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:200712,:200813(973)(2004CB217807)33e2mail:[e-mail]333(CNPC257061),,,,,S2Zorb:TE868;O64713:A:10052281X(2008)1121834212TheAdsorptiveDesulfurizationTechnologiesforUltra2CleanOilProductionZhangJingcheng33LiuYunqiAnGaojunChaiYongmingFuQingtaoLiuChenguang(StateKeyLaboratoryofHeavyOilProcessing,KeyLaboratoryofCatalysisofCNPC,ChinaUniversityofPetroleum,Dongying257061,China)AbstractComparedwiththeconventionalhydrodesulfurizationtechnologies,theadvantagesofadsorptivedesulfurizationforultra2cleanoilproductionareattractive,suchaslowerinvestmentandoperatingcost,muchmilderconditions,higherdesulfurizationefficiencyandsoon.Consequently,theinvestigationisbecomingpopularrecently.Theadvancesinthisfieldareintroducedbrieflyinthispaper,withtheemphasisonthedesigningprinciple.Inaddition,theopinionswithrespecttothefutureapplicationtrendofultra2cleanoilareproposed.Themainproblemsofcurrentworkarelowersulfurcapacity,selectivityandpoorperformanceofregeneration.Itisindicatedthatthedesignandoptimizationofadsorptiontechnologies,aswellastheresearchonadsorptionmechanismwillbethemostprospectiveareas.Keywordsultra2cleanoil;reactiveadsorptiondesulfurization;selectiveadsorptiondesulfurization;adsorptionmechanism;S2Zorbprocess120,SOx,,;,SOx,[1,2],,1,,,[3],,2008,2010,2011200811PROGRESSINCHEMISTRYVol.20No.11Nov.,20081[4]Table1ENsulfurregulationsforgasolineanddieselfuelsandtheimplementingtimesbymaincountriesandareasintheworld[4]ENsulfurstandardgasolinedieselENENENENENENENENsulfurcontent(gPg)50015050105003505010EN19982000200520111998200020052011US19902000200419932006Japan19992005200819972005Beijing,China20042005undeterminedundetermined20042005undeterminedundetermined2,,(FCC),,FCC80wt%,;,1P3,,,FCCFCC4[5]:,15wt%;,25wt%;,60wt%;(RFCC)FCC,,,70wt%[6]FCC200,312wt%;200300,4915wt%;300,4713wt%,,,(HDS)(Non2HDS)HDS,;,HDS,:(1)FCC(SHDS)[711],50gPg(),(10gPg,);(2)FCC,H2S,[1214];(3)42(42MDBT)4,62(4,62DBT),1,HDS[15];(4)[16,17]1HDS[2]Fig.1ReactivityofvariousorganicsulfurcompoundsinHDSversustheirringsizesandpositionsofalkylsubstitutionsonthering[2]Non2HDS,[1823],538111,(ADS),,;,1gPg,[24]ADS,,3(ADS)ADS,[25],,ADS:(reactiveadsorptiondesulfurization,RADS)(selectiveadsorptiondesulfurization,SADS)311RADS,,[1],SOxRADS20,ZnOMnO2CaOH2S[26,27],,Babich[1]RADSH2PN2,ZnOMoO3NiOCo3O4MnO2,ZnO,,50gPg,ZnSTawara[2831],Ni2MoPAl2O3Ni2MoPAl2O3,Ni2Mo;NiPAl2O3,,,,NiPZnO,NiPZnO13wt%Ni2702900125h-1,51gPg,1,0103gPg[31]NiPZnORADS2ZnO,,Ni[1],NiOPZnONiOH2Ni,S,Ni,;,,CS,S,NiNiS;,H2,SZnOZnS,Ni,(autoregenerative)[29]Bezverkhyy[32]2[1]Fig.2Mechanismofreactiveadsorptiondesulfurizationprocess[1],RTI(ResearchTriangleInstitute)TReND(transportreactorfornaphthadesulfurization)(ConocoPhillips)S2Zorb31111TReNDRTITReND,[33]FCC426535,TReNDFCC,(RON)012[33];6381202PTRsFCCPONA[34]Table2PONAandoctaneanalysisforFCCnaphthatestinginRTIsPTR[34]feedproductPONAanalysis(wt%)paraffins41154019olefins19172211monocycloparaffins12181111dicycloparaffins0185013alkylbenzenes22141916indanesPtetralins2128214naphthalenes015015octanenumberresearch91109018motor8018811531112S2ZorbS2Zorb[3538],FCC,S2ZorbPhillips,3[35]:,,,ZnO,Al2O3,SiO2NiO[36]3S2Zorb[35]Fig.3AdsorptionprincipleofS2Zorbprocess[35]S2Zorb3:,4[13],017211MPa,343413;,,,,;H2,Ni,;,,S2Zorb45[37]4S2Zorb[14]Fig.4S2Zorbprocessscheme[14][38,39],S2ZorbFCC98%,3wt%(015115),100%;,HDS,(50%),199910,220013(Borger),6000Pd,2001400gPgFCC,10gPg,[40]200311Farndale,20000Pd,FCC1500gPg10gPg,(R+M)P2110,,,5wt%,P318413,(RON)(MON)019018Borger,(R+M)P20151,012%S2Zorb(LakeCharles)(166P,2005)(Pasadena)120P,20075,,10gPg(PEC,PetroleumEnergyCenter)FCC,S2Zorb,347381113FCCTable3ListofFCCnaphthadesulfurizationprocessesprocessOctgain125Octgain220SCANfiningPrimeGCDTechS2Zorbprocessingcapacity(bblPday)150003100025000240003000025000investment(million)141923181618211718151318hydrogenconsumption(M3Pkl)662314221812powerconsumption(kWhPkl)1216914318812218414steamuse(kgPkl)2141281807013home2usefuel(LPkl)1316518214115513613catalystcost(PBBL)014301220122010101250127coolingwater(TonPkl)610514312311113311yieldloss(%)5017001800octaneloss001111011311001754FCCTable4ListofFCCnaphthadesulfurizationprocessessummaryofeconomicviabilityofFCCnaphthadesulfurizationequipmentprocessExxon2MobilOctgain125Octgain220SCANfiningIFPPrimeGCDTechCDHydroPCDHDSPhillipsS2Zorbrequiredcapacity(1000klPyear)225582317523093230492309323148constructionindex877696607815557500depreciationindex175139121163111100variableindex207119134119102100evaluationindex382259256282214200,S2ZorbSRT[41,42],(119314MPa),948m3PdPhilipsBorger,FCC10gPg,S2Zorb:,,,380(),;,HDS,S2Zorb,;,,[39],311132,,[4352](SRNA24)(MSB),[44]FCC(335gPg,41gPg),SRNA24MSB,MSBSRNA24:110MPa,100,LHSV12h-1,Hext20kAPm0183wt%XRDBET,,2,,[45],,,,CS,,[46]X(XPS),25NiCS,Ni;;;100;,Ni;200,312ADSSADS838120SADS,,,SADSSADSS2M31211,,Haji[53](4nmCA,22nmCA)DBT22nmCA,90wt%DBT116h,4nmCA15hDBT[54]XYMZSM25Silicalite2I,ZSM25Silicalite2IZSM25(0153nm),(01650168nm),Salem[55,56]5A13X550gPg,,13X3,;,13X;5ALangmuir,,,8065wt%;13X,100%[57]13XFCC(90),(90)1220gPg500gPg31212Lewis,,Lewis,,,Larrubia[58](FT2IR)(BT)(D