CATALYSI S I N DI RECT COAL LI QUEFACTI ON : STATUS AND DI RECTI ONS FOR RESEARCH

Fr ank Der byshi r e

Sut cl i f f e Speakman Car bons Li mi t ed
Guest St r eet , Lei gh, Lancashi r e, U. K.
The economi c vi abi l i t y and oper abi l i t y of pr ocesses to conver t coal s t o usef ul
l i qui d pr oduct s i s cont i ngent upon t he devel opment and appl i cat i on of ef f ect i ve
cat al yst s. New and i mproved cat al yst s can l ead to more f avour abl e pr ocess
economi cs by i ncr easi ng t he r at e of conver si on and t he sel ect i vi t y to t he desi r ed
pr oduct s and by al l owi ng oper at i on at r educed t emper at ur es and pressures.
The pr ocesses of pr i mar y coal di ssol ut i on and coal l i qui ds upgr adi ng ar e
di st i ngui shed. The st at us and l i mi t at i ons of cat al yst s used t o pr omot e t hese
r eact i ons ar e di scussed t oget her wi t h appr oaches whi ch coul d l ead to t he
devel opment of i mproved and novel cat al yst s.
I NTRODL' CTI ON
The pr oduct i on of di st i l l at e f uel s and chemi cal s f rom coal has never been
economi cal i n a f r ee market economy. The pr i nci pal f act or s whi ch cont r i but e t o
t he hi gh cost of coal - der i ved l i qui ds ar e t he l arge amount s of hydrogen whi ch
must be added t o r emove het er oat oms and to conver t mat eri al cont ai ni ng about 5
wt% hydrogen to pr oduct s wi t h bet ween 12 t o 14 wt%hydr ogen, t he sever e r eact i on
condi t i ons ( t emper at ur e and pr essur e) and t he r el at i vel y l ow r at es of conver si on
whi ch are exper i enced.
I n spi t e of t hese l i mi t at i ons t her e ar e val i d r easons f or pursui ng r esear ch and
devel opment i n coal l i quef act i on. Pr act i cal l y ever y f ut ur e energy scenar i o
envi si ons the devel opment of i ndi genous f ossi l f uel r esour ces to suppl ement and
r epl ace mat er i al s der i ved f rompet r ol eumcrudes. I n t he shor t t er m, si t uat i ons
coul d ar i se whereby t he suppl i es of i mport ed cr udes t o oi l - poor i ndust r i al i sed
nat i ons are r est r i ct ed and, i n t he l ong t er m, worl d pet rol eumr eser ves wi l l be
event ual l y be depl et ed.
As has occurred i n t he devel opment of t he pet rol eumprocessi ng and chemi cal
i ndust r i es, t he r out e t o si gni f i cant i mpr ovement s i n l i quef act i on pr ocessi ng
l i es i n t he successf ul devel opment and appl i cat i on of sui t abl e cat al yst
syst ems. I n t hi s paper some of t he more sal i ent aspect s of l i quef act i on
cat al yst s ar e r evi ewed i n t erms' pf t he l i mi t at i ons of our present under st andi ng
and appr oaches whi ch coul d l ead to i mproved and novel devel opment s. Ref er ence
i s made t o a much mor e ext ensi ve cr i t i cal revi ewwhi ch t he aut hor has r ecent l y
compl et ed f or t he I nt er nat i onal Energy Agency under t he sponsor shi p of t he
Uni t ed St at es Depar t ment of Ener gy (1). A compani on revi ewon cat al ysi s i n
syngas conver si on has al so been pr epar ed by Al ex Mi l l s ( 2 ) .
