at about 260
fpm. The coal discharges from the head pulley through a chute and drops
vertically to the flrst-stage reduction mill. Crushed material is removed by
a belt conveyor to a revolvinE mill. Coal is weighed during transport to the
mill on a belt scale.

This digital weigher records the coal flow and provides a

signal to control water addition to the m i l l and also to the feeding
arrangement in the coal day storage in Unlt 12 to ensure a uniform flow rate
that c~I be varied from 70 to 200 tph. The coal is sampled automatically as
it is discharged from the conveyor head pulley by gravity to a cone for
feedinE to the revolving mill.

II-1.2.8-3

.... i
p i ¸ ,. . . . . . . . . . . .

F r e s h c o a l f e e d i s mixed w i t h a r e c y c l e 8 1 u r r y from Unit 21

p l u s makeup water and a v i s c o s i t y a d d i t i v e . W a t e r i s added i n p r o p o r t i o n to
t~=e we~ &.,~ o f c o a l f e e d determined by t h e b e l t ~ c a l e s , The d e s i r e d c o a l - a s h -
water proportion in the mill discharge varies by weight
a c c o r d l n ~ to coal t y p e .

Slurry overflow from the mill passes through a tro..,el screen

and is discharged to a surge sump. The tro-..el screen has openings to restore
tramp material. The reject on the screen is dlsc~rded. A meter in the sump
monitors slurry viscosity and transmit8 this information to the plant control
system, where it is tied in with the =Ill wate~ feed controls.

The slurry is pumped from the mill sump to a safety screen

for scalping of tramp material from the slurry product, thereby ensurinE
adequate protection to downstream equipment from oversize material. The
oversized material removed by the screen deck is sluiced back to the feed
cone of the mill using a portion of the makeup water. The slurry passing
through the screen deck flows by gravity to a screen sump and is.pumped to
agitated slurry holding tanks.

The s l u r r y tanks are p o s i t i o n e d a d j a c e n t to each o t h e r ~rlth a

t i e - b e t w e e n . I f one of the. t a n k s i s out of s e r v i c e , t h e flow to t h e o t h e r s is
increased. T h e s e t a n k s a r e desigzied f o r working volume s t o r a g e of 4 hours a t
a normal o p e r a t i u g l e v e l that permits over another hour*s storage up t o a
maximum ] / q u i d l e v e l , l e a v i n g adequate f r e e b o a r d ~ l o v a n c e .

WorklnEvolume calculations are predicated on maintaining a

minimum operatln E level to provide proper submergence of bottom propeller. A
tank may be emptied below that level, but the agitator is turned off to
prevent damage to the shaft. A slurry feeding pump circulates slurry from the
slurry tanks t o t h e suction aide of the Easlfler charge pumps.

II-I.2.8-4
p P

The p r e c e d i n g d e s c r i p t i o n covers the o p e r a t i o n of the s l u r r y

preparation s u b s y s t e m when p r o d u c i n g t h e Texaco g r i n d specification for
normal o p e r a t l n E c ~ u d i t l o n s . The O p e r a t i n g C o s t s summary i s based on the
standard grind s p e c i f i c a t i o n which i s used over 85~ of the time,

Texaco uses additives in coal slurries t o improve slurry

viscosity and increase solids concentration. Consequently, a slurry additive
system was incorporated in the slurry preparation unit. Storage capacity
provides fc~ a maxlmtuno£ 30 days' storage. One unloading pu~p handles the
unloading stations.

One a r e a sump and pump p e r s l u r r y preparation module i s

provided. Spills and floor cleanup in the slurry preparation building are
sent to the gasification unit and is pumped back along with the gaslfier
recycle.

For some coals, it may be necessary to add basic material to

the slurry to prevent corrosion because of low pH. Provision was made to add
ammonia, if needed, to the water llne to the mill at plant startup. Such
addition ceases after the operative system reaches steady state pH of about
8.0.

D. Risk Assessment

Thl8 system includes impact crushers, wet grinding mills, wet

vibrating screens, slurry tanks, slurry pumps, and belt conveyors. All
equipment selected for coal grinding and slurry preparation is conwentional,
connercially available, and has a history of successful operation with coal
or in other applications. All pumps are spared. Lines and equipment have
appropriate corrosion-erosion allowances, along with wear plates according to
a c c e p t e d s l u r r y handling p r a c t i c e .

II-1.2.8-5

- ~J~,~'i~7"='.~;.T~..,~ ~: " ~ . ~ ; ~..~!~ ~ ~* :..:,!,';,~..~.,,~ ,f.~ '~'~/~ :.~ ,.:~'~.~c ~--~ -..~:-.~..~:,~ :'~.~t~'.~-- £~I .~.~ .....
 Built-in slurry h o l d i n g c a p a c i t y i n p r o c e s s sumps p r o v i d e s a
buffer against slurry surge from mills and screens in case of power failure.
Slurry pH is held slightly basic by automatic monitoring and controlling the
pH of the recycle streams.

The Coal G r i n d i n g and S l u r r y P r e p a r a t i o u Unit i s comprised o f

parallel grinding trains. The grinding trains are arranged into modules for
purposes of construction sequence. Each group of trains has a common header,
linking the trains to the slurry holding tanks.

