改性对ZSM_5分子筛芳构化性能的影响

2008-07-181982-。、、。、、,[1~3]。。HZSM-5、[4]ZSM-5、[5~6]。ZSM-5。、、、。HZSM-5,,。ZSM-5ZSM-5。1ZSM-51.1ZSM-5ZSM-5ZSM-5,,113001ZSM-5、、。ZSM-5。Zn。。GaZSM-5。P-Zn/HZSM-5。ZSM-5。HZSM-5、。ZSM-5TQ424.25A1001-0017200902-0054-05EffectofModificationonAromatizationPerformanceofZSM-5MolecularSieveGAOYuan,BAIYing-zhi,SHIYan,ZHAOLi-xiangandLIULuCollegeofPetrochemicalTechnology,LiaoningUniversityofPetroleum&Technology,Fushun113001,ChinaAbstract:Becauseoftheuniqueshape-selective,goodhydrothermalstability,characteristicsofanti-acidandanti-carbondeposition,ZSM-5molecularsieveiswidelyusedinaromatizationcatalyticprocess.ThemainmodificationmethodsofZSM-5molecularsievearomatizationcatalystathomeandabroadweresummarized.TheadditionofZnnotonlypromotedlow-carbonhydrocarbonsaromatizationreaction,butalsoenhancedtheanti-carbondepositionperformanceofcatalyst.Withtheadditionofphosphorus,liquidyieldandaromaticscontentincreased.ZSM-5hadobviouscatalysisonthelow-carbonhydrocarbonsaromatizationwhichwasmodifiedbyGaionexchange.P-Zn/HZSM-5showedhigherinitialactivityandgoodstability.Afterhydrothermaltreatment,HZSM-5molecularsievehadagoodstabilityofaromatization.Nano-HZSM-5zeolitecatalysthadastronghydrocarbonconversionproperty,throughthearomatization,isomerization,andalkylationreaction,hydrocarbonconvertedintoisohydrocarbonandaromaticswhichhadahighoctanevalue.Keywords:ModificationofZSM-5;aromatization;Zinc;phosphorus;nickel;Ga;nanoZSM-5Vol．31．No．22009·54·。[7],HZSM-5。H-ZSM-5、0.8％ZSM-51。Zn。BLZnH-ZSM-5LBH-ZSM-51616cm-1Zn[8]。ZnH-ZSM-5B,ZnOH+H-ZSM-5。1H-ZSM-5[7]Table1Effectofadditionofzinconproductdistributionandconversionofn-hexanearomatizationonH-ZSM-5catalystZnZnOZSM-5。Kazansky[9]ZnOZn-OLewis--C-HH-H。[10]ZnO／ZSM-5ZnOZnOZSM-5。ZnO。1.2ZSM-5。[11]。。。[12],5％。1.3ZSM-5GaZSM-5。[13]GaGaGa。[14]GaZSM-5ZSM-5Ga。GaGa／ZSM-5GaH-A1.Ga-SilicateGaH-Al.Ga-SilicateGa／ZSM-5。KwakBS[15]GaCl3HZSM-5Ga／Ga+H+0.4%～0.5%。ChoudharyVasantR[16]GaMFI400～500℃。1.4ZSM-5[17]Ga2.0%ZnZnO-Ga2O3/HZSM-5C3-4。Zn。Zn2.0%。Zn2.0%GaZnO-Ga2O3／HZSM-5C3-4Ga。Ga2.0%。Ga。1.5ZSM-5Zn／ZSM-5[18~19]、Zn、。。[20]PZn／HZSM-5BLP。[21]P-Zn／HZSM-5/%~~~/%HZSM-56.525.339.710.017.01.597.00.8%Zn/HZSM-513.215.828.12.937.62.494.02009312CHEMISTRYANDADHESION·55·P-Zn／HZSM-5。16h。C6+P-Zn／HZSM-5。、[22]。。1.6ZSM-5P,,。Ni、。Ni,Z,,[23]。[24]1.2MPa、VH2/VHC=400/1、320℃、LHSV=4h-1,NiP/ZSM-52。2[24]Table2Effectofcatalystpreparationmethodsonreaction2,,;,,,。BL。3。3[24]Table3EffectofcatalystpreparationmethodsonacidityofNiP/ZSM-5catalyst3,,B,L。。,B,,;,B,L,。B,,。,BL,B。,,。,,。2[25]ZSM-5。ZSM-5Zn。。ZnAZn、AZSM-5。