The recogni t i on t hat l i quef act i on t akes pl ace i n t wo l oosel y- def i ned st ages,
consi st i ng of coal di ssol ut i on f ol l owed by upgr adi ng of t he sol ubi l i sed
pr oduct s, has l ead t o t he concept of t wo- st age pr ocess conf i gur at i ons. The
pr ogr essi on f rom a si ngl e, noncat al yt i c pr ocess t o a cat al yt i c - cat al yt i c t wo
st age pr ogr ess i s summar i sed i n Tabl e 1 ( 3 ) . The adopt i on of a f ul l y cat al yt i c
pr ocess has l ead t o i ncr eases i n coal t hr oughput and i n t he yi el d and qual i t y of
di st i l l at e product s. I n addi t i on, si nce t he const r uct i on of t he f i r st
commer ci al - scal e pl ant s i n Ger many t her e has been appr eci abl e pr ogr ess i n
l ower i ng oper at i ng sever i t y and i mpr ovi ng t he sel ect i vi t y t o l i qui d pr oduct s,
188
Tabl e 2. Never t hel ess t her e i s st i l l a pressi ng need f or i nnovat i ons whi ch can
l ead t o f ur t her gai ns i n pr ocess per f or mance and oper abi l i t y.
bet ween t he pr ocesses of di ssol ut i on and upgr adi ng pr ovi des a conveni ent
di vi si on bet ween di sper sed and suppor t ed cat al yst s. Whi l e t her e ar e except i ons,
t he f or mer have been appl i ed pr i mar i l y t o pr omot e t he pr ocess of coal
di ssol ut i on and t he l at t er to upgr adi ng t he sol ubi l i sed coal l i qui ds. These
cat al yst s cannot real l y be used i nt er changeabl y. I t i s unl i kel y t hat
di sper sed cat al yst s coul d r eal i se t he sel ect i vi t y whi ch i s possi bl e wi t h
support ed cat al yst s; r est r i ct ed access t o t he r eact i on sur f ace of suppor t ed
cat al yst s pr ecl udes t hei r bei ng abl e to di r ect l y i nf l uence t he r eact i ons of
coal s and hi gh mol ecul ar wei ght coal der i ved pr oduct s.
The di st i nct i on
SUPPORTEDCATALYSTS
The cat al yst s whi ch have been appl i ed to coal l i qui ds upgr adi ng compr i se a
combi nat i on of t he met al s Co, Ni , Mo and W, t oget her wi t h pr omot i onal addi t i ves,
di st r i but ed over a porous suppor t of al umi na or si l i ca- al umi na. The cat al yst s
must be sul phi ded i n or der to at t ai n t hei r act i ve f orm. These cat al yst s ar e
used ext ensi vel y i n pet rol eum r ef i ni ng and evol ved f romcat al yst s whi ch wer e
or i gi nal l y devel oped f or hydr opr ocessi ng di st i l l at e coal l i qui ds. No concer t ed
at t empt s have been made to adapt themf or hydr opr ocessi ng hi gh boi l i ng coal
l i qui ds. Resear ch ef f or t s have f ocused mai nl y on cat al yst scr eeni ng and
eval uat i on and l i t t l e at t ent i on has been gi ven to i nvest i gat i ng novel
f or mul at i ons.
One of t he i mpor t ant concl usi ons emanat i ng f roma l ong pr ogr amof r esear ch by
Sul l i van and co- wor ker s at t he Chevr on Resear ch Company ( 4 , 5) i s t hat coal
l i qui ds can he adequat el y hydr opr ocessed over convent i onal cat al yst s pr ovi ded
t hat t he end- poi nt does not exceed about 370OC. The pr esence of hi gher
boi l i ng mat er i al s i s del et er i ous to cat al yst l i f e whi ch i s shor t ened by t he
f or mat i on of car bonaceous deposi t s, t he adsor pt i on of basi c compounds and t he
deposi t i on of met al s. These ef f ect s ar e consi der abl y more pr onounced i n t he
pr esence of non- di st i l l abl e coal - der i ved mat er i al s. Under t hese condi t i ons and
duri ng cont i nuous pr ocessi ng t her e i s a rapi d and massi ve r educt i on i n cat al yst
act i vi t y dur i ns t he f i rst 30 t o 50 hour s on st r eam, due pr i nci pal l y to t he
deposi t i on of car bonaceous mat er i al s whi ch ef f ect a dr ast i c r educt i on i n sur f ace
area. Subsequent l oss i n act i vi t y i s more gr adual and i s at t r i but ed to t he
accumul at i on of met al s. Ot her cont r i but or y causes ar e t he l oss of act i ve met al s
and si nt er i ng. Subst ant i al r esear ch has been conduct ed at t he Sandi a Nat i onal
Labor at or i es and t he Pi t t sbur gh Ener gy Technol ogy Cent er to i nvest i gat e t he
causes and mechani sms of deact i vat i on ( see r ef er ence 1). The deposi t i on of
carbon i s general l y at t r i but ed t o the adsor pt i on and r eact i on on cat al yst aci d
si t es of speci es such as pol ycondensed ar omat i cs and het er oat om- cont ai ni ng
compounds.
