MCM-分子筛的表面修饰及其催化合成乙酸异戊酯.docVIP

MCM-41分子筛的表面修饰及其催化合成乙酸异戊酯 第28卷第10期 Vo1.28No.10 催化 ChineseJournalofCatalysis 2007年10月 October2007 文章编号:0253—9837(2007)100910—05研究论文:910～914 MCM.41分子筛的表面修饰及其催化合成乙酸异戊酯 陈静,韩梅一,李桂云,王锦堂 (1南京工业大学理学院应用化学系,江苏南京210009;2重庆科技学院化学与生物2f_程学院,重庆4OOO5O) 摘要:通过后合成处理将苄基,三甲基硅烷基和磺酸基接枝到MCM一41分子筛上,制备了一种新型的有机一无机杂化s—B— MCM一41催化剂.采用x射线衍射,低温N2吸附一脱附和酸碱滴定对样品的结构和质子酸量进行了表征和测定.结果表明, s—B—MCM一41催化剂较好地保持了MCM一41分子筛的介孑L结构,BET比表面积高达798m/g,质子酸量为4.0mmol/g.将 s—B—MCM一41催化剂用于乙酸与异戊醇合成乙酸异戊酯的反应,考察了各种反应条件对酯化率的影响.在乙酸用量为0.1 mol,异戊醇用量为0.15tool,催化剂用量为0.2g,带水剂甲苯为15ml,反应温度为110～125℃,反应时间为2h的优化 条件下S-B—MCM一41上的酯化率可达99%以上;而MCM.41分子筛上的酯化率仅为54%.经3次重复使用后,s—B—MCM一41 催化剂上的酯化率依然保持在90%以上.初步探讨了s—B—MCM一41催化剂催化合成乙酸异戊酯的反应机理. 关键词:MCM一41分子筛;表面修饰;苯甲醇;三甲基氯硅烷;氯磺酸;乙酸;异戊醇;乙酸异戊酯 中图分类号:0643文献标识码:A SurfaceModificationofMCM-41MolecularSieveandItsCatalytic PerformanceforSynthesisofIso-amylAcetate CHENJing,HANMei一,LIGuiyun,WANGJintang (1DepartmentofAppliedChemistry,SchoolofScience,njingUniversityofTechnology,njing210009,Jiangsu,China; 2SchoolofChemistryandBioengineering,ChongqingUniversityofScienceandTechnology,Chongqing400050,China) Abstract:MCM一41molecularsievewassynthesizedbythesol—gelmethodandfunctionalizedwithbenzylsul— phonicacidandtrimerhylchlorosilaneusingapost—syntheticprocedure.Theorganicgroupswerecovalently bondedtothesurfaceofMCM一41byetherificationofSi—OHandthusanewS—B—MCM一41catalystwaspre— pared.ThestructureandBr6nstedacidamountofS—B—MCM一41catalystwerecharacterizedbyXRD,N,adsorp— tion-desorption,andacid—basetitration.TheresultsshowedthatthemesoporousstructureofMCM一41was maintainedintheS—B—MCM一41catalystwithaBETsurfaceareaof798m/gandacidcapacityof4.0mmol/g. Thesynthesisofiso—amylacetatefromaceticacidandiso—amylalcoholoverS—B—MCM一4】catalystanditscatalyt— icperformancewereinvestigated.Undertheoptimumconditionsofaceticacid0.1mo1.iso—amylalcohol0.15 mol,catalyst0.2g,water—entrainertoluene15ml,reactiontemperature110—125℃,andreactiontime2h, theesterificationfractionwasover99%.Bycomparison.theMCM一41molecularsieveonlyhadanesterification fract