仲丁基苯液相氧化反应动力学  

Liquid-phase oxidation kinetics of sec-butylbenzene

作　　者：董健 张胜露 孙伟振[1] 许志美[1] 赵玲[1] DONG Jian;ZHANG Shenglu;SUN Weizhen;XU Zhimei;ZHAO Ling(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]化学工程联合国家重点实验室,华东理工大学,上海200237

出　　处：《化工学报》2018年第11期4737-4745,共9页CIESC Journal

基　　金：教育部留学回国人员科研启动基金项目;国家自然科学基金项目(61333010);高等学校学科创新引智计划项目(B08021)。

摘　　要：非催化条件下仲丁基苯(SBB)液相氧化制备过氧化氢仲丁基苯(SBBHP)是生产苯酚和甲乙酮的关键步骤。基于烃类链式自由基反应机理,分别建立了氧充足和限氧条件下SBB氧化动力学模型,模型包含了反应物SBB、主产物SBBHP、副产物苯乙酮(ACP)、2-苯基-2-丁醇(PBO)等。通过分别拟合不同条件下的实验数据(388~403K),得到了相应的基元反应速率常数和活化能。结果表明,由于空间位阻效应,主反应生成SBBHP的活化能大于异丙苯(IPB)生成过氧化氢异丙苯(CHP)的活化能。连续实验进一步验证了动力学模型的可靠性。相关研究结果可用于仲丁基苯液相氧化过程的设计和优化,并且基元反应相关结果有利于丰富对烷基芳烃氧化反应机理的认识。Preparation of sec-butylbenzene peroxide(SBBHP)by liquid-phase oxidation of sec-butylbenzene(SBB)in absence of catalyst is a key step in production of phenol and methyl ethyl ketone.Based on free radical chain reaction mechanism of hydrocarbon oxidation,SBB oxidation kinetic model was established under oxygen-enriched and oxygen-limited conditions,including reactant SBB,main product SBBHP,and side products acetophenone(ACP)and 2-phenyl butanol(PBO).Rate constants and activation energies of corresponding elementary steps were obtained by fitting experimental data at various conditions of 388-403 K.The results showed that,due to steric hindrance effect,activation energy of main reaction of SBB to SBBHP was larger than that of isopropyl benzene(IPB)to IPB hydroperoxide(IPBHP).Continuous process experiments further verified reliability of the kinetic model.These results may be useful for design and optimization of SBB liquid-phase oxidation to SBBHP,and helpful to understand oxidation mechanism of aromatic hydrocarbons.

关 键 词：仲丁基苯 液相氧化 动力学模型 过氧化氢仲丁基苯 

分 类 号：TQ013.2[化学工程] TQ245