I t i s concl uded t hat t he exi st i ng gener at i on of suppor t ed cat al yst s cannot
adequat el y meet t he exact i ng r equi r ement s f or upgr adi ng pri mary coal l i qui ds.
Two pr ospect i ve appr oaches to r esol vi ng t hi s probl emar e i ndi cat ed. The f i r st
i nvol ves t he devel opment of new suppor t ed cat al yst s whi ch ar e l ess suscept i bl e
to deact i vat i on by t he mechani sms di scussed. Avenues f or r esear ch ar e
consi der ed i n r ef er ence (1). The second appr oach i s t o pr oduce mat er i al s whi ch
ar e more amenabl e t o upgr adi ng over suppor t ed cat al yst s t hr ough ef f ect i ve
cat al yt i c cont r ol of t he pr ocess of coal di ssol ut i on. Whi l e bot h of t hese
st r at egi es are consi der ed t o be i mpor t ant pr i or i t i es f or f ut ur e r esear ch, t he
remai nder of t hi s paper wi l l be gi ven to a di scussi on of di ssol ut i on cat al ysi s.
189
I t i s consi der ed t hat successf ul r esear ch i n t hi s ar ea coul d have an i mmedi at e
i mpact on l i quef act i on pr ocess devel opment .
DI SSOLUTI ON CATALYSTS
Al t hough many cat al yst s have been exami ned i n f undament al st udi es, l ar ge scal e
i nvest i gat i ons have been pr i mar i l y concer ned wi t h t wo gr oups of cat al yst
mat er i al s; metal sul phi des and aci d cat al yst s. The sul phi des of met al s such as
Mo and Fe ar e bel i eved to f unct i on as hydr ogenat i on cat al yst s whi l e met al
hal i des l i ke ZnCl z pr omot e bond cl eavage by an i oni c mechani sm. I n bot h
cases, ef f ect i ve cont r ol of t he di ssol ut i on pr ocess r equi r es i nt i mat e cont act
bet ween t he cat al yst and coal . I n t ur n, t hi s means t hat t he used cat al yst i s
associ at ed wi t h t he sol i d r eact i on pr oduct s, whi ch compl i cat es i t s recovery.
For t hi s r eason, l ow cost has been a pr i or i t y i n cat al yst sel ect i on as i t al l ows
use on a once- t hr ough basi s. Thi s has l i mi t ed t he choi ce of candi dat e cat al yst
mat er i al s. The devel opment of t echnol ogi es f or cat al yst r ecover y coul d
al l evi at e t he cost const r ai nt and have a maj or i nf l uence on br oadeni ng t he
r esour ce base f or the sel ect i on of cat al yst s.
I t i s al so t r ue t o st at e t hat r esear ch on cat al yt i c coal di ssol ut i on has been
r et ar ded by the per si st ent and mi sgui ded bel i ef t hat cat al yst s cannot i nf l uence
t he r eact i ons whereby t he sol i d coal f eed i s conver t ed t o sol ubl e products.