The unlt was designed in a partlcularly conservative manner;

that is, to provide a range of potentlal grind analyses. Thls provides the
possibility of varying the grind size to suit slurry concentration, carbon
conversion, and gaslfler performance for a wide range of coal analyses.

Based on e x p e r i e n c e with other coals, t h e equipmer,: i s n o t

e x p e c t e d to e n c o u n t e r undue c l o g g i n g or p l u g g i n g p r o b l e m s . The v i b r a t i n g
screen for each train is a safety or s c a l p i n g screen t o remove tramp o r
oversized produc~, thereby furnishing protection against oversize material
that might Lnterfere with operation in downsCream equipment. The screen has a
b u i l t - ~ feed splitter to produce three feedstreams. Each of these streams is
sen~ to one of three separate screening sections of the multlfeed screen.
Each screen as spared-as further insurance against screen blinding.

The a r e a s of uncertainty include the ability to produce on a

c o n t i n u o u s b a s i s t h e coal s l u r r y r e q u i r e d f o r the normal o p e r a t i n g condition
c a s e ~r~thout c o n t a i n i n g o v e r s i z e s o l i d s and the a b i l i t y to h a n d l e t h e s e c o a l
slurries. A syst~m is incorporated t o p r o v i d e an a d d i t i v e ahead of the
grinding m i l l f o r modifying s l u r r y v i s c o s i t y . Screens a r e s u b j e c t to b l i n d i n g
at h i g h e r s o l i d s c o n c e n t r a t i o n and a r e s p a r e d . The h a n d l i n g o f c o a l s l u r r i e s
and s u s p e n s i o n of ~olids particles in ~ater are arduous applications for
valving. Special attention was a p p l i e d to the detail of valve design to
ensues l o n g - t e r m c o n t i n u o u s o p e r a t i o n w i t h o u t undue m a i n t e n a n c e .

!I-1.2.8-6

• . ~ ~*r~'~t'.~ ~ ' . ~'~f~ "~ ~ ~,.,~.~.~.~ •.

.. .~, ~.U. ~:~. <~..,~ . ~.~.~, ,~.,._i ,:: . ~ ~,,T~ ~ • ~ . .~ ~ ~'...1 .,1., .. ~°~,.
 The c o a l g r i n d i n g and s l u r r y p r e p a r a t i o n ~yaCem mumC d e l i v e r
c o a l , ~round to t h e proper grind s i z e specification, while still achieviug
the design slurry concentration. Failure t o meet e i t h e r of these desired
condStions r e s u l t s in difficulties $n t h e p r o c e s s units d o w n s ~ r e a n o~ t h e
unit, principally i:: g a s ~ i c a t i o n . To a c o u s i d e ~ a b l e extent, downstream
facilities were d e s i g n e d to compensate £or d e v i a t i o n i n s l u r r y c o n c e n t r a t i o n .

A flexible coal grinding s y s t e m was designed to produce the

r e q u i r e d g r i n d s i z e D i s t r i b u t i o n and s l u r r y c o n c e n t r a t i o n , w h i l e a t t h e same
time protecting against oversize particles. This permits t h e c a p a b i l i t y of
producing a d i v e r g e n c e of c o a l g r i n d s i z e d i s t r i b u t i o n s . This approach gives
the plant ~he c a p a b i l i t y of tailoring the grinding system to o p t i m i z e the
overall gasification system p e r f o r m a n c e .

The c o a l s l u r r y presents special problems f o r h i g h - p r e s s u r e

charge pumps. Some e x p e r i e n c e was o b t a i n e d i n t h e Texaco p i l o t plant where
equivalent coal slurries ~;ere pumped t o t h e g a s i f i c a t i o n p r e s s u r e of 1,200
psig. It is preferable t o u s e pumps w~-th no wa~e~ d i l u t i o n . A number o f
s u p p l i e r s are a v a i l a b l e f o r s e l e c t i o n on t h i s b a s i s .

II-1.2.8-7
 E. Process Flow and Control Di~raw,,, (lncludtu~Material
Balance)

Process Flow and Control Diagrams for Coal Grinding and

Slurry Preparation Un~t 24 are as follows:

Draw~n 8 No. Titl_._..~e

D-24-MP-I NP PFCD Coal Grinding and Slurry Preparation Unit 24 - Coal

Grinding

D-24-MP-2NP PFCD Coal Grinding and Slurry Preparation Unit 24 - Slurry

Preparatlou

D-24-HP-3NP PFCD Coal Grinding and Slurry Preparation Unit 24 - Viscosity

a
Additive System
\.

II-1.2.8-~

P .....~.. p
 I ,2 L., -~ I "e
FEED CONVEYOR AEGUCTION [ L ~L eO~V~ ~ I COAL SAMPLER MILl.

