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RecentadvancesinRandDofcommercialcatalystsforacrylonitrilesynthesis,styreneproductionandtoluenedisproportionationprocessesQinglingChen*,XinChen,LianshengMao,WencaiChengShanghaiResearchInstituteofPetrochemicalTechnology,SINOPEC1599PudongBeilu,Pudong,201208,Shanghai,ChinaAbstractThispaperreportstheprogressesinRandDandcommercialapplicationoftheindustrialcatalysts,developedandproducedbySRIPTforacrylonitrile,styreneandtoluenedisproportionationprocesses.Theresearchworksofdevelopingauniquemethodofcatalystpreparation,addingproperamountofsodiumionstotheMo±Bioxidessystemtoimprovecatalyticactivityandattritionresistance,andaddingbromineionstoincreaseacrylonitrileselectivityhavebeenconducted.Thenewcatalystforacrylonitrileproduction,MB-96,hasbeensuccessfullyusedinaplantof25000t/awithanacrylonitrileyieldof82mol%.Inthedevelopmentofthecatalystsforethylbenzenedehydrogenation,thestudiesonthestructureofactivephaseandtheeffectsofpotassiumandceriumaspromotersshowthatunderreactionconditionspotassiummainlypromotestheelectronicexchangebetweenFe2‡andFe3‡ions,whileceriumimprovesthestabilityofFe±Kphase.Thenewcatalyst,GS-05,hasbeensuccessfullyusedinanethylbenzenedehydrogenationplantof60000t/awithanethylbenzeneconversionof65±66wt%andastyreneselectivityhigherthan96wt%.Inthedevelopmentofthecatalystsfortoluenedisproportionationandtransalkylation,thestudiesonimprovingthesynthesisofmordenite,cokeformationbehaviorofcatalystandmodifyingsurfaceacidityhavebeendone.ThenewcatalystHAT-095hasbeensuccessfullyusedinaplantof1007000t/awithareactiontemperatureofonly634Kunderahighspacevelocityof1.44hÿ1andahighconversionof45mol%,showinghighactivityandhighstability.#1999ElsevierScienceB.V.Allrightsreserved.Keywords:Commercialcatalyst;Acrylonitrile;Styrene;Toluenedisproportionation1.IntroductionCatalysishasmademajorcontributionstomanyareasofpetrochemicalindustry.Beforeacatalystiscommercialized,appliedresearchanddevelopment,whichareindispensable,arecarriedoutinthelabora-toryandpilotplantofShanghaiResearchInstituteofPetrochemicalTechnology(SRIPT).Inrecentyears,aseriesofcatalystsforimportantpetrochemicalssuchasacrylonitrile,styrene,benzeneandxylenes,havebeendevelopedbySRIPT.Accord-ingtotherespectivedevelopmentfeaturesofthesecatalysts,someimportantappliedfundamentalresearchconductedinlaboratoriesandengineeringscaling-upofthecatalystsandcorrespondingpro-cessesinmodelorpilotplantfordevelopmentareselectivelydescribedinthispaper.TheoutstandingperformanceofthecatalystsproducedbySRIPTinCatalysisToday51(1999)141±146*Correspondingauthor.0920-5861/99/$±seefrontmatter#1999ElsevierScienceB.V.Allrightsreserved.PII:S0920-5861(99)00016-4largecommercialplantstoreplacetheirforeigncoun-terpartsarealsobrie¯yintroduced.2.RandDofimportantpetrochemicalcatalysts2.1.CatalystforacrylonitrileproductionbypropyleneammoxidationTheRandDofacrylonitrilecatalystbeganintheearly1960s.Sincethen,alotofappliedresearchworksformulti-componentmetaloxidecatalystsbasedonMo±Bi±Fesystemwereconducted,includ-ingtheresearchofcatalystonformulation,mainactivephase,preparation,cationlatticedefect,redoxproperty,roleofbi-valentortri-valentmetalaspro-moter,etc.FollowingisabriefintroductiontothemajorfeaturesoftheRandDofacrylonitrilecatalyst.PatentsrelatingtothecatalystswereauthorizedinChina,USAandEurope[1±6].Auniquemethodofpreparingacrylonitrilecatalystfor¯uidizedbedreactorhasbeendeveloped[1].Underparticularconditions,astablewatersolutionofbismuthmolybdateisprepared,thenthesolution,whichwillnotprecipitatewithin48h,ismixedwithothercomponentstoformaslurry.Theslurryisheated,spray-driedandcalcinedinaconventionalwaytoformthedesiredcatalyst.Becausethereisnoprecipitateinthemixedsolution,goodmixingofcatalystcomponentsandeasyconveyanceofslurryincontinuousproductionareensured,andthecatalystpreparedinthiswayhashigheractivity.Thecatalysts,usingthesamecatalystcomponents,thesamepreparationconditionsanddifferentmolyb-dates(e.g.bismuthmolybdate)usedaskeyphaseareprepared.ThecorrespondingcatalyticactivitiesofthecatalystswereevaluatedandareshowninTable1.Table1showsthatthecatalystpreparedbyuseofg-bismuthmolybdatesolutionhashigheractivitythanthecatalystsmadefroma-bismuthmolybdatesolu-tionora-bismuthmolybdateprecipitate.Throughtheresearchontheroleofalkalimetalasapromoter,itwasfoundthatproperadditionofsodium,whichhadbeenwidelyconsideredasadetrimentalcomponentinpropyleneammoxidation,notonlyincreasesacrylonitrileyield,butalsoimprovesattri-tion-resistance,animportantpropertyinacommercial¯uidizedbedreactor.Whensodiumisaddedtotheacrylonitrilecatalystcontainingmulti-metaloxidessuchasK0.1Ni2.5Co4.5-Fe3Bi1P0.5Mo12Ox,itcanbeinaformofanyofitsdecomposablecompoundsaddedtoammoniummolybdateandnitratesolution.Sodiumcanalsobeaddedtoanammonia-stablesilicagelsupport,buttheSiO2/Na2Oratio(wt%)ofthesilicagelmustbeintherange200±400.Theeffectsofthesodiumamountonacrylonitrileyieldandcatalystattritionlosswereexamined[2].TheresultsareshowninTable2.ItisveryinterestingandimportanttolearnfromTable2thattheadditionofaproperamountofsodiumtoamulti-componentacrylonitrile