Si tl oh i de Cat al yst s
For most met al s, t he t her modynami cal l y st abl e f ormunder l i quef act i on condi t i ons
i s R sul phi de or mi xt ur e of sul phi des. For t unat el y, a number of sul phi ded
met al s are act i ve cat al yst s for coal di ssol ut i on. A wat er or oi l - sol ubl e
cat al yst pr ecur sor i s nor mal l y i nt roduced to t he coal or coal - sol vent sl ur r y i n
a manner i nt ended to di sper se i t ef f i ci ent l y. The sul phi ded cat al yst i s
subsequent l y produced by t he i n- si t u r eact i on of t he pr ecur sor wi t h sour ces of
sul phur . For a gi ven met al , the cat al yst act i vi t y wi l l be a f unct i on of i t s
di sper si on and t he st oi chi omet r y of t he sul phi de phase.
Di sper si on i s very di f f i cul t to quant i f y. I t i s al ways descr i bed qual i t at i vel y
and i nf erred f rom exper i ment al data. Logi cal l y, i t wi l l be dependent upon t he
pr ecur sor composi t i on and the mode of i ts addi t i on. Ther e i s a need to devel op
met hods to quant i t at i vel y assess cat al yst di sper si on. Wi t hout t hi s i nf or mat i on,
t her e i s no means to di st i ngui sh ef f ect s due t o di f f er ences i n di sper si on f r om
t hose caused by changes i n ot her par amet er s.
The ki net i cs of f or mat i on of the act i ve phase wi l l be det er mi ned by t he
di sper si on and composi t i on of t he cat al yst pr ecur sor and t he avai l abi l i t y of
sul phur - cont ai ni ng speci es. Thi s r eact i on i s of some r el evance si nce, i f t he
r at e i s sl ow, t he i ni t i al and cr i t i cal r eact i ons wi t hi n t he coal mat r i x may be
t her mal l y cont r ol l ed, despi t e t he ost ensi bl e pr esence of cat al yst .
I ncr easi ng t he par t i al pr essur e of H2S wi l l pr omot e pr ecur sor conver si on and
can have an i mpor t ant i nf l uence on cat al yst act i vi t y. I n t he pr esence of added
pyr r hot i t e, i ncr easi ng t he H2S part i al pr essur e has been shown to enhance t he
hydr ocr acki ng of di phenyl et her and di phenyl met hane ( 6) . Resear ch on upgr adi ng
pet rol eum f eedst ocks wi t h unsuppor t ed vanadi um cat al yst s showed t hat t he
cat al yst act i vi t y passed t hr ough a maxi mum bet ween 10- 25 mol e per cent HzS
( 7 ) . St udi es wi t h suppor t ed cat al yst s have demonst r at ed t hat i ncr easi ng t he
par t i al pr essur e of Hz S accel er at es t he rat e of
I
190
hydr odeni t r ogenat i on (8-11). One expl anat i on of t hese phenomena i s t hat t he
HzS part i al pr essur e ser ves bot h to mai nt ai n t he cat al yst i n i t s sul phi ded
st at e and to cont r ol i ts st oi chi omet r y. However , i t has al so been f ound t hat
HzS al one can pr omot e cr acki ng r eact i ons and i t s di r ect par t i ci pat i on i n
hydr ogenol ysi s r eact i ons may wel l cont r i but e t o t he ef f ect s obser ved i n t he
presence of cat al yst s.
Some t hought s ar e pr esent ed her e concer ni ng t he mechani sms by whi ch sul phi de
cat al yst s may pr omot e coal di ssol ut i on. I ndi sput abl y, t hey pr omot e
hydr ogenat i on of t he coal . I t i s al so pr obabl e t hat t hey pr ovi de sever al ot her
f unct i ons al t hough, as yet , t here have been no cl ear i ndi cat i ons of these.
McMi l l en ( 12- 14) , and ear l i er Vernon (15), have descr i bed a mechani smby whi ch
t he addi t i on of H- at oms to t he i pso posi t i ons of l i nkages to ar omat i c syst ems
can i nduce bond cl eavage. Fr ee H at oms coul d be made avai l abl e f romone of
sever al sour ces i ncl udi ng t he cat al yt i c di ssoci at i on of mol ecul ar hydrogen.
