Table Of ContentA C S S Y M P 0 S I U 6M3 4S E R I E S
DeactivaatnidoT ne sting
ofH ydrocarbPorno-cessing
Catalysts
PauOl' ConnoErD,I TOR
AkzNoo beCla talysts
TornT akatksauE,D ITOR
ChiyoCdoar poration
GeoffrLe.Wy o olerEyD,I TOR
MobiTle chnolCoogmyp any
Developferdo mas ymposisupmo nsored
byt heD ivisioofPn e troleCuhme mistIrnyc,.
att h2e1 O thN ationMaele ting
oft heA mericCahne micSaolc iety,
ChicagIol,l inois,
August20-12959,5
•
AmericCahne micSaolc ieWtays,h ingtDoCn ,
•
LibraoryfC ongresCsa taloging-in-Publication Data
Deactivaatnidto ens toifnh gy drocarbon-procacteaslsyisPntagsu l
I
O'Connoerd,i tToorr,uT akatsuekdai,t Goero,ffr ey Woolerye,d itor.
L.
p. cm.-(ACsSy mposisuemr iIeSsS,N00 97-615663;4 )
"Develofrpoemda s ymposisupmo nsobryet dh eD ivisoifo n
PetrolCehuemm istIryn,ca .tt, h e2 10tNha tional Meetthien g of
AmericaCnh emicaSlo cieCthyi,ca goI,l linAouigsu,s2 t0 -251,9 95."
Inclubdiebsl iograrpehfiecarle anncdei sn dexes.
ISBN0 -8412-131-46
1.P etroleum-Refining-C2o.nC garteaslsyesst.s -Congresses.
3.C atalpyosits oning-Congresses.
I.O 'ConnoPra,u lI.I T.a katsuTkoar,u1 ,9 48-. IIIW.o olery,
GeoffreyL oganI.V .Am ericanC hemicaSlo cieDtiyv.i soifo n
PetrolCehuemm istVry..Am erican Chemical Societ(y2.1 0tMhee:t ing
1995C:h icagIol,lV .I).S eries.
TP690.A1D14939 6
665.5'33-dc20 96-17665
CIP
Thibso oki sp rintoenda cid-frreeecy,c lpeadp er.
Copyrigh1t9 96
©
AmericaCnh emicSaolc iety
All RightRse servedT.h ea ppearaonfct eh ec odea tt heb ottoomf t hefi rspta geo fe ach
chaptientr h ivso lumien dicattheecs o pyriogwhnte rc'osn setnhta rte progracpohpiicoe fst he
chaptmeary b em adef orp ersonoarli nterunsaelo rf ort hep ersonoarli nterunsaelo f
specicfliice nTthsi.cs o nseinsgt i veonnt hec ondition, thhoawtteh vece orp,i peary t hes tated
per-cofpeyet hroutghhe C opyriCglheta raCnecnet eIrn,c 2.2,2 R osewooDdr ivDea,n vers,
0192f3o,r c opyibnegy ontdh apte rmitbtyeS de ctio1n0s7o r1 08o ft heU .SC.o pyright
MA
Law. Thicso nsednote sn ote xtentdoc opyionrgt ransmisbsyia onnym eans-grapohri c
electroniacn-yfo otrh epru rposseu,c ha sf org enerdails tribuftoirao dnv,e rtiosri ng
promotiopnuarlp osfeosr,c reatai nnge wc ollecwtoirvkef, o rr esaloer,f ori nformation
storaagnedr etriseyvsatle mTsh.ec opyifnegfe o era cchh aptiesir n dicatientd h ec odaet t he
bottoomft hefi rspta goef t hec hapter.