CO~IIENT COAL FEED

COAL. LBflm 4eO.r255
WATERe LB/HR 4~919
I.. TOTAL,,.L.B/ltR 527, 174
AVlm. ira.lOSna~lrv 1.444
PARTICLE SIZE 2'5(0
TEIIPERATUR~'+OF AUmIENi"

• SAUPLE

,,p
E~--- MAKE-IJp WATER
L
¢

LJ

!
II'21"III'Ilip) C ~ i ~ l ~ Ul~lq.O~Itl:t~U-il~ ;~i~.~FLOII pull~

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1 ' "~""~ _~ u I~o...L,.I~o "F~ml~umTI, , i "'~:

' I
 @
- i,i
7

WOTIII
I, THll~IIILk'T $1nE~U DATA IS FOR TII£ ~IIAL
~ T 1 H O COHDITIOI~I r~fl OWKIIOOULE,

A C

,!
I, I
T

,i r
T

LJ SLURRY/
SLURRY TANK
. I

/,

REd£CTS
IHNFI

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¥1SCOSITYA ~ E (0-24-~P-3 NP i
/±

MILL ~ Pl~P ,~REF.~ SUtP PU~

241~1 tll), L~.~A

US. UEP~THE3IT OF I~E.fl~Y
V,R, GIMCE & CO,
I 5~.WB B.P.D.
• fo~ n~[GN REI'(~r
i._'-z=. I I I~" COAL - TO - I~THANOL - TO - ORSOLII~ PLANT

i~,~! ,
I , ~-,,..P ~ ,
I ~.lV~IR COAL G~I~IltO _

e ,I
 ' , " + ' ~ ' r,m',' + + i'" ~ : -+~.,,,'i
;,'~ ; +";, ,.+. ., .t ., + . . . . .I. ' , , , +., , , , , , . . . . . . . .
14 ~+ , .,." .t+.+, + , ,,,+

, ,, t --
.... + I + .
i_ _ i i
4+
SLURRYTAHKS SLUI~YI"AHKAAITATOR AREAS ~

,4)
¢

[D":t'I'MF'I HP~>"SLLIRRY IL~i+URN/GA~zP,IEK (~.'tRT-LiP I+ $1~UTOO'+IH)

L
~1"~"2"4"~'1"-~':'~'>'COAL-WATERSI.tlRR.+/SCREENSUIIP
m ,

DP, A Z ) I $

+ -

AREA~ PLISP SLURRYFEEDPUl~

i i D ~

__ II I

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..
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f I=,,~.,.o.o,i +--+-
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 I ,,, 6 7
11 l, J

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COAt,WATER5LURR¥/Ct.ARIi:IF..R

G~IFIB CHARGEPLUS

E
DZ4I~2HP.DC,A
] 'I"JD[ACO I}i&VBIA~XI~T CORI:'Oe~TIO~- U,S. DEPARTMENT OF ENERGY
e~s~rr WJ~ GRAr~ & CO,
5 0 , 0 0 0 B.P.D.
COAL - TO - HETHAHOL - TO - GASOLINE PLANT

--
[ fOR CLI£~q' A P P R O V A L
I r~ LIL'~X~R APPeOVkL'
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,ADDITIVTAHK
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ITYPICAI, PER STATION)

CARIJHLO~DINSTATJ~qS
G :1~ I

J
A~OITIVETAH~cLq
tiXLOADIt~

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U.S, DEPARTHENT OF ENERGY
-~'Tr V J ~ 6 ~ O E & CO. ~'~
] 50,0~ B.P.O.
,,el ' -
":. Foer;~,m nrp~T
] F ~ CL.~4T ~pPEOVAL
I F ~ UClgICOA APPROVAL
I
1~'°" I
CL~L - TO - HETH~IOL - TO - GASOLINE PLANT

! F~ almT s= .~ l_
n ii
44~
Ol~¢ltlWlrloM
"-'::,"-,- I li
I w...._.,, vzse~'rv~mzvE smzN_ | D"24-MP-3 NP
8
 F. Plot Plan/General Arrangement Drawln~s

Plot Plan/General Arrangement Drawings for Coal Grinding and

Slurry Preparatlon Unit 24 are as follows:
°.

Drawing No. Tftle

,t
D-24-MH-2NP General Arrangement Coal Slurry and Grinding - Unlc 24 Slurry
Preparation B u i l d i n g - Plan

'!i"
D-24-MH-3NP General Arrangemont Coal Slurry and Grinding - Unit 24 Slurry
Preparation Building - Sections

D-24-MH-4NP General Arrangement Coal Slurry and Grinding - Unlt 24 Slurry

Tanks and Pump Buildlng - Plan and Section

.!

IL

:i
I

Ii

11-1.2.8-9
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,,f . ~ -- . m

NOTE5
XF/oOR ...¢r./MP//p//MPJ A/07 J',q~,,t.I
. . . .

U.S, DEPARTMENT OF ENERGY

W.P.. GRACE & C O . KENTUCKY
50,000 B.RD.
'y;:- . . . _ ° COAL- TO - METHANOL ~-TO - GASOLINE PLANT
** .:..~ ; . .
COAL SLURRY & GRINDING-UMIT Z4 ...~. I l-
THE RALPH M. PAR:|ON$ CHMPANY ~ -pARATION BUILDING -- ~ .
SLURRYPR, D-24 MH . 2NP
" __ r m~ ,.
"44,,

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,r__.~
t .~ .

