TS1催化环己酮氨肟化反应的研究进展王巧焕

2017444342·55·TS-1*(321004)[]TS-1MFITi4+Si4+H2O2TS-1[]TS-1[]TQ426[]A[]1007-1865(2017)04-0055-03ResearchProgressontheCatalyticAmmoximationofCyclohexanoneonTs-1WangQiaohuan,QuLiwen,JiangLei,ShenHuanmei,XuChunhui*,TuGaomei,ZhuWeidong(KeyLaboratoryoftheMinistryofEducationforAdvancedCatalysisMaterials,InstituteofPhysicalChemistry,ZhejiangNormalUniversity,Jinhua321004,China)Abstract:Titanosilicate(TS-1)isazeolitewithanMFI-typestructure,anditscharacteristicisofTi4+substitutionforasmallpartoftheframeworkSi4+insilicalite-1,leadingtoitsuniquepropertiesforcatalyticoxidation.Inparticular,TS-1possessessuperiorcatalyticselectivitiesinaseriesofselectiveoxidationsoforganicswithH2O2ororganicperoxides.ThispaperrepresentsanoverviewofthecurrentstatusandproblemsintermsofthefundamentalresearchandindustrialapplicationsofTS-1catalyzingtheammoximationofcyclohexanonetocyclohexanoneoxime.Additionally,thefurtherinvestigationonfundamentalresearchandapplicationsisanticipated.Keywords:TS-1cyclohexanonecyclohexanoneoximeammoximation(TS-1)TS-1MFI(straightchannels0.57nm×0.51nm)Z(zig-zagchannels0.54nm)(intersections0.90nm)Ti4+Si4+Ti4+H2O2TS-1[1][2][3][4]TS-1-6ε-(CPL)CPLBeckmannε-2080EniChemS.p.AH2O2TS-1SumitomoChemicalBeckmannε-MFIBeckmannε-(1)ε-“”2060EniChemS.p.A2003SumitomoChemical696.7%96.4%[5]O+NH3+H2O2TS-1NOH+2H2OOHighsilicaMFIO+NH3+H2O2TS-1NOH+2H2OOHighsilicaMFI1Beckmannε-Fig.1CombinedprocessbetweenammoximationandvaporphaseBeckmannrearrangement(HTS)—“”7[6]99.5%99%[7]2003820049TS-1TS-1[8]TS-1TS-1TS-1TS-11TS-1TS-1TS-1Si-O-TiTi-O-TiTS-1()[]2017-01-12[](21476214)(Y201327788)[](1990-)*20174·56·()TS-1H2O2[9,10]1983Taramasso[11](TEOS)(TEOT)(TPAOH)TS-1TS-1(278K)CO2TS-11992Thangaraj[12]TS-1(TBOT)TEOTTiO2TBOTTEOSTS-1TS-1TPAOHTS-197%[13]TPAOHTuel[14](C6DN)+(TPABr)TS-1TPA+MFIC6DNShibata[15][16]TPABr(MA)(n-BA)TS-1Khomane[17]TPABr(Tween20,Tween60,Span60,Span80TX-100)TS-1Tuel[18](TBPOH)(TEPOH)TS-1TBPOHMELTEPOHMFIXTBP+TEP+TS-1TS-12~7umTPAOH0.1~0.4umTS-10.5umTPAOHTPAOHHuang[19]n-BATPAOHTPAOH/SiO2=0.05()TS-1TS-198%99.4%Deng[20]TPAOH/SiO2TS-1TS-1(TPAOH/SiO2)TS-1TS-1Padovan[21]TiO2-SiO2TPAOHTS-195%0.5nm90%Uguina[22]TiO2-SiO2PadovanTS-1SiO2/TiO2=30()1/2100%TS-1TPAOHTS-1[11]TPAOHTS-1TPAOH/SiO20.4-1.0TS-1TPAOH/SiO2TPAOH/SiO20.4TS-1TPAOHTS-1TS-1TPAOHTS-1TiTS-1TS-12TS-1TS-1TS-1TS-1TS-1TS-1TS-1Palkovits[23]TS-1TS-1()Xin[24]TS-1TS-1TS-1Yip[25,26]TS-1TS-1/TS-1TS-1[27,28]TS-1TS-1TS-180%85%TS-1Giuseppe[29]20μmTS-1TPAOHTS-132080TS-1TS-1TS-1[30]H2O2TS-1(2A)TS-1[31]H2O2TS-1TS-1TS-1(