H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应的理论研究

催化学报 , 2009, 30(5): 453-458.

H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应的理论研究

聂小娃 ^1, , 刘新 ^2, , 宋春山 ^3, , 郭新闻 ^4,

1.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

2.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

3.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;宾夕法尼亚州立大学能源与矿物工程系能源研究所,宾夕法尼亚,16802,美国

4.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

基金项目: 教育部新世纪优秀人才支持计划(NCET-04-0268) 国家自然科学基金(20573013) 高等学校学科创新引智计划(111计划) 大连理工大学青年教师培养基金(2007009)

关键词：苯 , 乙醇 , 乙烯 , 烷基化反应 , 反应机理 , H-ZSM-5 , 理论计算

Theoretical Study on Alkylation of Benzene with Ethanol and Ethylene over H-ZSM-5

采用ONIOM2(B3LYP/6-31G(d):UFF)计算方法研究了H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应历程.选取40T簇模型模拟了H-ZSM-5分子筛位于孔道交叉点的酸性位.从生成能和反应活化能角度分析并比较了苯与乙醇和乙烯烷基化反应机理.结果表明,苯与乙醇的烷基化按照分步机理进行,速控步骤的活化能为170.34 kJ/mol.而乙烯作为烷基化剂与苯反应时同时存在联合机理和分步机理,且二者之间存在一定程度的竞争,其中联合机理的活化能为167.24 kJ/mol,分步机理速控步骤的活化能为155.20 kJ/mol.比较苯与乙醇和乙烯发生烷基化反应的机理可以看出,二者作为烷基化试剂对烷基化反应性能影响不大.

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