苯和甲醇在H-ZSM-5催化剂上甲基化的反应机理

引用本文: 李玲玲, 陈韧, 戴戬, 孙野, 张作良, 李晓亮, 聂小娃, 宋春山, 郭新闻. 苯和甲醇在H-ZSM-5催化剂上甲基化的反应机理[J]. 物理化学学报, 2017, 33(4): 769-779. doi: 10.3866/PKU.WHXB201612162 shu

Citation: LI Ling-Ling, CHEN Ren, DAI Jian, SUN Ye, ZHANG Zuo-Liang, LI Xiao-Liang, NIE Xiao-Wa, SONG Chun-Shan, GUO Xin-Wen. Reaction Mechanism of Benzene Methylation with Methanol over H-ZSM-5 Catalyst[J]. Acta Physico-Chimica Sinica, 2017, 33(4): 769-779. doi: 10.3866/PKU.WHXB201612162 shu

苯和甲醇在H-ZSM-5催化剂上甲基化的反应机理

李玲玲 ^1, ,
陈韧 ^1, ,
戴戬 ^1, ,
孙野 ^1, ,
张作良 ^1, ,
李晓亮 ^1, ,
聂小娃 ^2, ,
宋春山 ^2,3, ,
郭新闻 ^2,

1.
辽宁科技学院冶金工程学院, 辽宁本溪 117004;
2.
大连理工大学化工学院, 精细化工国家重点实验室, PSU-DUT联合能源研究中心, 辽宁大连 116024;
3.
宾夕法尼亚州立大学能源与矿物工程系能源研究所, PSU-DUT联合能源研究中心, 大学城 16802, 宾夕法尼亚, 美国
基金项目:
辽宁省教育厅科学研究一般项目基金（L2014503），辽宁省自然科学基金项目（201602403），辽宁科技学院博士科研启动基金项目（1406B08）及国家自然科学基金项目（21503027）资助

摘要: 采用“our own-N-layered integrated molecular orbital + molecular mechanics”（ONIOM）和密度泛函理论（DFT）结合的方法，在5T、12T、104T₉和104T₁₂ H-ZSM-5 模型中研究了苯和甲醇甲基化的分步和协同机理。描述了中间体物种和过渡态的结构。考察了H-ZSM-5催化剂Brø；nsted （B）酸强度对苯和甲醇甲基化反应机理的影响。反应活化能结果表明，在B酸强度更强的H-ZSM-5 催化剂上，苯和甲醇甲基化反应更容易发生，反应活化能更低。随着B酸强度增强，分步机理的反应活化能比协同机理的反应活化能降低的更多。B酸强度增强对分步机理更有利。当分步机理成为主导反应路径时，分步机理中甲醇脱水步骤生成的甲氧基中间体进一步生成大体积烃类的副反应会导致H-ZSM-5 催化剂因积炭而失活。合理调变H-ZSM-5 催化剂的酸强度对提高催化剂的催化活性和稳定性有重要意义。

关键词:

English

Reaction Mechanism of Benzene Methylation with Methanol over H-ZSM-5 Catalyst

1.
Department of Metallurgical Engineering, Liaoning Institute of Science and Technology, Benxi 117004, Liaoning Province, P. R. China;
2.
State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China;
3.
EMS Energy Institute, PSU-DUT Joint Center for Energy Research and Department of Energy & Mineral Engineering, Pennsylvania State University, University Park, PA 16802, USA
Received Date: 31 October 2016
Revised Date: 16 December 2016
Available Online: 16 December 2016
Fund Project:
The project was supported by the Scientific Research Foundation for the general Program of Department of Education of Liaoning Province of China (L2014503), Natural Science Foundation of Liaoning Province, China (201602403), Research Fund for the Doctoral Program of Liaoning Institute of Science and Technology, China (1406B08) and National Natural Science Foundation of China (21503027).

Abstract: The stepwise and concerted mechanisms of benzene methylation with methanol were studied with the 5T, 12T, 104T₉, and 104T₁₂ H-ZSM-5 models using the“our own-N-layered integrated molecular orbital + molecular mechanics”(ONIOM) in combination with density functional theory (DFT) methods. The structures of intermediate species and transition states were described. The effect of the Brønsted (B) acid strength of HZSM-5 catalyst on the reaction mechanism of benzene methylation with methanol was considered. The reaction activation energy results indicate that benzene methylation with methanol preferentially occurs over H-ZSM-5 catalyst with greater B acid strength, and a lowering of the activation barrier was observed. With increasing B acid strength, the reaction activation energy of the stepwise mechanism decreases more than that of the concerted mechanism. Increasing the B acidic strength is more beneficial to the stepwise mechanism. When the stepwise mechanism becomes the dominant reaction path, the secondary reaction arising from further formation of bulky hydrocarbons through the methoxide intermediate produced in the methanol dehydration step of the stepwise mechanism might lead to the inactivation of the H-ZSM-5 catalyst owing to coke formation. Reasonable modulation the acid strength of the H-ZSM-5 catalyst is important in improving its catalytic activity and stability of the catalyst.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

苯和甲醇在H-ZSM-5催化剂上甲基化的反应机理

English

Reaction Mechanism of Benzene Methylation with Methanol over H-ZSM-5 Catalyst

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中国化学会秘书处

苯和甲醇在H-ZSM-5催化剂上甲基化的反应机理

English

Reaction Mechanism of Benzene Methylation with Methanol over H-ZSM-5 Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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