However , even at hi gh l evel s of di sper si on, a l ar ge pr opor t i on of t he cat al yst
cent r es must be di st ant i n mol ecul ar di mensi ons f rom t he bonds whi ch ar e
broken. The f aci l i t y wi t h whi ch hydr ogen i s known t o move t hr ough t he st r uct ur e
of coal s suggest t hat i t shoul d be abl e to di f f use f romt he si t es wher e i t i s
gener at ed by a spi l l - over mechani sm, Fi gur e 1. Thus t he cat al yst can be vi ewed
as a means to i nj ect H- at oms i nt o t he coal or t he coal - sol vent mi xt ure and
t hereby i ncr ease t he pool of avai l abl e hydrogen. Thi s hydr ogen wi l l be
avai l abl e f or ar omat i c hydr ogenat i on, t he pr omot i on of bond cl eavage r eact i ons
and r adi cal st abi l i sat i on.
I n t he pr oposed mechani sm, t he cat al yst does not par t i ci pat e di r ect l y i n bond
cl eavage whi ch i s dependent upon the l evel of t her mal ener gy i nput . Thi s coul d
expl ai n why, for a gi ven coal , di f f er ent cat al yst s have been f ound t o show
evi dence of l i quef act i on act i vi t y over t he same r ange of t emper at ur e, Fi gur e 2
(16). The t hr eshol d t emper at ur e wi l l depend upon t he t ypes and di st r i but i on of
connect i ng l i nkages and i s expect ed t o di f f er f romcoal to coal and to showa
syst emat i c change wi t h coal rank.
The ef f ect i veness of t he cat al yst can be st r ongl y i nf l uenced by t he pr esence and
composi t i on of a l i quef act i on sol vent . Whi l e space pr ecl udes an ext ended
di scussi on of t hi s subj ect , i t seems t hat t hose sol vent char act er i st i cs whi ch
have been f ound to be desi r abl e i n t her mal l i quef act i on al so hol d f or
cat al yt i c coal conver si on. The sol vent can pr ovi de addi t i onal r out es f or t he
t r anspor t of H- at oms produced by t he cat al yt i c di ssoci at i on of Hz. The
presence of pol ycondensed ar omat i cs i n the sol vent has been f ound t o be
par t i cul ar l y advant ageous ( see r ef er ence 1).
The possi bi l i t y t hat t her e exi st s a t emper at ur e t hr eshol d, bel ow whi ch
hydr ogenat i on cat al yst s have l i t t l e ef f ect on l i qui d yi el ds pl aces a l ower l i mi t
on t he t emper at ur es r equi r ed f or l i quef act i on. However t hi s const r ai nt need not
hi nder t he devel opment of mor e ef f ect i ve cat al yst s.
Cat al yst s wi t h hi gher act i vi t i es f or di ssoci at i ng mol ecul ar hydr ogen wi l l
i ncrease t he avai l abi l i t y of hydr ogen at oms and may make i t possi bl e to oper at e
at more el evat ed t emper at ur es ( t her eby i ncr easi ng t he r at e of conver si on) whi l e
suppr essi ng condensat i on react i ons. Reduct i ons i n oper at i ng pr essur e may al so
be r eal i sed. A number of si ngl e met al s and met al compounds whi ch possess t he
desi r ed at t r i but es have been excl uded f romr esear ch pr ogr ams because of t hei r
191
cost . The scope of f undament al r esear ch shoul d not be r est r i ct ed by such
consi der at i ons. Unt i l t he ext ent of any pot ent i al benef i t s ar e det er mi ned
exper i ment al l y, j udgement s of economi c vi abi l i t y can onl y be subj ect i ve.
Al t hough cat al yt i c hydr ogenat i on does not appear to si gni f i cant l y enhance t he
yi el d of product l i qui ds bel ow a cer t ai n t emper at ur e r ange, i t has been shown
t hat react, i on at l ower t emper at ur es can ef f ect st r uct ur al modi f i cat i ons to t he
coal whi ch ar e advant ageous to t he pr oduct i on of l i qui ds upon subsequent
hi gh- t emper at ur e r eact i on (17,18). The i nf l uence of t he cat al yst can t hus be
augment ed by r eact i ng t he coal i n successi ve st ages of i ncr easi ng t emperat ure.