Thec itatoifot nr adnea measn d/noarm eosf m anufactuirnte hrisps u blicatiisno no tt ob e
constrausea dn e ndorsemoerna tsa pprovbayAl C So ft hec ommercpiraold ucotrss e rvices
referenhceerde inno;r s houltdh em erer eferehnecer eitno a nyd rawinsgp,e cification,
chemicparlo cesosr,o thedra tbae r egardaesad l icenosrae s a conveyaonfca en yr ighotr
permisstioot nh eh olderre,a deorr,a nyo ther peorrsc oonr porattioom na,n ufacture,
reproduucseeo,,r s elaln yp atentiendv entoiroo no pyrigwhotrekdt hamta yi na nyw ayb e
relattehde retRoe.g istenraemde st,r ademaertkcsu.,s, e idn t hipsu blicateivoenn,w ithout
speciifnidci cattihoenr eaorfen, o tt ob ec onsideurnepdr otebcytl eadw .
PRINTEDI NT HE UNITEDS TATES AMERICA
OF
AdvisoBryo ard
ACS SymposiumS eries
RoberJt.A laimo CynthAia.M aryanoff
Proct&e Gra mblPeh armaceuticalRs. W .J ohnsPohna rmaceutical
ResearIcnhs titute
MarkA rnold
UniverosfiI toyw a RogeAr .M inear
UniverosfiI tlyl inois
DavidB aker atU rbana-Champaign
UniverosfiT teyn nessee
OmkaramN alamasu
ArindaBmo se AT&TB elLalb oratories
PfizeCre ntrRaels earch
VincePnetc oraro
RoberFt.B radyJ,r . UniverosfiM tiyc higan
NavaRle searLacbho ratory
GeorgWe. Roberts
MaryE .C astellion NortCha roliSntaa tUen iversity
ChemEdCiotm pany
JohnR .S hapley
MargarAe.tC avanaugh UniverosfiI tlyl inois
NationSacli enFcoeu ndation atU rbana-Champaign
ArthurB .E llis DouglaAs.S mith
UniverosfiW tiys conastiM na dison ConcurrTeencth noloCgoirepso ration
GundaI .Ge org L.S omasundaram
UniverosfiK tayn sas DuPont
MadeleiMn.eJ oullie MichaDe.lT aylor
UniverosfiP teyn nsylvania Parke-DPahviasr maceuRteiscaela rch
LawrenPc.eKl emann WilliCa.mW alker
NabisFcooo dGsr oup DuPont
DouglaRs.L loyd PeteWri llett
TheU niverosfiT teyx aastA ustin UniverosfiS thye ffiel(dE ngland)
Foreword
1Jm ACS SYMPOSIUMS ERIEwSa sfi rsptu blisihen1d 9 7t4o
proviad em echanifsomr p ublishsiynmgp osia qiuinbc okolky
form.T hep urposoeft hisse riiesst o publciosmhp rehensive
bookdse velopfreodm symposiwah,i cahr eu sual"lsyn apshots
int imeo"f t hec urrernets earbcehi ndgo neo n a topipcl,u s
somer eviemwa terioantl h et opicF.o rt hirse asointi, s n eces
sartyh atth ep aperbsep ublisahseq du ickalspy o ssible.
Beforae s ymposium-bbaosoekid sp utu ndecro ntratchte,
proposteadb loef c ontenitsrs e viewfeodra ppropriatteon ess
thet opiacn df orc omprehensivoefnt ehsecs o llectSioomne.
paperasr ee xcludaetdt hipso inta,n do therasr ea ddedt o
rounodu tt hes copoef t hev olumeI.na dditiao drnaft, ofe ach
papeirs p eer-reviperwieodtr o fi nala cceptaonrcr ee jection.
Thisa nonymourse viepwr oceissss upervibsyet dh eo rganiz
er(so)ft hes ymposiuwmh,ob ecomteh ee ditoro(fts h)e b ook.
Thea uthotrhse nr evitshee ipra perasc corditnotg h er ecom
mendatioonfsb otht her eviewearnsd t hee ditorpsr,e pare
camera-recaodpyya ,n ds ubmitth efi nalp apertso t hee ditors,
whoc hectkh aatl nle cessraervyi sihoanvseb eenm ade.
