SBA-15分子筛负载对甲苯磺酸催化合成过氧化二异丙苯的性能和反应过程模拟  

Catalysis and Simulation of SBA-15 Zeolite Supported p-Toluenesulfonic Acid for the Synthesis of Dicumyl Peroxide

作　　者：张小龙 张毅城 李庆朝 查飞[1] 常玥[1] 唐小华[1] ZHANG Xiaolong;ZHANG Yicheng;LI Qingchao;ZHA Fei;CHANG Yue;TANG Xiaohua(College of Chemistry&Chemical Engineering,Northwest Normal University,Lanzhou 730070,China;Shandong Yanggu Huaitai Chemical Co.,Ltd.,Yanggu 252300,China)

机构地区：[1]西北师范大学化学化工学院,兰州730070 [2]山东阳谷华泰化工股份有限公司,阳谷252300

出　　处：《高等学校化学学报》2024年第6期98-106,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22268039);甘肃省高校产业支撑计划项目(批准号:2023CYZC-18)。

摘　　要：采用浸渍法制备了SBA-15分子筛负载对甲苯磺酸(TsOH)催化剂TsOH/SBA-15,探究了其催化α-甲基苯乙烯(α-MS)和异丙苯过氧化氢(CHP)反应制备过氧化二异丙苯(DCP)的活性,并对反应过程进行了模拟分析.当进料比n(α-甲基苯乙烯)/n(异丙苯过氧化氢)=2.0, TsOH/SBA-15用量为CHP质量的0.15%,于44℃反应2.5h, DCP的产率为62.1%.模拟计算结果表明,反应过程有异步协同反应和分步反应两种机理,在异步协同反应中α-MS, CHP和TsOH只需要经过一个过渡态即可完成,而分步反应中反应物需要经过两个过渡态以及一个中间体才能完成,两种路径均涉及2次H^(+)的转移.在44℃下,异步协同反应的反应能垒(ΔG)为121.8 kJ/mol,分步反应中两个过渡态对应的反应能垒分别为74.1和78.3 kJ/mol.SBA-15 zeolite suppored p-toluenesulfonic acid(TsOH/SBA-15)was prepared using the impregnation method.The catalytic activity of TsOH/SBA-15 in synthesis of dicumyl peroxide(DCP)fromα-methylstyrene(α-MS)reacted with isopropylbenzene hydroperoxide(CHP)was evaluated.Under the conditions of m(TsOH/SBA-15)/m(CHP)=0.15%,n(α-MS)/n(CHP)=2.0,44℃and 2.5 h,the yield of DCP was 62.1%.Simulation analysis suggested that the reaction process follows two mechanisms of asynchronous synergistic reaction and step-by-step reaction.α-MS,CHP,and TsOH undergo a single transition state in the asynchronous synergistic reaction process,while there are two transition states and one intermediate in the step-by-step reaction,both requiring H^(+)proton trans⁃formation.The reaction energy barrier in the asynchronous synergistic reaction was calculated to be 121.8 kJ/mol at 44℃,while the reaction energy barriers were 74.1 and 78.3 kJ/mol in the two transition states in the step-by-step reaction,respectively.

关 键 词：对甲苯磺酸 SBA-15分子筛 过氧化二异丙苯 异丙苯过氧化氢 反应能垒 

分 类 号：O643.36[理学—物理化学] TQ203.2[理学—化学]