2B)[32]Tatsumi[33]2,5-TS-1TS-12,5-TS-12006Song[34]Ti-MWWTi-MWW()(2B)2017444342·57·NH3(A)+(B)NH3+H2O2ONHNOHNH2OHOimine[Ti]hydroxylamineH2O2/[Ti]NH3(A)+(B)NH3+H2O2ONHNOHNH2OHOimine[Ti]hydroxylamineH2O2/[Ti]2TS-1Fig.2PossibleammoximationpathwaysLiu[35]-TS-1C=OTS-1NH3H2O2TS-1TS-1TS-1TS-1TS-1TS-1TS-14TS-1TS-1TS-1TS-1NH3H2O2NH2OHTS-1TS-1TS-1TS-1[1]ClericiMGIngallinaPEpoxidationoflowerolefinswithhydrogenperoxideandtitaniumsilicalite[J]Cheminform1993140(1)71-83[2]ThangarajAKumarRRatnasamyPCatalyticpropertiesofcrystallinetitaniumsilicalitesIIHydroxylationofphenolwithhydrogenperoxideoverTS-1zeolites[J]Nanoscale1991131(1)294-297[3]ThangarajASivasankerSRatnasamyPCatalyticpropertiesofcrystallinetitaniumsilicalitesIIIAmmoximationofcyclohexanone[J]JournalofCatalysis1991131(2)394-400[4]SchuchardtUPastoreHOSpinacéEVCyclohexaneoxidationwithhydrogenperoxidecatalyzedbytitaniumsilicalite(TS-1)[J]StudiesinSurfaceScience&Catalysis1994841877-1882[5]BarsJLDakkaJSheldonRAAmmoximationofcyclohexanoneandhydroxyaromaticketonesovertitaniummolecular[J]AppliedCatalysisAGeneral1996136(1)69-80[6]HTS[J]200534(z1)377-379[7]LiZChenRJinWetalCatalyticmechanismandreactionpathwayofacetoneammoximationtoacetoneoximeoverTS-1[J]KoreanJournalofChemicalEngineering201027(5)1423-1427[8]TS-1[J]201433(7)1748-1752[9][C]2009[10]WuPTatsumiTAnoveltitanosilicatewithMWWstructureIIIHighlyefficientandselectiveproductionofglycidolthroughepoxidationofallylalcoholwithH2O2[J]JournalofCatalysis2003214(2)317-326[11]TaramassoMPeregoGNotariBPreparationofporouscrystallinesyntheticmaterialcomprisedofsiliconandtitaniumoxidesUS4410501[P]1983-10-18[12]ThangarajAEapenMJSivasankerSetalStudiesonthesynthesisoftitaniumsilicaliteTS-1[J]Zeolites199212(8)943-950[13]IwasakiTIsakaMNakamuraHetalSynthesisoftitanosilicateTS-1crystalsviamechanochemicalrouteusinglowcostmaterials[J]Microporous&MesoporousMaterials2012150(1)1-6[14]TuelACrystallizationoftitaniumsilicalite-1(TS-1)fromgelscontaininghexanediamineandtetrapropylammoniumbromide[J]Zeolites199616(2-3)108-117[15]ShibataMGabelicaZSynthesisofMFItitanosilicatesfrommethylamine-TPABrmedia[J]Zeolites199719(4)246-252[16]TPABr-TS-1[J]199838(3)363-367[17]KhomaneRBKulkarniBDParaskarAetalSynthesischaracterizationandcatalyticperformanceoftitaniumsilicalite-1preparedinmicellarmedia[J]MaterialsChemistry&Physics200276(1)99-103[18]TuelATaaritYBSynthesisandcharacterizationoftitaniumsilicaliteTS-1preparedusingphosphoniumions[J]Zeolites199414(4)272-281[19]HuangDGZhangXLiuTWetalSynthesisofhigh-pe