As a ruleo,n lyo rigirneasle arpcahp erasn do rigirneal
viewp aperasr ei ncludientd h ev olumeVse.r batriemp roduc
tionosfp revioupsulbyl isphaepde rasr en ota ccepted.
ACS BOOKSD EPAR1MENT
Contents
Preafce..............................................................ix . ..............................................
O R E
VE VI W
1.P hilosophiOcvaelr vieowfT esting.....................2 . ...............................
PauOl' ConnoGre,o ffreyL .W oolerayn,d T oruT akatsuka
2. AdvantagPeoss,s ibiliatnidLe ism,i tatioofnS smal l-Scale
TestinogfC atalyfsotFrsix ed-BePdr ocess.e.s. ..........6. ...................
S.T .S ie
3.E valuatPionrge S tructuarnedM orpholoogyf H ydrocarbon-
ConversiCoant aly.s.t.s........................4.2. ...............................................
R.M ann,K .K halaafn,dA Al-Lamy
CATALYSTD EACTIVATION BY COKE
4. DeactivatoifZo eno liCtaet alybsytC so k.e..............6.2. .......................
T.M asudaan dK .H ashimoto
5.M odeso fC okinga ndD eactivatoifAo cni dZ eolite
Cataly.s.t.s. ..............................7.7. .............................................................
M. GuisnePt.M, a gnouxa,n dK .M oljord
6. CatalyCsotkin g,A ctivatianodnD ,e activa.t.i.o.n........9.1. ..................
P.A SermonM,. S.W .V onga,n dM .M atheson
7.N MR TechniqufeosrS tudyitnhgeC okingo fZ eolite-Based
Cataly.s.t.s. ..............................9.9. .............................................................
J.L .B onardMet.C, . B arragaen,dJ .F raissard
8. CharacterizaotfFi louni Cda talyCtriacc kingC atalyCsotk e
13
by C NMR andM assS pectrome.t.ry...............1.1.7. ...........................
B.J .M cGheeJ,.M .A ndreseCn.E, . S napeR,.H ughes,
C.L .K oona,n dG .H utchings
v
DEACTIVATION OFF LUIDC ATALYTIC CRACKING
CATALYSTS
9. CatalyDsetc aya sa SidRee actioofnt heC haiPnr ocesses
ofC atalyCtriacc king.........................1.3.4. ................................................
B.W .W ojciechoawnsdkN i.M .R ice
10. CatalyDseta ctivatiinFo lnu iCda talyCtriacc king:
A Revieowf M echanismsa ndT estiMnegt hod.s. .........1.4.7. ...............
PauOl' ConnoEr.,B revooArd C,. P ouwelasn,d
H.N .J .W ijngaards
11. SodiuDme activatoifFo lnu iCda talyCtriacc king
Catal.y..s...t... .................................................................................1..5...9.. ..
XinjZihna oa ndW u-ChenCgh eng
12. ContaminanMte-taDle activatainodMn e taDle-hydrogenation
EffectDsu rinCgy cliPcr opyleSntee amionfgF luiCda talytic
CrackinCga talysts........................1.7.1. .....................................................
LorTi. B oockT,h omaFs. P ettain,dJ ohnA Rudesill
DEACTIVATION OF REFORMINGC ATALYSTS
13. CatalyDseta ctivatiinAo dni abatPirce reforming:
ExperimentMaelt hodasn dM odelsf oPrr ediction
ofP erforman.c.e............................1.8.6. .....................................................
ThomasS .C hristenasnedJn e nRso strup-Nielsen
14.M echanisomfD eactivatiinRo enf ormiCnagt alysts
atS tarotfR un ..............................2.0.1. .....................................................
YaofanLgi uG,u oqinPga na,n dJ iujYiann g
DEACTIVATION OFH YDROPROCESSICNAGT ALYSTS
15. CatalyDseta ctivatiinCo onmme rciRaels idue
Hydrodesulfur.i.z.a.t.i.o.n. ..................2.0.8. ...............................................
