固载化AlCl_3催化合成金刚烷_武丽美

石油化工PETROCHEMICALTECHNOLOGY2007年第36卷第12期[收稿日期]2007-07-05;[修改稿日期]2007-09-12。[作者简介]武丽美(1983—),女,山东省泰安市人,硕士生,电话0411-88993637,电邮merry6664048@163.com。联系人:纪敏,电话0411-88993637,电邮jimin@dlut.edu.cn。固载化AlCl3催化合成金刚烷武丽美,崔捷,纪敏,贺民,田福平,蔡天锡(大连理工大学化工学院精细化工国家重点实验室,辽宁大连116012)[摘要]以固载化AlCl3为催化剂催化桥式四氢双环戊二烯(endo-TCD)异构化合成金刚烷。采用N2吸附、原子吸收和化学分析方法对载体的比表面积、孔分布和催化剂中氯化物负载量进行了表征;考察了载体类型、催化剂颗粒大小、反应温度、单釜反应时间对催化剂性能的影响。实验结果表明,以γ-Al2O3为载体制备的固载化AlCl3催化剂具有较高的活性和较好的金刚烷选择性;升高反应温度、延长单釜反应时间及使用大颗粒催化剂有利于提高金刚烷选择性。在以20～40目γ-Al2O3为载体的固载化AlCl3催化剂7.5mL、endo-TCD0.5g、环己烷用量20mL、反应温度413K、H2压力2.5MPa、单釜反应时间4h的条件下,endo-TCD转化率为100.0%,金刚烷选择性达24.6%,反应12次后金刚烷选择性降至14.0%。该催化剂可重复使用,失活原因是生成的焦油覆盖了催化剂表面的强酸中心。[关键词]四氢双环戊二烯;金刚烷;异构化;固载化;三氯化铝催化剂[文章编号]1000-8144(2007)12-1210-05[中图分类号]TQ032.41[文献标识码]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;ad