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tZ.#.5: i
p.,,:..,.<~-~.,j ,,, ill I ' ,..:,
" ~ [~ U,S.DEPARTMENTOF ENERGY
-'/,~* 24-a,)',~-~Np SKZrr W,R, GRACE & CO. KEm'UCKV
~:.::~ i ,~,~,~,~ ,,-, , 50,000 B.RD.
~ . . - :_-.._-:
' : AL T O - METHANOL - TO - GASOLINE PLANT
=7.......'~: I c.,ea,mo., ....... CO ........ --- --.l~
_ ~.,-- :. . . . . i~C-;*,-~, - !t - . . . . . 1~,41p...:~.,l / u=~.."'-'-'..'.At.R~. . . . uG- UNIT 2 4 E ---- --I 0 ! ....
' ~-~- " ' ",l , ~~r~'KIIPrlO. - II[ ~. '.~ '.=.u l." r. . . bW'/.J"
vii# 1.~H,1
I.r:,,....~,.,1
THE RALPH M. PARSONS COMPANY
PASADEN ..r.~,.*,,.
ICOALSLue't~r--~--'-~'/O~I~"--ILOING [~*""~'~__~t
I SLURRY pREp~_~l.,=u, ~u / u-r.,.:w'r~.
.u , - . - ,~NP
N
4 i =,I i ~ ! " r';,. #~CiAi~ '. . . . . . . -- .-- SEc/IV~l i

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,~ECTION ©
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,'!.o!o.. .!
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4¢_ . I 6 I 7 J

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~"llil~'llri~ "IT 'r

..I
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I'-~q" E

U.S. DE~PARTMENT OF ENERGY

eAS~'rr W.R. G R A C E & C O . KEmUCKV
...... ,

I A,.o. J
so,ooo S, eO. f
::-:.:==:..~,,~,~,r I - .... ILe,,: I,.ee,.n ,/t~,,r~O COAL - TO - METHANOL - TO - GASOLINE PLANT I
i " r~vus rcLrCR^n AOD~Mr~_E~C=U?[ It ¢Au= i;",;';'T'~-:~'~.amP°L . . . . ImP|
;:: "i-
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I. .. .. .. .. .. .. .. .. .. . ~ ,t.,,,,~',~SOe
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,L,,*~ N c v . = k2~pm~J ,FPB #- 1
-=,,= -,-,~'~ ~-" t ,',~'-0 u 2000 I 61B2 I I
MP N¥ COALSLURRYCGRINDING-UMT24 I" -- I I- | /~1
['" .... ;_,~,R~c.w.,~ ~,v,pa°~'== i l THE EALPH M. PARStINS CO A SCURRY TANKS~ FUMPem.~.G r=-A"_%:'~_,,-, A~,o I/°~1
PLDN I~,,SE(~I'tON | U--='--'"' '--"" I /'.--
,~ 6 t

I
p ~': P

G. Single-Line Diagram

See Volume 11, 1.2.5(G), for Coal Grindiug and S l u r r y

Preparation Unit 24 sin~Ze-llne diagram.

f"

II-1.2.8-10

..... i
 1.2.9 METHANOL SYNTHESIS - U N I T 25

A L u r g i methanol s y n t h e s i s u n i t has been s e l e c t e d to c~nvert s y n t h e s i s

gas, a f t e r partial CO s h i f t and a c i d gas r e m o w l , to m e t h s u o l . Approximately
17~000 s t p d o£ m e t h a n o l a r e required to p r o d u c e t h e nominal 50,000 bpd o f
gasoline. Because of the large amount of synthesis gas. four parallel trains
are provided. Because of physical constralnts on equipment size. each
methanol synthesis unit has two reactors in parall~l.

Also included is a single-traln Pressure Swine .~Isorg~Ion (PSA) module

to serve all of the methanol synthesis modules, The PSA ~eslgn is based on
Union Carblde's HYS~V process.

A. Basis of..Desi~a

The l a r g e amount o f s y n t h e s i s gas t o be c o n v e r t e d to o b t a i n t h e

r e q u i r e d methanol volume n e c e s s i t a t e s several parallel trains. Based on t h e
c u r r e n t s t a t u s of r e a c t o r and c a t a l y s t d e v e l o p m e n t , f o u r t r a i n s have been
used i n t h e d e s i g n to cQnvert s y n t h e s ~ s gas t o m e t h a n o l . Each t r a i n h a s two
r e a c t o r s operating in p a r a l l e l .

Feed, product, and f u e l / p u r g e gas b y - p r o d u c t scream c o m p o s i t i o n s

are g i v e n i u t h e f o l l o w i n g t a b l e s .

II-1 •2 . 9 - !

