固载化AlCl3催化合成金刚烷武丽美

　　　　　　PETROCHEMICALTECHNOLOGY　　　　　20073612[]2007-07-05;[]2007-09-12。[](1983—),,,,0411-88993637,[e-mail]。:,0411-88993637,[e-mail]。AlCl3武丽美,崔　捷,纪　敏,贺　民,田福平,蔡天锡(,116012)[]AlCl3(endo-TCD)。N2、、;、、、。,γ-Al2O3AlCl3;、。20～40γ-Al2O3AlCl37.5mL、endo-TCD0.5g、20mL、413K、H22.5MPa、4h,endo-TCD100.0%,24.6%,1214.0%。,。[];;;;[]1000-8144(2007)12-1210-05　　　[]TQ032.41　　　[]ASynthesisofAdamantaneoverSupportedAlCl3CatalystWuLimei,CuiJie,JiMin,HeMin,TianFuping,CaiTianxi(StateKeyLaboratoryofFineChemicals,SchoolofChemicalEngineering,DalianUniversityofTechnology,DalianLiaoning116012,China)[Abstract]Adamantane(ADH)wassynthesizedbyisomerizationofendo-tetrahydrodicyclopentadiene(endo-TCD)oversupportedAlCl3catalyst.SurfaceandporepropertiesofthesupportswerecharacterizedbyN2adsorption,andhalideloadingsincatalystswereanalyzedbyatomicabsorptionspectrometryandchemicalmethod.Effectsofsupporttypes,particlesizesofcatalyst,reationtemperatureandreactiontimeonconversionofendo-TCDandselectivitytoADHwereinvestigated.SupportedAlCl3/γ-Al2O3catalystexhibiteshighactivityandselectivitytoADH.Withincreasesofreactiontemperature,reactiontimeandparticalsizeofcatalyst,supporttoADHrises.Underoptimalreactionconditions:AlCl3/γ-Al2O3ascatalyst,supportparticalsize20-40mesh,bulkvolume7.5mL,endo-TCDdosage0.5g,cyclohexane20mL,reactiontime4h,reationtemperature413KandH2pressure2.5MPa,conversionofendo-TCDandselectivitytoADHare100.0%and24.6%respectively.After12timereusesofthecatalyst,selectivitytoADHdropsto14.0%.Causeofitsdeactivitionisthatstrongacidcentersoncatalystsurfacearepartiallycoveredbysomebyproductssuchastar.[Keywords]tetrahydrodicyclopentadiene;adamantane;isomerization;immobilization;aluminiumtrichloridecatalyst　　[3,3,1,13.7],,,、、、、、、[1]。AlCl3[2,3],、。。[4,5][6]。1976,,·1210·　12.AlCl3(、、)[5]。,,523K,,HCl,。HF,AlCl3,ZnCl2、,,。Getty[7],AlCl3LewisBrönsted,,。AlCl3(endo-TCD),、、()。1　1.1　AlCl3CCl4。CCl4γ-Al2O3(773K2h,)773KAlCl3,AlCl3N2573K4h,573KN21h,。1.2　BETMicromeriticsASAP2010N2,623K4h。:0.25mol/LHNO32.5h,,,;,AA646Al,VolhardCl[8]。1.3　。5.0mL(3.08g)AlCl3、20mL0.5gendo-TCD(97%,)100mL,H22.5MPa。。Agilent6890,HP-5,30m,。,,,,。2　2.1　γ-Al2O3,SiO2,SiO2-Al2O3AlCl3,,1。1,γ-Al2O3endo-TCD,SiO2endo-TCD,SiO2-Al2O3endo-TCD。endo-TCD,Si,。1　AlCl3Table1　CatalyticperformanceofsupportedAlCl3catalystsCatalystsConversionofendo-TCD,%Selectivitytoexo-TCD,%SelectivitytoADH,%AlCl3/γ-Al2O3100.040.917.70AlCl3/SiO2-Al2O399.250.413.90AlCl3/SiO282.397.70.73　　Reactionconditions:endo-TCD0.5g,cyclohexane20mL,cata-lyst5.0mL,H2pressure2.5MPa,413K,6h.endo-TCD:endo-tetrahydrodicyclopentadiene;exo-TCD:exo-tetrahydrodicyclopentadiene;ADH:adamantane.32。