非催化条件下异丙苯液相过氧化反应动力学

doi:10.11949/j.issn.0438-1157.20141807

化工学报 ›› 2015, Vol. 66 ›› Issue (5): 1710-1715.DOI: 10.11949/j.issn.0438-1157.20141807

• 催化、动力学与反应器 • 上一篇下一篇

非催化条件下异丙苯液相过氧化反应动力学

刘明鑫, 许志美, 孙伟振, 张明华, 赵玲

华东理工大学化学工程联合国家重点实验室, 上海 200237

收稿日期:2014-12-08 修回日期:2015-02-26 出版日期:2015-05-05 发布日期:2015-05-05
通讯作者: 孙伟振
基金资助:
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)。

Reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene

LIU Mingxin, XU Zhimei, SUN Weizhen, ZHANG Minghua, ZHAO Ling

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2014-12-08 Revised:2015-02-26 Online:2015-05-05 Published:2015-05-05
Supported by:
supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the National Natural Science Foundation of China (61333010) and the 111 Project (B08021).

摘要/Abstract

摘要： 研究了非催化条件下异丙苯(IPB)液相氧化主副反应动力学,包括主要副产物α-甲基苄醇(MBA)和苯乙酮(ACP)生成规律以及重要链终止产物ROOR (DCP)的分解反应路径。基于烃类链式自由基反应机理,建立了包含反应物IPB、主产物过氧化氢异丙苯(IPBHP)、副产物MBA、ACP以及链终止产物DCP的反应动力学模型。动力学模型预测结果与实验数据吻合良好。通过对373～404 K下实验数据的拟合,得到了不同温度下各基元反应速率常数和活化能。模拟计算表明,两个副反应活化能均大于主反应;链终止产物DCP的分解反应通过氧气的参与进行。研究结果可为异丙苯液相氧化工业反应过程的设计和优化提供基础参数,并且有利于深化对烷基芳烃液相氧化反应机理的认识。

关键词: 异丙苯, 氧化, 反应动力学, 过氧化氢异丙苯, 参数估值

Abstract: Both main and side reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene (IPB) were investigated, including byproduct formation such as α-methyl benzyl alchohol (MBA) and acetophenone (ACP), and decomposition pathway of ROOR (DCP). Based on free radical chain reaction mechanism, a kinetic model was developed, in which IPB hydroperoxide (IPBHP), MBA, ACP and DCP were considered. The prediction by this kinetic model is agreed well with the experimental data, if the rate constants were used which were obtained by fitting of the experimental data at 373—404 K. The activation energies estimated were larger for all side reactions than for the main reaction. DCP decomposition requires the presence of oxygen. These data obtained could be helpful for deep understand of the reaction mechanism of liquid phase of alkyl aromatics and could be used as the fundamental data for design and optimization of industrial liquid phase oxidation of IPB.

Key words: isopropyl benzene, oxidation, reaction kinetics, isopropyl benzene hydroperoxide, parameter estimation

中图分类号:

刘明鑫, 许志美, 孙伟振, 张明华, 赵玲. 非催化条件下异丙苯液相过氧化反应动力学[J]. 化工学报, 2015, 66(5): 1710-1715.

LIU Mingxin, XU Zhimei, SUN Weizhen, ZHANG Minghua, ZHAO Ling. Reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene[J]. CIESC Journal, 2015, 66(5): 1710-1715.

