钛硅分子筛在环己酮肟气相贝克曼重排反应中的失活.doc

钛硅分子筛在环己酮肟气相贝克曼重排反应中的失活 第4卷第期Vol.4No. 文章编号：（05-98700）-0889-06 催化学报 00年月December00 研究论文：889!894 ChineseJournalofCatalysis 钛硅分子筛在环己酮肟气相贝克曼重排反应中的失活 尹双凤，徐柏庆 （清华大学化学系一碳化学与化工国家重点实验室，北京00084） 摘要：对比了不同孔径的钛硅分子筛催化剂T（S和TS（S对环己酮肟气相贝克i-MCM-4i／Ti摩尔比=7）-i／Ti摩尔比=5）曼重排反应的催化性能，分析了它们在重排反应中的积碳量和孔体积的变化.结果表明，这些钛硅分子筛催化剂的失活主要是由积碳引起的，且积碳速率受催化剂孔径的制约.在重排反应过程中，TS-催化剂微孔孔道内的积碳量随反应时间线性增加，微孔体积随反应时间线性下降；而二次孔内的积碳量随反应时间呈指数增加，孔体积随反应时间呈指数递减.关键词：贝克曼重排反应，TS-分子筛，Ti-MCM-4分子筛，失活，积碳，环己酮肟，己内酰胺中图分类号：文献标识码：O64A DeactivationofTitanosilicalite（TS-，Ti-MCM-4）intheVapor-PhaseBeckmannrearrangementofCyclohexanoneOxime YINshuangfeng，XUBOCing! （StatekeyLaboratoryofClChemistryandtechnology，DePartmentofChemistry， tsinghuaunioersity，Beijingl00084，China） Abstract：TS-（Si／Timolarratio=5）andTi-MCM-4（Si／Timolarratio=7）molecularsievesweretested at0Cforthesynthesisofcaprolactambythevapor-phaseBeckmannrearrangementofcyclohexanoneoxime（CHO）.TS-showedhigheractivity，caprolactamselectivityandstabilitythanTi-MCM-4，indicatingthattheporesiZeofthemolecularsievesisanimportantfactorinfluencingthecatalyticperformance.Thedeactiva-tionofthetitanosilicalitemolecularsieveswasaresultofcokedeposition.ThecokedepositiononTi-MCM-4wasmuchmorerapidandheavierthanthatonTS-，whichsuggeststhatthelargerporesiZeisbeneficialtotheformationofcokeorcokeprecursors.ThecokeamountandporevolumeofTS-weremeasuredafteritreacted -（CHO）withCHOat70CandWHSV=4.5hfordifferenttimes.Theresultsshowedthatthemicroporevol-umeoftheTS-catalystdecreasedlinearlywiththereactiontimewhilethemesoporevolumedeclinedexponen-tially.TheamountofthecokeinsidetheporesoftheusedTS-catalystwasinproportiontothereactiontime. theamountofthecokeoutsidethemicroporesorinthemesoporesoftheTS-catalystincreasedexpo-However， nentiallywiththereactiontime.Thus，thedeactivationoftheTS-catalystwasmainlycausedbythecokefor-mationoutsidethemicroporesoftheZeolitecrystals.Keywords：Beckmannrearrangement，TS-molecularsieve，Ti-MCM-4molecularsieve，dea