Per haps t he most pr omi si ng appr oach to t he devel opment of novel cat al yst s l i es
i n research i nt o mul t i component syst ems whi ch, i n compar i son t o work on si ngl e
met al s, ar e essent i al l y unexpl or ed. Ther e ar e good r easons t o ant i ci pat e t hat
syner gi st i c ef f ect s wi l l l ead t o exci t i ng di scover i es. Syner gi smhas been
r epor t ed f or Fe - Mo cat al yst s (19). I t i s supposed t hat t he t wo met al s pr ovi de
compl ement ary f unct i ons whi ch r esul t s i n non- addi t i ve behavi our. A f ur t her
exampl e of thi s i s gi ven bel ow. The use of a second component coul d al so r educe
cat al yst cost i f t he concent r at i on of a more expensi ve component can be r educed.
Aci d Cat al yst s
Aci d cat al yst s can pr omot e t he cl eavage of t he l i nkages whi ch connect coal
st ruct ural uni t s and cr ack t he st r uct ur es whi ch compr i se t hese uni t s. Sever al
of Lhe cat al yst s of i nt er est f or coal di ssol ut i on ar e met al hal i des, such as
ZnCl z, whi ch possess a l ow mel t i ng poi nt and devel op si gni f i cant vapour
pr essur e at sub- pyr ol ysi s t emper at ur es. Thi s f aci l i t at es t hei r penet r at i on and
di spersi on i n t he coal mat ri x. Cr acki ng r eact i ons proceed by an i oni c mechani sm
i n whi ch pr ot onat i on of the r eact ant s i s t he i ni t i al and rat e - l i mi t i ng st ep.
The dr i vi ng f or ce i s t he st r engt h of t he aci d. By usi ng st r onger aci d cat al yst s
t he rat e of r eact i on can be accel er at ed and t he r eact i on t emper at ur e can be
r educed.
Pr ocess devel opment r esear ch conduct ed by Zi el ke and co- wor ker s at t he
Consol i dat i on Coal Company i n t he 1960s and 1970s demonst r at ed t hat i t i s
possi bl e t o l i quef y coal s at f ast r at es of t hr oughput and wi t h hi gh sel ect i vi t y
to gasol i ne- r ange pr oduct s, usi ng a zi nc chl or i de cat al yst . The di sadvant ages
were ( i ) t hat t he use of massi ve concent r at i ons of ZnCl z necessi t at ed t he
devel opment of t echni ques f or cat al yst r ecover y and ( i i ) t hat t he cor r osi ve
nat ur e of the cat al yst cr eat ed pr obl ems i n pl ant const r uct i on and oper at i on ( see
r ef er ence 1).
I t i s possi bl e t hat many of t hese t echni cal di f f i cul t i es coul d be r esol ved.
However , t her e i s a f ur t her probl em r el at i ng to t he pr ocess chemi st r y. I n
gener al , aci d cat al yst s do not pr omot e hydr ogenat i on. As a consequence of t hei r
i nabi l i t y to adequat el y st abi l i se t he cr acked pr oduct s, cr acki ng r eact i ons ar e
accompani ed by condensat i on r eact i ons l eadi ng t o t he pr oduct i on of hi gh
mol ecul ar wei ght mat eri al s. A possi bl e sol ut i on i s to i nt r oduce a second
component whi ch can pr ovi de a hydr ogenat i on f unct i on, Tabl e 3 ( 2 0 ) . As
di scussed above, t her e ar e i ndi cat i ons t hat r esear ch i nt o mul t i component
cat al yst f or mul at i ons can l ead to i mproved cont r ol of t he r eact i on chemi st r y of
coal conver si on. I n t hi s case, i t coul d bri ng t he more desi r abl e f eat ur es of
aci d cat al ysi s cl oser to pr act i cal r eal i sat i on.