HirokKio yamaE,i icNhaig aai,n dH ideaKkuim agai
16.D eactivatoifLo ing hNta phthAar omatizatiCoant alys.t. ....2.1.9. .......
S.F ukasNe.,I garasKh.Ai i,m otoa,n dK .K ato
17.E ffecto fP rocesCso nditiaonndsC atalyPsrto perties
onC atalyDseta ctivatiinRo ens iduHey droprocessing..2.2.9. .............
M.A bsi-HalaanbdAi Stanislaus
vi
18.C atalyDseta ctivatiinHo ynd rodemetalliza.t.•.i..o...n... ..•...............2. 38
J.P.J ansseAn.sD ,. v anL angeveSl.Td .,S ie,
andJ . AM.o ulijn
TESTINGO F CATALYSTP ERFORMANCE
19.A ctiviatyn dC oking Rateo fC atalyDsetasc tivated
byF ast-CokinSgp eciAedsd edt ot heF eed..............2.5.4. .....................
DadyB .D adyburjZohre,n yLui uS,h igeki Matoba,
ShiniOcshain aain,d T etsuSyhai rooka
20.P iloRte actoTre stinogft heE ffecto fN aphthBao iling
Poinint CatalyRteifco rming.....................2.6.8. ......................................
K.M oljorKd.,G randIe.,T anema,n dA .H olmen
21.V anadiuMmo biliitynF luiCda talyCtriacc kin.g. ........................2. 8.3.
RichaFr.dW ormsbechWeur-,C henCgh engG,w anKi m,
andR oberHt. H arding
22.I mprovedM ethodfso Tre stinagn dA ssessiDnega ctivation
froVma nadiuImn teractwiitohnF luiCda talyCtriacc king
Cataly...s...t.. .................................................................................2...9...6.. ..
BrucLee rnearn dM icheDle eba
23.R iseSri mulatToers:t inogfA dsorptiEoffne ct...s... ....................... 312
JacePkr uskAih,m etP ekediazn,dH ugod eL asa
24.D evelopmenotfa B ench-ScFalluei Cda talyCtriacc king
Microri..s..e....r.. .....................................................................................3 22
M.P.H elmsinMg.,M akkeea,n dJ .A .M oulijn
25.E valuatioofCn o keS electiovfFi ltyu iCda talyCtriacc king
Cataly.s...t..s... .........................................................................•.....3..4...0... .
E.B revoorAd.C, . P auwelFs.P, . P .O lthof,
H.N .J .W ijngaaradsn,dP auOl' Connor
26. CorrelatoifCo ant alyPsetr formancBee tweeLna boratory
Testsa ndC omme rciUanli tfso Hry drotreaRteisnigd uOaill. .. ..3 54
YoshimiMtisyua ucThaik,e sHhais higucNhaio,t Kiom bara,
andK atsuhFiusjai ta
27.L ifTee stinogfL ighHty drocarbAorno matizaCtaitoanl y.s...t...s 3 67
K.H irabayaFs.hI gia,r asahnidT, . K ondou
vii
28. PerformancTee stinogfH ydroconverCsaitoanl y.s.t.s. ....3.7.9. ...........
W. H.J .S tork
29. Developmenotfa T estP roceduTroeE valuaFtleu id
CatalyCtriacc kinCga talyRsetg enerab.i.l.i.ty. ........4.0.1. .....................
V.L .N .M urthyS,.D ebnatMh.,R amaR ao,S .K .R ay,
A K.D asa,n dS .G hosh
MODELING OF CATALYSPTE RFORMANCE
30. A CatalyDseta ctivaMtoidoenl f oRre siduOaill
HydrodesulfurizaantidAo pnp licattioDo ene p
HydrodesuurlifzatoifoD ni eseFlu el. ...............................4. .1..4. ............
