H-β和H型丝光分子筛催化苯与叔丁醇叔丁基化反应机理  

Mechanism of the Tert-Butylation Reaction between Benzene and Tert-Butyl Alcohol Catalyzed by H-βand H-Mordenite Zeolite

作　　者：李玲玲[1] 陈韧[1] 孙野[1] 李晓亮[1] 聂小娃[2] 宋春山[2] 郭新闻[2] Li Lingling;Chen Ren;Sun Ye;Li Xiaoliang;Nie Xiaowa;Song Chunshan;Guo Xinwen(Department of Metallurgical Engineering,Liaoning Key Laboratory of Optimization and Utilization of Non-Associated Low-Grade Iron Ore,Liaoning Institute of Science and Technology,Benxi,Liaoning 117004,China;School of Chemical Engineering,State Key Laboratory of Fine Chemicals,PSU-DUT Joint Center for Energy Research,Dalian University of Technology,Dalian,Liaoning 116024,China)

机构地区：[1]辽宁科技学院冶金工程学院辽宁省低品位非伴生铁矿优化应用重点实验室,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

出　　处：《化学世界》2021年第4期230-235,共6页Chemical World

基　　金：辽宁省自然科学基金(Nos.2019-MS-175,20170540476,2019-ZD-0519);辽宁省工业攻关及产业化(No.2020JH2/10100019);辽宁省百千万人才和辽宁省教育厅科学研究一般项目基金(No.L2019lkyqn-03)资助项目。

摘　　要：采用分层计算(ONIOM2)[密度泛函理论∶分子力场(DFT∶UFF)]和密度泛函理论结合的方法,研究了116T H-β和H-型丝光(H-MOR)分子筛催化苯与叔丁醇叔丁基化反应机理。描述了叔丁基化反应中共吸附复合物和过渡态的构型。根据298和433 K时自由能垒的计算结果,对比研究了分子筛的催化性能。在298和433 K时,苯叔丁基化反应的自由能垒相近,推测该反应温度范围内反应温度对苯转化影响很小,与H-β分子筛相比,由于反应自由能垒更低,H-MOR分子筛对苯叔丁基化生成叔丁基苯反应有更好的催化活性。The mechanisms of tert-butylation reaction between benzene and tert-butyl alcohol catalyzed by 116 T H-βand H-mordenite(H-MOR)zeolite were systematically investigated by using own-N-layered integrated molecular orbit+molecular mechanics(ONIOM2)(DFT∶UFF)method combined with density functional theory calculation.The configurations of co-adsorbed complex and transition state along the tert-butylation paths were described.The catalytic performances of zeolites were comparatively studied based on the free energy barrier results calculated at 298 and 433 K.At 298 and 433 K,the free energy barriers of tert-butylation of benzene were similar,which implied that the reaction temperature within this range has little effect on the conversion of benzene.In comparison with H-βzeolite,H-MOR zeolite showed better catalytic activity to the tert-butylation of benzene for the formation of tert-butyl benzene due to a lower free energy barrier.

关 键 词：苯 叔丁醇 反应机理 分子筛 理论计算 

分 类 号：O641[理学—物理化学]