. . . . .,...,..~..,,.,.,~--~wwmm.u,*,~'~,~,~.~:.',~'~ `£~.~.~`-`:~:.~`~.~:~.::~;~::~~.¸~:~.~~~~~

i , I 2 I a I
 Feed 8~reams

Makeup Oas
Component lb mol/hr molg

H2 96,813.76 67.54
CH4 322.59 0.22
co 40,826.39 28.48
co2 4,300.52 3~00
N2 814.21 0.57
273.28 0.19
TeCal Dry, lb mol/hr 143,350.75 100.00
~2o h

Total Wet, Ib mol/hr 143,350.75

Total, l b / h r 1,566,940
Pressure, psla 750
Temperature, oF 82

ZZ-1.2.~2

I'

s ..... I e I
'., 2$"01-12~1 25-01-1205 25-01-i~02
• . ~ ~PARATOR60Ti'~ L~--/~N~.~P/,~TOR ~OTrOUS L.P. FLASH01~ HOTESI
 . . . . . . . , ...... , . , . ,.,, ,,., .,, ,, .,,, ,.,,, ,.,, ., ,,, , , . , . . ,,.,,,,.,., . . . . . . . . . ,.. ..... , , _ p

P r o d u c t Streams

"Wild" Methanol Crude Methanol a

Component (lb mollhr) (molZ) (lb mollhr) (molZ)

P'2 i19.31 0.24 0.57 12 ppmv

C114 58, 20 O, 12 1.23 26 ppmv
CO 21.94 O. 05 O. 26 5 ppmv
CO2 290.90 O. 60 29.12 O. 06
N2 48.88 0.10 0.42 9 ppmv
Ar 30.64 0.06 0.42 9 ~mv
CH301{ 44,092.78 90.59 43,694.08 91.~5
Hydrocarbons 0.70 16 ppmv 0.52 11 ppmv
Hlgh Bollers 53.06 O. 11 52.80 O. II
Low B o i l e r s 37.10 O. 08 31.97 0.07
H20 3 ~920,48 8.0_____~5 3,913.51 8.20
Total, l b mol/hr 48,673.99 100.00 47,724.90 100.0
Total, l b hr 1,505,720 1,476,610
Pressure, psla 415 10
T e m p e r a t u r e , °Y I00 94

aComposi~ion of methanol produced Mien the )~G unit is down and "wild"
methanol Is let do~x to I0 psla prior to storing in crude methanol tanks.

II-1.2.9-3
 C By-products

m
Flash Gas From Flash Gas From
"Wild" Methanol Crude Methanol a
Component (lb mol/hr) (molZ) (lb mol/hr) (molZ)
i i

H2 270,77 61.56 118.74 12.60

CH4 29.98 6.82 56.97 6.05
CO 19.95 4.53 21.68 2.30
Co 2 28.77 6.54 261.78 27.79
N2 61.35 13.95 48.46 5.14
Ar 24.47 5.56 30.22 3.21
CH3OH 4.46 1.01 398.70 42.32
Hydrocarbons - - 0.17 0.02
High B o l l e r s - - 0.26 0.03
Low Boilers 0.II 0.03 5.13 0.54
T o t a l Dry, lb m o l / h r 439.86 100.00 942.11 100.00
H20 0.03 6.97
Total Wet, ib mol/br 439.89 949.08
Total, ib/hr 5,700 29,070
Pressure, psla 45 10
Temperature, °F I00 94

a F l a s h gas from crude m e t h a n o l i s produced when m e t h a n o l i s sent to

storage.

I I - l . 2.9-4

r
p ........ 0

Purge Gas Leakage Gas

Component (Ib mol/hr) (molg) (lb mol/hr) (mo1~)

H2 3,483.28 71.43 502.60 69.98

CH4 216.08 4.43 18.32 2.55
CO 174.16 3.57 98.20 13.67
(D2 136.68 2.80 21.36 2.97
N2 645.96 13.25 58.04 8.08
Ar 200.64 4.11 17.56 2.44
CH3OH 19.84 0.41 2.20 0.31
T o t a l Dry, l b m o l / h r 4,876.64 100.00 718.28 100.00
H20 0.04 -
T o t a l Wet, l b m o l / h r 4,876.68 718.28
To~al, Ib/hr 48,130 7,390
Pressure, psla 994 750
TemF~rature, OF I00 127

B. P r o c e s s S e l e c t i o n Rationale

Data were r e q u e s t e d from I C I , L u r g i , and Topsoe f o r a 17,000-stpd

methanol plant for thls project. Such data, together with meetings with each
of the potential llcensgrs and information available from other sources,
formed the bases of a process selection study. Based on an evaluation against
predetermined criteria, the Lurgl process was selected for incorporation in
the gasoline plant. Key attributes of the Lurgi process contributing to its
selection are as follows:

II-I. 2.9-5

p
 C.
(I) Lurgi's methanol plant experience based on synthesis gas from
heavy oll gaslflcatlon as well as from natural gas reforming.
At the present time, there are four operating plants using
vacuum or heavy residue and four oEhers are under
construction. Also one plant using coal as feedstock is under
construction in the United States. This is s u p p o r t e d by
Lurgi's extensive experience wlth coal and coal gasification
through its own process - and Lurgi's experience in Rectlsol
acld gas removal plants prior to methanol aynthesls.

(2) The L u r g i p r o c e s s , because of its special reactor design,

recovers heat at a higher temperature l e v e l .

(3) The Lurgi process utilizes an i s o t h e r m a l reactor which

enables optimization of catalyst and recycle gas
requirements.

C
C. ,Process Description

Refer to Process Flow and Control Diagrams D-25-MP-1NP, -2NP,

-3NP, and -4NP for equipment arrangement and material balance.