[26]HZSM-5Zn、GaP2HZSM-5ZnGaP／HZZnGaP／HZ3h。X、N2、、、、、。HZSM-5、。0.1MPa、400℃、2.0h-1HZSM-5、。[27]300℃、350℃、400℃500℃Zn／HZSM-5FCC。PreparationmethodConversion/%Liquidproductselectivity/%Isomerizedproductselectivity/%Aromatizedproductselectivity/%Co-impregnation79.8041.8310.8317.79Stepimpregnation85.1833.7314.187.32Desorptiontemperature/℃200350AcidityBacidityLacidityBacidityLacidityCo-impregnationmethodacidconcentration/Ag-1cm-22.71.43.91.6Stepimpregnationmethodacidconcentration/Ag-1cm-24.71.26.11.6ZSM-5Vol．31．No．22009·56·FT-IR。Zn／HZSM-5400℃Zn2％／HZSM-536h74.25％。B300～400℃500℃L400℃、400℃83.62％、95.44％92.23％BL。3HZSM-5ZSM-5、[28]。[29]ZSM-5、HZSM-5。、HZSM-5。HZSM-5HZSM-5、“”。HZSM-5。[30]HZSM-520～50nm、ZnOGaOHZSM-5TEMXRFIRXRD。ZSM-5、L／B、L／B。HZSM-5。BL。L／B。LBL／B1.4～1.7ZSM-5。50％30％C7-C9C4～C684％80％。4ZSM-5、、、、。HZSM-5,,。ZSM-5。。1.Zn/H-ZSM-5J.,1996,257458~462.2.:Zn-HZSM-5J．1995233289~294.3,.Zn/ZSM-5J.1994103:247~253.4HOUZVICKAJNIENHUISJGHANSIDAARSeta1．ZSM-5－AnactiveselectiveandstablecatalystforskeletalisomerisationofnbuteneJ．ApplCatalA19971651~2443~449．5GUISENTMGNEPNSAITTALEBDeta1．ConversionoflightalkanesintoaromatichydrocarbonsJ．ApplCatalA1992872255~270．6NAGAMRORIYKAWASEM．Convertinglighthydrocarbonscon－tainingolefinstoaromaticsJ．MicroporousandMesoporousMa－terials1998214~6439~445.7,.Zn/H-ZSM-5Zn2009312CHEMISTRYANDADHESION·57·5。。。1.5g。5Table5EffectofmonomeramountongraftcopolymerizationReactioncondition:CMC:0.4g;H2O:50.0mL;APS:60.0mg;Temperature:70℃;Time:3.0h3。:0.4g50.0mL1.5g60.0mg70℃3.0h244.1％65.1％。1,,,.J.,20042:54~62.2BLAIRH,GUTHRIEJ,LAWT-K,etal.ChitosanandmodifiedchitosanmembranesI.PreparationandcharacterizationJ.JApplPolymSci,1987,33641~656.3.M.:,2003:301~305.4,,.－J.,2002,226:36~38.5,,.J.,2003,193:282~287.6,,,.N-J.:B,2001,312:153~160.7,,,.J.,2007,365:448~450.8FUZ-S,SUNB-B,CHENJ,etal.PreparationandphotochromismofcarboxymethylchitinderivativescontainingspirooxazinemoietyJ.DyesPigm,2008,762:315~318./℃/%/%0.682.755.10.9133.459.21.2187.062.41.5244.165.11.8244.254.542J.2001262:6~9.8．Zn／H-ZSM-5D．1999.9KAZANSKYVBKUSOVLMKHODAKOVAYU．Isthecationicpolymerizationofiso-olefinsinamoderatelyconcentratedsulfuricacidarealcarbenium-ionreactionJ.AppliedCatalysis.AStudSurfSciCatal198949B1173~1176.10,．ZnO／HZSM-5J．1994,235~39.11,.Ni/ZSM25J.2004,124:13~17.12,.J.,2007,272:24~27.13,．ZSM-5J.,1994,107628~634.14.J．199526549~53.15KWAKBSSACHRLERWMH.EffectofGa／ProtonBalanceinGa／HZSM-5CatalystsonC2conversiontoaromatjcsJ.JCatal.19941452456.16CHOUDHARYVRKINAGAKCHOUDHARYTV．EffectiveLow-TemperatureAromatizationofEthaneoverH-Gallo-Allm－mosib