192
I Ref er ences
>
1.
1
1 2.
3.
4.
5.
6.
Der byshi r e, F J (1988) Cat al ysi s i n coal l i quef act i on: new di r ect i ons f or
r esear ch.
I EA Coal Resear ch, London, UK ( i n pr ess)
Mi l l s, G A (1988) Cat al yst s f or f uel s f romsyngas,
I EA Coal Resear ch. London, UK ( i n press)
Weber W, St ewar t N (1987) Di r ect coal hydr ol i quef act i on.
EPRI J our nal : 12(1); 40-41
Sul l i van R F (1986) Tr anspor t at i on f uel s f rom t wo- st age l i quef act i on
pr oduct s.
Amer i can Chemi cal Soci et y, Di vi si on . of Fuel Chemi st r y. Pr epr i nt s; 31(4);
280-293
Sul l i van R F, Fr umki n H A (1986) Ref i ni ng coal l i qui ds: wher e we st and.
Amer i can Chemi cal Soci et y. Di vi si on of Fuel Chemi st rr. Pr epr i nt s; 31(2);
325-339
Sweeny P G, St enber g V I , Hei R D, Mont an0 P A (1987) Hydr ocr acki ng of
di phenyl et her and di phenyl met hane i n t he pr esence of i ron sul phi des and
hydr ogen sul phi de.
Fuel : 66; 532-541 (1987)
Gat si s J G (1975) Cat al yt i c conver si on of hydr ocar bon mi xt ures.
US Pat ent 3.915.842; 6 pp (28 Oct 1975)
Hi r schon A S, Lai ne R M (1985) Cat al yt i c hydr odeni t r ogenat i on of an SRC I 1
coal l i qui d: ef f ect of hydr ogen sul phi de.
- Fuel ; 64; 868-872
Sat t er f i el d C N., Guel t eki n S (1981) Ef f ect of hydr ogen sul f i de on t he
cat al yt i c hydr odeni t r ogenat i on of qui nol i ne.
I &EC Pr ocess Desi gn & Devel opment ; 20; 62-68
Y
I
10. Yang S H and Sat t er f i el d C N (1983) Some ef f ect s of sul f i di ng of a
Ni Mo/ AhOs cat al yst on i t s act i vi t y f or hydr odeni t r ogenat i on of
qui nol i ne.
J our nal of Cat al vsi s; 81, 168-178
11. Yang S H, Sat t er f i el d C N (1984) Cat al yt i c hydr odeni t r ogenat i on of
qui nol i ne i n a t r i ckl e- bed react or. Ef f ect of hydr ogen sul f i de.
I &EC Pr ocess Desi gn & Devel opment ; 23; 20-25
12. McMi l l en D F, Mal hot r a R, Chang S- J , Ni genda S E (1985) Sol vent r adi cal
medi at ed hydr ogenol ysi s i n coal l i quef act i on.
I n: Pr oceedi ngs - 1985 I nt er nat i onal Conf er ence on Coal Sci ence, Sydney,
NSW, Aust r al i a, Per gamon Pr ess pp 91-94
13. McMi l l en D F, Mal hot r a R, Hum G P, Chang S- J (1987)
Hydr ogen- t r ansf er - pr omot ed bond sci ssi on i ni t i at ed by coal f r agment s.
J our nal of Energy and Fuel s; 1; 193-198
193
14. McMi l l en D F, Hal hot r a R, Chang S- J , Ni genda S E (1985) Hydr ogenol ysi s i n
coal l i quef act i on and pyr ol ysi s: t he r el at i ve i mpor t ance of sol vent r adi cal s
ai d f ree hydr ogen at oms.
Ameri can Chemi cal Soci et y, Di vi si on of Fuel Chemi st r y, Pr eDr i nt s; 30 (4);
297-307
15, Vernon L Y (19801 Fr ee r adi cal chemi st r y of coal l i quef act i on: rol e of
mol ecul ar hydr ogen.