The synthesis gas coming from t h e A c i d Gas Removal U n i t i s

compressed i n Makeup Gas Compressor 25-01-1801 from 750 p s i a t o 998 p s i a . The
gas t8 a d d e d to t h e r e c i r c u l a t i n g gas, and the two gases are compressed to
s y n t h e s i s p r e s s u r e i n Recycle Gas Compressor 25-01-1802.

The g a s i s h e a t e d t o 437°F i n F e e d / E f f l u e n t Exchangers 25-01-130i

and -1302 by a p o r t i o n of the hot reactor effluent gas i n c o u n t e r c u r r e n t
flow.

C
I I - I . 2.9-6

, 5
p P

Converslon of H 2 with CO and CO 2 to methanol takes place in

Synthesls Reactors 25-O1-2501 and - ~ O 2 , which are equipped with parallel
vertical tubes holding the catalyst. The hea~ released during the exothermlc
conversion reaction Is transferred in sltu to boiling water, which ensures
exact temperature control and eliminates damage to the catalyst caused by
overheating. The reactor outlet temperature is regulated easily and closely
by controlllng the pressure in Steam Drums 25-01-1201 and -1202,

As already mentioned, a portion of the hot reactor effluent gas

heats the reactor inlet gas. Boiler Feedw~ter Preheater 25-OJ-1303 Is
installed in parallel with the Interchangers to preheat the boiler feedwater
2n countercurrent flow to the remaining reactor effluent gas. Further coollng
of the gas and condensation of methanol and water occur in Air Coolers
25-01-1304 and -1305 and Water Coolers 25-01-:,306 and -1307. To avoid an
accumulation of inerts in the synthesis loop, the system i~ ~ u r g e d
continuously, with the purge gas beln E routed to either PSA Unlt 25-01-2801
or the plant fuel gas system. The condensate is s e p a r a t e d in M e t h a n o l
Separator 25-01-1203 and supplled by level control to Flash Drum 25-01-1204,
where raw methanol is expanded to 415 psla. Flash gases released by thls
expansion are routed to the fual gas heade& and p under normal operatln E
condltlon8, the resultant "wild" methanol flows to Methanol-to-Gasollne Unit
31.

When t h e MTG u n i t is down, " w i l d " m e t h a n o l i s expanded f u r t h e r to

I0 psla In Low-Pressure Flash Drum 25-01-1205. Low-Pressure Flash Drum Pump
25-01-1503 supplles crude methanol to the c r u d e methanol tanks in
Intermediate Tankage - Unit 63. Low-Pressure Flash Drum Eductor 25-01-2802
uses purge gas to produce a vacuum in the low-pressure flash drum. Flash
gases from the low-pressure letdown flow to the fuel gas system.

D. Rick Assessment

Compressed synthesis gas from the Acid Gas Removal Unit is mixed
with the recycle gas from the product separator and compressed to synthesis
pressure. Synthesis gas is charged to the reactor after heat exchange with

II.1.2.9-7

I • I • I 3 l 4~
V

the reactor effluent. The design of the isothermal methsnol synthesis reactor
Is based on experience in the construction of Fischer-Tropsch plants. The
exotherm£c conversion of hydrogen with cnrbon monoxide and carbon dioxide to
methanol takes plato In the tubes filled with copper-based catalyst. The
reaction heat is used to generate steam from the boiler water surrounding the
tubes. The reaction mixture exchanges the major portion of Its sensible heat
with the reacto~ feed in a heat exchange. It is cooled to ambient
|

temperature wlth air and cooling water and sent to the product separator,
"Wild*' methanol is produced after the product separator bottoms is flashed at
medium pressure and sent to the MTG plant.

Lurgl's methanol synthesis process is a highly commerclallzed,

efficient, and tellable process. MaEeup gas and recycle gas compressors are
key items, but operating pressures and flows are not extreme. Service Is
clean and nonfoullng.

j'

The outstaudlnE features of the methanol synthesis catalyst are

hlgh-converslon efficiency, long llfe, and almost complete suppression of
side reactions. The methanol reactor may be compared to a shell-and-tube heat
exchangez with no mechanlcally moved part in the overall reactor system.

The c a t a l y s t t e m p e r a t u r e i n the s y n t h e s i s r e a c t o r i s c o n t r o l l e d by
the vapor p r e s s u r e of the e v a p o r a t i n g b o i l e r water around the tubes, which
ensures t h a t the copper c a t a l y s t i s not exposed to extreme t e m p e r a t u r e s . This
f
would r e s u l t i n premature aging of the c a t a l y s t c a u s e d by r e c r y s t a l l i z a t i o n
of the copper. The r e a c t o r d e s i g n and t h e r e a c t o r c o n t r o l of the c a t a l y s t
t e m p e r a t u r e by steam p r e s s u r e o f f e r s the f o l l o w i n g major advant~g2s:

- Constant catalyst temperatures even at upset operating

c o n d i t i o n s by maloperatlon.

- Gentle catalyst treatment by avoiding excessive temperatures

and sudden temperature changes.

11-1.2.9-8

..F i I ° I ,
 P

- Almost complete utillsatlon of the reaction heat f o ~ ~.gh-

pressure steam generation.

- Excellent turndown ratio.

- High flexibility regarding variations of CO and C0 2 content

in the synthesis gas.

