催化学报

催化学报 ›› 2009, Vol. 30 ›› Issue (5): 453-458.

• 研究论文 • 上一篇    下一篇

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1, 宋春山1,2, 郭新闻1   

  1. 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
  • 出版日期:2009-05-25 发布日期:2013-02-05

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

NIE Xiaowa1, LIU Xin1, SONG Chunshan1,2, GUO Xinwen1,*   

  1. 1State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, Liaoning, China2EMS Energy Institute, Department of Energy and Mineral Engineering, Pennsylvania State University, University Park, PA 16802, USA
  • Online:2009-05-25 Published:2013-02-05

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2247

被引次数

23

摘要： 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.

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

Abstract: With the help of DFT calculations, the reaction mechanisms of benzene alkylation with ethanol and ethylene have been studied. The alkylation of benzene with ethanol occurs via the stepwise mechanism. Alkylation of benzene with ethylene occurs through both concerted mechanism and stepwise mechanism. These two paths are only slightly different in the activation energy.

Key words: benzene, ethanol, ethylene, alkylation, reaction mechanism, H-ZSM-5, theoretical calculation