Fuel ; 59; 102-106
16. Char cnsset H, Bacautl R, Besson M, J eunet A, Ni ckel B, Ober son M (1986) On
the chemi cal ef f ect s of cat al yst s i n t he di r ect l i quef act i on of coal .
Fuel Processi ng Tecl i nol ogy; 12; 189-201
17. Der byshi r e F J , Davi s A , Epst ei n M , St ansber r y P (1986) Temper at ur e- st aged
cat al yt i c coal l i quaf ac ti on.
m; 65; 1233-1240
18. Bol t on C, Ri emer C , Snape C E, Der byshi r e F J , Ter r er M- T (1988) Ef f ect of
10s t emperat ure cat al yt i c hydr ogenat i on on pyr ol ysi s and hydr opyr ol ysi s of a
bi t umi nous coal .
w; ( i n pr ess)
19. Garg D, Gi vens E N (1983) Rel at i ve act i vi t y of t r ansi t i on met al cat al yst s
i n coal l i qi i ef acti oi i .
Ameri can Chemi cal Soci et y, Di vi si on of Fuel Chemi st r y, Pr epr i nt s; 28 ( 5) ;
200-209
20. Nobl er D P, Bel l A T (1980) Hydr oqenol ysi s of di benzyl et her usi ng zi nc
chl or i de- met al co- cat al yst syst ems.
J ournal of Cat al ysi s; 61; 494-196
194
Tabl e 1 - Hi st or y of Pr ocess Devel opment and Per f or mance for Bi t umi nous Coal
Li quef act i on
Conf i gur at i on
Si ngl e st age Si ngl e st age Two st age Two st age
noncat al gt i c cat al yt i c noncat al yt i d cat al yt i c/
( 1982) ( 1982) cat al yt i c cat al yt i c
( 1985) ( 1986)
Di st i l l at e 41 52 62 70
(wt% coal maf )
Di st i l l at e 12. 3 20. 2 20. 2 26. 8
qual i t y/ gravi t y
O A P I
Noti hydrocarbons
( w t % )
S
0
N
0. 33 0. 20
2. 33 1. 0
1. 0 0.50
0. 23
1. 9
0. 25
0. 11
<1
0. 16
Sour ce: Weber and St ewar t , 1987 ( 31
Tabl e 2 - I mpact of Cat al ysi s on Pr ocess Condi t i ons and Sel ect i vi t y
Pr ocess
Si ngl e St age
I G Far ben
Ruhr kohl e ,
H- coal
Two St age
Inoncatalgtic/catalgtic)
Bri t i sh Coal
Lummus
Two St age
( cat al yt i c/ cat al yt i c)
HR I
Temp OC Pr essur e MPa Li aui d/ gas r at i o
480 30- 70 2. 4
475 30 2. 3
450 12 4. 0
100- 425 20
410- 460 18
4. 8
10. 8
400- 440 17 12. 0
Sour ce: var i ous
195
Table 3 - Effect of hydrogenation component on ZnClz - catalysed cracking
of dibenzylther
(atalyst % Ether 3; Y i el d
Conversion To1r;eire Insoluble Resin
Nolle 3 . n I . 1
znc:12 1cn.o 3 . 9 9 i . 0
S i 3 8 . 2 19.5 2 . 5
Ni+ZnClz 96.5 6 5 . 6 6.0
196
I
I
Figure 1
' C
/
CATALYST
HYDROGEN SPILLQVER
DISTRIBUTION OF W-ATOMS BY
Produced by catalytic dissociation of H2.
H-Atoms induce bond cleavage and stabilise radicals.
Fi gure ' 2
25tp(Mh' t TrC'
EVIDENCE FOR EXISTENCE OF A
THRESHOLD TEMPERATURE IN
CATALWIC COAL LIQUEFACTION
(BITUMINOUS COAL: TETRALIN: CATALYST =
40: 95: 0.8; HEATING RATE 3"CIMIN)
H. Charcosset and others (1986), Fuel procesSng Technology, E, 184201
19 7