Although the c a t a l y s t is sensitive to s u l f u r , commercial

operation of this type of reactou design in conjunction with Rectlsol units
has shown that sulfur poisoning is not a problem.

The teehn~.cal risk of methanol s~Ithesls by the Lurgl process is

Judged to be. v e r y l o w ,

1.2.9-I PRESSURE SWING ADSORPTION (PSA) UNIT

The Heavy Gasollne Treating (HGT) unit used to reduce

durene in the finished gasoline to about 2 wtZ durene requires a small flow
'of hlgh-purlty hydrogen. A PSA unit produces this hydrogen stream from the
methanol synthesis purge streaw,

A. Basls of Desl~n

Feed to the PSA unit is the purge gas stream from

the methanol synthesis unit. Product hydrogen is fed to the HGT unit to
eatalytlcally hydrotreat a heavy gasollne stream. The PSA purge or tall gas
£s sent to the p l a n t fuel gas system. Feed, product, and tall g a s
compositions are shown below.

II-1.2.9-9

~ m
P
 C°
Feed and Product Streams

Pr~A Hydrogen PSA

Feed Product T a l l Gas
Component ( l b mol/hr) ( l b mol/hr) ( l b mol/hr)
,,,. ,.

H2 566.03 329.06 236.97

CH4 35.13 Trace 35.13
CO 28.32 Trace 28.32
CO2 22.12 - 22.12
N2 104.98 0.25 104.73
Ar 32.62 0.08 32.54
CH30H 3.23 - 3.23
Totnl dry, ib mol/hr 792.43 329,39 463.04
H20 8 ppm "- 13 ppm
Tot~1 wet, Ib mol/hr 792.43 329.39 463.04
Total, lb/hr 7,821.0 673.6 7,147.1
Pressure, psta 994 650 60
Temperature, °F 100 110 100

B. P r o c ei s s S e l e c t i o n R a t i o n a l e

The p r o c e s s s e l e c t i o u o£ PSA was made t o meet t h e

r e q u i r e m e n t b y Mobil f o r a 99.9 p u r i t y .hydrogen f o r h y d r o t r e a t i n g use in the
HCT u n i t . The p r i n c i p a l s u p p l i e r o£ t e c h n o l o g y m e e t i n g t h i s requiremeut is
Union Carbide.

immemmmr"

II-1.2.9-10

I , I 2 I
.......... , ,.,, ~ ~ --

!
 I

p ~wIJlrlJRi p~.r~ flf rMtlt~l~Qi ¸ J~ I m ~Dw e r

P

C. Process Description
-!

The b a s i c PSA p r o c e s s i e one in which i m p u r i t i e s are

absorbed from the f e e d gas at high pressure and t h e n a r e d e s o r b e d a t low
p r e s s u r e . The p r o c e s s o p e r a t e s on a r e p e a t e d c y c l e h a v i n g two b a s i c steps -
adsorption and r e g e n e r a t i o n . T h e r e Iv no c h a n g e i n t e m p e r a t u r e e x c e p t f o r
t h a t caused by the h e a t o f a d s o r p t i o n and d e s o r p t l o n .

The U n i o n C a r b i d e HYSIV PSA u n i t employs a p a t e n t e d

PSA p r o c e s s to p u r i f y a c r u d e h y d r o g e n f e e d s t r e a m and p r o d u c e a h i g h - p u r i t y
hydrogen product stream. The p r o c e s s u s e s f o u r a d s o r b e n t beds to p r o v i d e a
c o n t i n u o u s and c o n s t a n ~ hydrogen product flow. One a d s o r b e r i s a l w a y s on
adsorption while the other three are in various stages of regeneration.
During t h e a d s o r p t i o n s t e p , f e e d gas e n t e r s the bottom of the adsorber and
all impurities a r e a d s o r b e d . H i g h - p u r i t y hydrogen p r o d u c t i s a v a i l a b l e a t the
top o f t h e a d s o r b e r a t 2 to 3 ~ s i l e s s t h a n t h e f e e d p r e s s u r e . Following the
a d s o r p t i o n s t e p , an a d s o r b e r i s r e g e n e r a t e d i n f o u r b a s i c s t e p s :

(I) The a d s o r b o r is depre~surlzed in a direction

recurrent with the f e e d f l o w to a low-pressure
level. This recurrent flow is used to re-
p r c s s u r l z e and p u r e e o t h e r a d s o r b e r s .

(2) The a d s o r b e r is depressurizad in a counter-

current direction t o waste p r e s s u r e and remove
i m p u r i t i e s from t h e s y s t e m .

(3) The adsorber is puxged at low p r e s s u r e with

pure hydrogen (from another adsorber) to
complete the removal of impurities from the
adsorbent.

11-1.2.9-11

. . . . J 0

$ 6
ii
V

I
CI,
(4) The p r e s s u r e of the adsorbor is raised to
adsorption pressure with pure hydrogen £n
preparation for another adsorption step.

