乙苯液相过氧化反应的自由基动力学模型研究  

Radical Kinetic Model of Liquid-Phase Peroxidation of Ethyl Benzene

作　　者：顾晓吴[1] 孙伟振[1] 赵玲[1] 高焕新[2] 金国杰[2] 

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237 [2]中国石油化工股份有限公司上海石油化工研究院,上海201208

出　　处：《石油化工》2010年第4期411-416,共6页Petrochemical Technology

摘　　要：在140～155℃内,采用半连续实验研究了用乙苯氢过氧化物作为引发剂的乙苯液相过氧化反应动力学。基于烃类氧化的自由基反应机理,将乙苯液相过氧化反应的主产物乙苯氢过氧化物和副产物α-甲基苄醇、苯乙酮分别作为独立组分,根据乙苯氢过氧化物的O—O键均裂、O—H键断裂等不同的引发方式,分别建立了3个相应的自由基动力学模型。通过模型拟合和辨识,发现乙苯氢过氧化物的引发方式主要为O—O键的均裂,O—H键的断裂可以忽略。以乙苯氢过氧化物O—O键的均裂为引发方式的乙苯液相过氧化自由基动力学模型计算值与实验值相对误差小于8%。The free radical kinetics of liquid-phase peroxidation of ethylbenzene in the temperature range of 140 - 155 ℃ with ethylbenzene hydroperoxide as initiator was studied through semi-continuous experiment. Based on reaction mechanism of hydrocarbon oxidation, according to different initiation modes（ O--O bond homolysis and O--H bond breaking of ethylbenzene hydroperoxide）, three free radical kinetic models were established. The main product ethylbenzene hydroperoxide and the by- products（a-methyl benzyl alcohol and acetophenone） were treated as independent components in the three models. By model fitting and identification, it was found that the main initiation mode of ethylbenzene hydroperoxide was O--O bond homolysis while O--H bond breaking could be ignored. The kinetics model for O--O bond homolysis could fit experimental data well and the relative error was less than 8%.

关 键 词：乙苯 液相过氧化 乙苯氢过氧化物 自由基 动力学模型 

分 类 号：TQ031.7[化学工程]