2,γ-Al2O37.09nm,SiO211.14nm。γ-Al2O3,SiO2-Al2O3,SiO2[—AlCl2]9.86%,11.26%,14.75%。AlCl3AlCl3,HCl[7,9,10]。90%[—O—AlCl2][10]。2　Table2　Physicalpropertiesofsupports　Physicalparametersγ-Al2O3SiO2-Al2O3SiO2Specificsurfacearea/(m2·g-1)321323332Bulkdensity/(g·cm-3)0.650.600.53Porevolume/(cm3·g-1)0.570.620.93Averageporediameter/nm7.098.0211.14Massfractionof[—AlCl2],%9.8611.2614.75　　2,3,[—AlCl2],3。1,·1211·　　　　　　PETROCHEMICALTECHNOLOGY　　　　　200736endo-TCD,AlCl3,。Schleyer[3]。Lewis,endo-TCD。　　,,(exo-TCD)[11]。1endo-TCDAlCl3/SiO2exo-TCD,,。,γ-Al2O3。2.2　20～40、40～6060～100γ-Al2O3AlCl3,,12。1,,。endo-TCD98%,20～4014,40～6012,60～10010。3。5.0mL,20～40[—AlCl2]0.67g,40～60[—AlCl2]0.63g,60～100[—AlCl2]0.62g。2,。,7,:20～4040～6060～100。endo-TCD,,,。8,3endo-TCD98%(1),10%,,3。γ-Al2O37.09nm,(0.74nm)[11],。,。2.3　3。3,393Kendo-TCD100.0%,。,,393K10.1%,433K30.1%,exo-TCD,。exo-TCD[12]。exo-TCDendo-TCDexo-TCD[13],。·1212·　12.AlCl3,,。,413K。3　Table3　EffectofreactiontemperatureoncatalystperformancesReactiontemperature/KConversionofendo-TCD,%SelectivitytoADH,%Selectivitytoexo-TCD,%Selectivitytootherbyproducts,%393100.010.175.614.3403100.014.159.426.5413100.019.144.936.0423100.028.232.149.7433100.030.117.452.5　　Reactionconditions:endo-TCD0.5g,cyclohexane20mL,AlCl3/γ-Al2O3catalyst(60-100mesh)5.0mL(bulk),H2pressure2.5MPa,6h.2.4　3。3,,exo-TCD,。2h,exo-TCD64.2%,13.8%;8h,exo-TCD22.7%27.3%。,,。endo-TCD。endo-TCD,exo-TCD,[12]。,,exo-TCD,,。,exo-TCD,。,。,4h。2.5　,20～40γ-Al2O3AlCl3,,4。4,、。endo-TCD100.0%,24.6%,exo-TCD27.5%。,endo-TCD100.0%,,exo-TCD。12,14.0%,exo-TCD60.6%。3　(1)endo-TCD,γ-Al2O3AlCl3,,·1213·　　　　　　PETROCHEMICALTECHNOLOGY　　　　　200736。(2)AlCl3、、、。20～40γ-Al2O3AlCl3,endo-TCD0.5g、20mL、7.5mL、H22.5MPa、4h、413K,endo-TCD100.0%,24.6%。(3)endo-TCD,AlCl3。　　　1　NavrátilováM,SporkaK.SynthesisofAdamantaneonCommeri-callyAvailableZeoliteCatalysts.ApplCatal,A,2000,203(1):127～1322　,,..,1999,28(8):546～5613　SchleyerP.ASimplePreparationofAdamantane.JAmChemSoc,1957,79(12):32924　,,..,1998,27(1):34～375　Kammizumi,Sodegauro-Cho,Kimitsu,Chiba;Kmazuasayama,Ichihara,Chiba.ProcessforProducingAdamantineCompounds.USPatAppl,US3944626.19766　,,..,2002,31(5):345～3487　GettyEE,DragoRS.Preparation,Characterization,andCatalyticActivityofaNewSolidAcidCatalyst.InorgChem,1990,29(6):1186～11928　VosburghWC.AnIntroductiontoQuantitativeChemicalAnalysis.NewYork:HenryHolt,1941.2639　XuT,KobN,DragoRS,etal.ASolidAcidCatalystattheThresholdofSuperacidStrength:NMR,Calorimetry,andDensity