Tom TakatsuYkuak,i taWkaad aa, ndS hin-ichi Inoue
31.M odelingC atalyDteiacc tivatoifBo enn zenHey drogenat.i.o.n4. 2.8. .
PauFl. M eiearn dM arvinM .J ohnson
INDEXES
AuthoIrn de.x. ................................4.3.9. .............................................................
AffiliatioInn de.x. ...................................4.4.0. .....................................................
SubjeIcntd e.x.................................4.4.0. .............................................................
Preface
CRUDEP ETROLEUMC ONSISTINOGF HEAVY HYDROCABRONSi sc on
verteidn tmoa nyp roducitnsl argree fineriuessu,a lilnyp rocesstehsa t
makeu seo f specific heterocgaetnaeloyussSt esl.e cttinhgec orrect
catalfyosrat s peciafipcp licaitsia o cno mpleaxn dd ifficutlats ka,n da ccu
rataen dr elialbalbeo rattoersytn se edt ob ed evelopfeodrt hipsu rpose.
As timep assetsh ec atalyusstesdi nt hev ariopurso cessleoss et heir
activaintdys ,e lectiavlisdtoey c linTehse.r efoervea,l uathiyndgr ocarbon
conversciaotna lyrsetqsu irae gso ods imulatoifot nh ec ataldyesatc tiva
tionb ehavioTrh.i si sa fieldo fg reaitn teretsott hes cientainsdt s
engineewrhso aret ryitnogt escta talyisnta s p ropewra yi no rdetro
improvkee yh ydrocarbon-conpvreorcseisossnue csha sc atalyctriacc king
andh ydroconversion.
Thefi eldo ft estiinsog n ei nw hicmho stc ompaniaerse w illitnog
sharteh eikrn owledagnedp roceduarnedso nei nw hicthh en eedf ore du
catioenx,c hangaen,ds tandardiziasct lieoanr plrye senAtl.s ot hel arge
growtohf h ydrocarbon-conpvreorcseisosinen ts h eA siaP acifirce gion
implitehsa mta nyn ews cientainsdte sn gineaerresb ecomiinngv olviend
thifise ldA.t t hem oment thaerrene o c learre ferewnocrek ost hetrh an
occasional sympprooscieuemd iwnhgisc,ha reo ftent oob roaodr too
theoretoircc aolv eorn lyp arotf t het opiacn dm ainlrye porotn recent
developments.
Theo bjectoifvt eh ibso oki st os ervea sa practirceafle rewnocrek o n
testifnogr t hem ainh ydrocarbon-conpvreorcseisosanep sp liiendo il
refineriecsa:t alyctriacc kihnygd,r oprocesasnidnr ge,f orminTgh.e se
fieldsw erec ombinebde causoef t hec leaarn alogiaensdc ongruence
betweetnh ea reassu,c ha sd eactivaotfia ocnt ivsei tebsy c okem,a ss
transfpehre nomenoaf h ydrocarbionntsos olicda talyhsytdsr,o carbon
chemistarnydr eactikoinn etiacnsd,d ownscaloifnc go mmercicaoln di
tiontsor ealissmtailcl -stceasltes .
As thet itrleev eatlhsi,vs o lumfeo cusoens d eactivaatnidot ne sting;
howevearn,a lytmiectahlo dasn dc haracteritzeacthinoinq aunedsp rocess
modelianrgea lsdoi scussaestd h,e svei tdails cipldienseesrv aet tentiino n
ordetro d esiag pnr opeerv aluatpiroont ocol.
Thisb ookw ilble w armlwye lcomendo to nlyby t hep eopldei rectly
workinignt hidsy namifice ldb,u ti tw ilall sboe o fs ignificianntte rteos t
scientainsdte sn gineeirnsv olviendt heg eneraarle aosf h eterogeneous
catalycsaitsa,l ycshta racterizanadt piroenp aratcihoenm,i craela ction
engineerainndgh ,y drocarpbroonc essing.
ix