参考文献 20

[1]	Schmidt R J. Industrial catalytic processes:phenol production [J]. Applied Catalysis A: General, 2005, 280 (1): 89-103
[2]	Ren Yongli (任永利), Mi Zhentao (米振涛). Study on catalyst hydrogen peroxide oxidation of benzene into phenol [J]. Chemical Industry and Engineering Progress (化工进展), 2002, 21 (11): 827-830
[3]	Han L, Wang Y, Zhang J, et al. Acidic montmorillonite/cordierite monolithic catalysts for cleavage of cumene hydroperoxide [J]. Chinese Journal of Chemical Engineering, 2014, 22 (8): 854-860
[4]	Yadav G D, Asthana N S. Selective decomposition of cumene hydroperoxide into phenol and acetone by a novel cesium substituted heteropolyacid on clay [J]. Applied Catalysis A: General, 2003, 244 (2): 341-357
[5]	He Yufeng, Wang Rongmin, Liu Yuyang, et al. Study on oxidation mechanism of cumene based on GC-MS analysis [J]. Journal of Molecular Catalysis A: Chemical, 2000, 159 (1): 109-113
[6]	Crites C O L, Hallett-Tapley G L, Frenette M, et al. Insights into the mechanism of cumene peroxidation using supported gold and silver nanoparticles [J]. ACS Catalysis, 2013, 3 (9): 2062-2071
[7]	Zhang Meiying, Wang Lefu, Ji Hongbing, et al. Cumene liquid oxidation to cumene hydroperoxide over CuO nanoparticle with molecular oxygen under mild condition [J]. Journal of Natural Gas Chemistry, 2007, 16 (4): 393-398
[8]	Maksimov Y V, Suzdalev I P, Tsodikov M V, et al. Study of cumene oxidation over zirconia-, titania-and alumina-based complex oxides obtained by sol-gel methods: activity-structure relationships [J]. Journal of Molecular Catalysis Chemical, 1996, 105 (3): 167-173
[9]	Wen Fei (文飞), Cheng Youwei (成有为), Guo Xia (郭霞), Wang Lijun (王丽军), Li Xi (李希). Liquid phase catalytic oxidation of cumene [J]. Chemical Reaction Engineering and Technology (化学反应工程与工艺), 2009, 25 (4): 376-379
[10]	Sun Weizhen, Shi Yi, Chen Jie, et al. Alkylation kinetics of isobutane by C4 olefins using sulfuric acid as catalyst [J]. Industrial & Engineering Chemistry Research, 2013, 52 (44): 15262-15269
[11]	Sun Weizhen, Zhao Ling. Simulation of secondary oxidation of p-xylene in liquid phase [J]. Industrial & Engineering Chemistry Research, 2010, 50 (5): 2548-2553
[12]	Song J, Gao L, Lin J, et al. Kinetics and modeling of chemical leaching of sphalerite concentrate using ferric iron in a redox-controlled reactor [J]. Chinese Journal of Chemical Engineering, 2013, 21 (8): 933-936
[13]	Sun Weizhen (孙伟振), Huang Huan (黄欢), Gu Xiaowu (顾晓吴), Zhao Ling (赵玲). Modeling of liquid phase oxidation kinetics of aromatic hydrocarbon based on free radical chain reaction mechanism [J]. CIESC Journal (化工学报), 2010, 61 (7): 2119-2123
[14]	Xu Xiaotao (许晓涛), Zhang Weixing (张未星). Kinetics of 1, 1, 1, 3, 3-pentachloropropane synthesis reaction [J]. CIESC Journal (化工学报), 2014, 65 (1): 176-181
[15]	Hattori K, Tanaka Y, Suzuki H, et al. Kinetics of liquid phase oxidation of cumene in bubble column [J]. Journal of Chemical Engineering of Japan, 1970, 3 (1): 72-78
[16]	Yu Xuemin (于学敏), Li Ziming (李自明), Wang Jinquan (王金泉), et al. Study of cumene liquid-phase oxidation reaction kinetics [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 1984, 35 (2): 130-138
[17]	Di Somma I, Marotta R, Andreozzi R, et al. Dicumyl peroxide thermal decomposition in cumene: development of a kinetic model [J]. Industrial & Engineering Chemistry Research, 2011, 51 (22): 7493-7499
[18]	Andrigo P, Caimi A, Cavalieri P, et al. Phenol-acetone process: cumene oxidation kinetics and industrial plant simulation [J]. Chemical Engineering Science, 1992, 47 (9): 2511-2516
[19]	Bhattacharya A. Kinetic modeling of liquid phase autoxidation of cumene [J]. Chemical Engineering Journal, 2008, 137 (2): 308-319
[20]	Hendry D G. Rate constants for oxidation of cumene [J]. Journal of the American Chemical Society, 1967, 89 (21): 5433-5438

非催化条件下异丙苯液相过氧化反应动力学

Reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[2]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[3]	宋瑞涛, 王派, 王云鹏, 李敏霞, 党超镔, 陈振国, 童欢, 周佳琦. 二氧化碳直接蒸发冰场排管内流动沸腾换热数值模拟分析[J]. 化工学报, 2023, 74(S1): 96-103.
[4]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[5]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[6]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[7]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[8]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[9]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[10]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[11]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[12]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[13]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[14]	洪瑞, 袁宝强, 杜文静. 垂直上升管内超临界二氧化碳传热恶化机理分析[J]. 化工学报, 2023, 74(8): 3309-3319.
[15]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.