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©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.:(1975),,,,(,C1,300072):,,:;;:TE624.9+3:A:100821143(2002)0120042204AdvancesinresearchesinthecatalystsforanilinehydrogenationtocyclohexylamineYANJing,WANGRi2jie(StatekeylaboratoryofC1chemicalsandchemistry,DepartmentofCatalysisScienceandEngineering,SchoolofChemicalEngineering,TianjinUniversity,Tianjin300072)Abstract:Themechanismofhydrogenationofanilinetocyclohexylamineisintroduced.Emphasisisputonthecatalystsforliquidphaseandgasphasehydrogenation.Theresearchofnon2noblecatalystforgasphasehydrogenationisrecommended.Keywords:aniline;cyclohexylamine;hydrogenationCLCnumber:TE624.9+3Documentcode:AArticleID:100821143(2002)0120042204,,,,,,,[1]1995,4450,3000,10%[2],,,:,,,,,,,,NH2+3H2NH21,,(pH10.5,0.01%)CO2,(96.4)10120021INDUSTRIALCATALYSISVol.10No.1Jan.2002©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.()(n20D)134-17.732.22265(d2525)0.8647(d204)0.81911.45852C6H7N(gas)+3H2C6H13N(gas)Hor=-187.3kJ/mol(1)2C6H7N(gas)+6H2C12H23N(liquid)+NH3Hro=-437.71kJ/mol(2)(1),(2),,3Greenfield[3](I)(II)(1)NH22H2NH2NH3H2abNH2(1)(III)(II)(Ib)(2)IV(3)N-(V)(4),NH2+NHNH2NHb(2)NH2NHH2NH+NH3(3)NH2NHN+NH3(4)(160170)2NH2NH+NH3(5),300,200,NH2H2+NH3(6)Becker[4]/,VIII(Ni,Pd,Ru,Rh,Pt)200G22292%(100%)(6mm),,(68%,58%)/,JBK21,35099.8%,95.5%(250),,,,,N2250;,(200),,260,(3mm),,N24,VIII,[8,9,11,12,15,16],[5,6,7,13,14,17],20021:43©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[5]RuPd0.13wt%,2627MPa98%10018090%,200CrMnAl2O30.12wt%Ru/Pd,Ru/PtRu/Pd/Pt[6],Al2O3Me(II)Al2O4(MeFe,Zn,Ni,Cu),Na,K28MPa,,110Monsanto[7]Ru,25MPa,160180,1%8%,N25%Ru,3%160180,90%,,,441112Bayer30MPa[8]CoMn,,0.25wt%/VVI20090%1200015000h[9],,CoNi,CoNiMnCuCaSrBa,CoNiMnSiMg,,,140180,200240,2500030000h[10]2Fe2O3,,;,1%O299%N2,400,500,600,700800,700,250,50%,88%,,,,,,,[11]0.12MPa,150250,ThCrMo,,10%,,90%5wt%,90%,20wt%[12]Ni/,,210240,,90%,83%41241211Vishwanathan[13,14]Rh,RhNiRhRh0.51wt%100%Rh,(015016nm),Rh20%,Rh,3wt%Rh,4420021©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[5]1%Pd19020%41212G.Mink[15]NaOHLa2O3Ni,Ni,,90%99%,La,,,(,),,,La2O3,,NaOH,NaOHSP3,Nid,Ni,Ni,Ni,Ni,,La,Ni,La2O3[16],Co,,Co2O3,16017035mm1m,96%,1000h5,,,,,,,,,,,,[2],:[1].[J].,1996,(3):34.[2].[J].,1996,(4):30.[3]GreenfieldH.HydrogenationofAnilinetoCyclohexylamine[J].JOrgChem,1964,29:3082.[4]JrgenB,etal.Aminationofcyclohexanoneandcyclohex2anol/cyclohexanoneinthepresenceofammoniaandhydro2genusingcopperoragroupVIIImetalsupportedonacarri2erasthecatalyst[J].AppliedCatalysisA:General,2000,197:229.[5]Immel,etal.Processforthepreparationofamixtureofcy2clohexylamineanddicyclohexylamineusingasupportedno2blemetalcatalyst[P].US5322965,1994.[6]Immel,etal.Ruthenuimsupportedcatalyst,itspreparationanditsuseinthepreparationofsubstitutedorunsubstitutedcyclohexylamineandsubstitutedorunsubstituteddicyclo2hexylamine[P].US5023226,1991.[7]MerternH,etal.Productionofcyclohexylamine[P].US4384142,1983.[8]DarsowG,etal.Processforpreparingamixtureofcyclo2hexylamineanddicyclohexylamine[P].US5728883,1998.[9]DarsowG,etal.Processforpreparingamixtureofcylco2hexylamineandicylcohexyalmine[P].US5705700,1998.[10],.[J].,1998,19(6):5542558.[11]ChenYZ.Methodforpreparingcylcohexylamine[P].US5714635,1998.[12]NewJapanChemicalCo.Methodforproductionofcylco2hexylamine[P].US4914239,1990.[13]VishwanathanV,NarayananS.Adirectcorrelationbe2tweendispersion,metalarea,andvapourphasehydro2genationofaniline:afirstreport[J].ChemSoc,ChemCommune,1990:78.[14]VishwanathanV,NarayananS.Gasphaseanilinehydro2genationoversupportedrhodium/aluminacatalyst[J].In2diaJChem,SectA,30A,1991:679.[15]MinkG.HydrogenationofanilinetocylcohexylamineamineonNaOH-promotedorLanthanasupportedNick2el[J].ReactKinetCatalLett,1998,65(1):59.[16],.[J].,1988,(3):16.20021:45