O p e r a t i o n o f t h e PSA u n i t is completely automatic

wlth all control valves being actuated by an e l e c t r l c / p n e u m a t l c control
systems Controls are provided to r e g u l a t e Internal system pressures and
flows. The c a p a c i t y of the u n i t can be v a r i e d from IOOZ o f d e s i g n to zero by
v a r y i n g t h e hydrogen w l t h d r a w a l r a t e ,

The h y d r o g e n p r o d u c t i s a v a i l a b l e a t c o n s t a n t f l o w ,
p r e s s u r e , and t e m p e r a t u r e . Hydrogen r e c o v e r i e s can be m a i n t a i n e d a t a flow
rate as low ae 30Z o f r a t e d d e s i g n f l o w . At the lower w i t h d r a w a l r a t e s , the
hydrogen r e c o v e r y d e c r e a s e s u n l e s s t h e c y c l e time i s i n c r e a s e d .

D. P~Lsk
,i, | Assessment

Over 190 PSA h y d r o g e n u n i t s have been c o n s t r u c t e d

w o r l d w i d e d u r i n g the past 15 y e a r s or are c u r r e n t l y under c o n s t r u c t i o n . Seven
u n i t s have been d e s i g n e d to p r o c e s s a methanol purge s t r e a m .

The PSA u n i t can be o p e r a t e d ~rlth a n y p r o d u c t i o n

race desired, f r o m 100Z o f d e s i g n down t o z e r o f l o w , while maintaining
product h y d r o g e n p u r i t y . I t i s t h e f e a t u r e of o p e r a t i n g a t zero hydrogen floI¢
Chat a l l o ~ a the PSA u n i t to r e c o v e r r a p i d l y from u p s e t s c a u s e d b y c h a n g e s i n
the feed condition. The P SA u n i t c a n be s t a r t e d up o r shut down
i n s t a n t a n e o u s l y . For l o n g e r shutdown p e r i o d s , a s h o r t purging p r o c e d u r e may
be n e c e s s a r y . A weekend s h u t d o w n w i t h ~mmediate r e s t a r t ~rlthout F J r g i n g i s
common p r a c t i c e w i t h some P S A u n i t s .

The operation of the PSA u n i t is automatic and

r e q u i r e s no d i r e c t o p e r a t o r attention. The a d s o r b e r e switch automatically
. through the various cycle steps. These s t e p s a r e c o n t r o l l e d by t i ~ e d e l a y

C
1 7 - I . 2.9-12

-l"
 relays and p r e s s u r e s w i t c h e s . I f the f e e d r a t ~ i s i n c r e a s e d or d e c r e a s e d , the
c y c l e time may be a d j u s t e d to o b t a i n m~ximum performance. This a d j u s t m e n t may
he made at the PSA c o n t r o l panel or from a remo~':¢ l o c a t i o n .

The PSA u n i t shuts down a u t o m a t i c a l l y on c y c l e

advance failure, l o s s of i n s t r u m e n t a i r , or l o s s of adso.-ption p r e s s u r e . Each
a d s o r b e r i s i s o l a t e d a t the p r e s s u r e c o r r e s p o n d i n g to i t s particular step in
the cycle sequence a t the time of shutdown. Thus, a l l a d s o r b e r s a r e r e a d y f o r
subsequent a t a r t u p .

The o n l y moving p a r t s i n t h e PSA u n i t are control

components and a u t o m a t i c v a l v e s . C o n s i d e r a b l e care has gone i n t o 8 e l e r . , t i o n o f
t h e v a r i o u s c o n t r o l s and v a l v e s . The proposed d e s i g n i s t h e r e s u l t o f over 15
y e a r s of c o n t i n u a l updating b a s e d on f i e l d - o p e r a t i n g experience. Union
Csrbide's mo8t r e c e n t survey of operating units showed t h a t the average
oustream availability of the units between scheduled shutdowns exceeded
99.8Z.

Units built in the last several years h a v e shown

even b e t t e r reliability and e x p e r i e n c e periods well in excess of 1 year
between unscheduled s h u t d o w n s . No p h y s i c a l deterioration or reduction in
a d s o r b e n t c a p a c i t y o f t h e a d s o r b e n t has been observed in a n y o f t h e e x i s t i n g
units. This covers a period of over 15 y e a r s . Union Carbide c o n c l u d e s from
t h i s t h a t the l i f e o f the a d s o r b e n t i s good f o r t h e l i f e of t h e e q u i p m e n t .

II-1.2.9-13

s ! e
I , I_
I
 0
p 'i,'," - - ' - " - - - ' - - - " "'~'
.... • '-~"-°"'"'" ' " . . . . ".- - -.- -." ." ' '.' ~ .' ~ ".~ ".' ~." . - - - - --"---.,..-,.,,,
. . . . ....,--- P

CI.
E. proce.s Flov and Control DiaErams (Includlng
Material Balance)

Process Plow and Control Diagrams for Methanol

Synthesis Unit 25 a r e as f o l l o w s :

Drawing No. Title

D-25-MP-1NP PFCD Methanol Synthesis - U n i t 25 Gas C o m p r e s s i o n

D-25-MP-2~P PFCD Methanol Synthcsis - U n i t 25 Gas R e a c t i o n

D-25-MP-3NP PFCDMethanol Synthesis - Unit 25 Pressure Swing

Adsorption

D-25-MP-4NP M a t e r i a l B a l a n c e M e t h a n o l S y n t h e s i s - U n i t 25
t'

C
Tr-1.2.9-14

i,'