Liquid-phase oxidation kinetics of sec-butylbenzene

doi:10.11949/j.issn.0438-1157.20180215

Abstract

Abstract:

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.

Key words: sec-butylbenzene, liquid-phase oxidation, kinetic models, sec-butylbenzene hydroperoxide

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（388~403 K），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。

关键词: 仲丁基苯, 液相氧化, 动力学模型, 过氧化氢仲丁基苯

CLC Number:

DONG Jian, ZHANG Shenglu, SUN Weizhen, XU Zhimei, ZHAO Ling. Liquid-phase oxidation kinetics of sec-butylbenzene[J]. CIESC Journal, 2018, 69(11): 4737-4745.

董健, 张胜露, 孙伟振, 许志美, 赵玲. 仲丁基苯液相氧化反应动力学[J]. 化工学报, 2018, 69(11): 4737-4745.

References 30

[1]	Suresh A K, Sharma†Man M, Sridhar T. Engineering aspects of industrial liquid-phase air oxidation of hydrocarbons[J]. Industrial & Engineering Chemistry Research, 2000, 39(11):3958-3997.
[2]	Emanuel N M, Zaikov G E. Oxidation of Organic Compounds:Medium Effects in Radical Reactions[M]. Amsterdam:Elsevier, 1984.
[3]	Andrigo P, Caimi A, dOro P C, et al. Phenol-acetone process:cumene oxidation kinetics and industrial plant simulation[J]. Chemical Engineering Science, 1992, 47(9/10/11):2511-2516.
[4]	Bhattacharya A. Kinetic modeling of liquid phase autoxidation of cumene[J]. Chemical Engineering Journal, 2008, 137(2):308-319.
[5]	Krongauz V V, O'Connell J F, Ling M T K. Kinetics of catalyst-free thermal and photo-oxidation of cumene[J]. Journal of Thermal Analysis & Calorimetry, 2014, 116(3):1285-1299.
[6]	Reichardt C, Welton T. Solvents and Solvent Effects in Organic Chemistry[M]. New York:John Wiley & Sons, 2011.
[7]	Sun W, Pan Y, Zhao L, et al. Simplified free-radical reaction kinetics for p-xylene oxidation to terephthalic acid[J]. Chemical Engineering & Technology, 2010, 31(10):1402-1409.
[8]	Shang J, Sun W, Zhao L, et al. Modeling of CO2-assisted liquid phase oxidation of para-xylene catalyzed by transition metals/bromide[J]. Chemical Engineering Science, 2015, 127: 52-59.
[9]	Sun W, Ling Z. Simulation of secondary oxidation of p-xylene in liquid phase[J]. Industrial & Engineering Chemistry Research, 2010, 50(5):2548-2553.
[10]	Sun W, Sun J, Xu Z, et al. Experimental study and modeling of homogenous catalytic oxidation of m-xylene to isophthalic acid[J]. Industrial & Engineering Chemistry Research, 2015, 54(13):3293-3298.
[11]	裘俊峰, 许志美, 赵玲, 等. 高效液相色谱法分析环己基苯液相氧化体系的组成[J]. 石油化工, 2016, 45(8):910-914. QIU J F, XU Z M, ZHAO L, et al. Analysis of the cyclohexylbenzene oxidation system by high performance liquid chromatography[J]. Petrochemical Technology, 2016, 45(8):910-914.
[12]	万骏. 间二甲苯液相催化氧化制备间苯二甲酸反应过程研究[D]. 上海:华东理工大学, 2004. WAN J. Reaction process research on preparation of isophthalic acid by MX liquid-phase catalytic oxidation[D]. Shanghai:East China University of Science and Technology, 2004.
[13]	Marl G F, Sheldon R A. Chemical Reactions/Oxidation[M]//Ullmann's Encyclopedia of Industrial Chemistry. Weinheim:Wiley-VCH, 2007:1-58.
[14]	Russell G A. Oxidation of unsaturated compunds(Ⅲ):Products of the reaction of indene and oxygen; stereochemistry of the addition of a peroxy radical and oxygen to a double bond[J]. Journal of the American Chemical Society, 1956, 78(5):1035-1040.
[15]	Sheldon R. Metal-catalyzed Oxidations of Organic Compounds:Mechanistic Principles and Synthetic Methodology Including Biochemical Processes[M]. Amsterdam:Elsevier, 2012.
[16]	Hattori K, Tanaka Y, Suzuki H, et al. Kinetic of liquid fase oxidation of cumene in bubble column[J]. Journal of Chemical Engineering of Japan, 1970, 3(1):72-78.
[17]	Bamford C H, Dewar M J S. The autoxidation of tetralin[J]. Proceedings of the Royal Society A Mathematical Physical & Engineering Sciences, 1949, 198(1053):252-267.
[18]	Cao G, Servida A, Pisu M, et al. Kinetics of p-xylene liquid-phase catalytic oxidation[J]. AIChE Journal, 1994, 40(7):1156-1166.
[19]	Hendry D G. Rate constants for oxidation of cumene[J]. Journal of the American Chemical Society, 1967, 89(21):5433-5438.
[20]	Traylor T G, Russell C A. Mechanisms of autoxidation. Terminating radicals in cumene autoxidation[J]. Journal of the American Chemical Society, 1965, 87(16):3698-3706.
[21]	Melville H W, Richards S. The photochemical autoxidation of iso-propylbenzene[J]. Journal of the Chemical Society (Resumed), 1954:944-952.
[22]	Thomas J R. The thermal decomposition of alkyl hydroperoxides[J]. Journal of the American Chemical Society, 1955, 77(1):246-248.
[23]	Feng W, Vynckier E, Froment G F. Single event kinetics of catalytic cracking[J]. Industrial & Engineering Chemistry Research, 1993, 32(12):2997-3005.
[24]	Quintana-Sólorzano R, Thybaut J W, Marin G B. A single-event microkinetic analysis of the catalytic cracking of (cyclo) alkanes on an equilibrium catalyst in the absence of coke formation[J]. Chemical Engineering Science, 2007, 62(18/19/20):5033-5038.
[25]	Toch K, Thybaut J W, Vandegehuchte B D, et al. A single-event microkinetic model for "ethylbenzene dealkylation/xylene isomerization" on Pt/H-ZSM-5 zeolite catalyst[J]. Applied Catalysis A:General, 2012, 425:130-144.
[26]	黄华江. 实用化工计算机模拟:MATLAB在化学工程中的应用[M]. 北京:化学工业出版社, 2004. HUANG H J. Practical Chemical Computer Simulation:Application of MATLAB in Chemical Engineering[M]. Beijing:Chemical Industry Press, 2004.
[27]	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.
[28]	Low D I R. The unsteady state absorption of oxygen in cumene[J]. The Canadian Journal of Chemical Engineering, 1967, 45(3):166-170.
[29]	Steele W V, Chirico R D, Knipmeyer S E, et al. Vapor pressure, heat capacity, and density along the saturation line:measurements for benzenamine, butylbenzene, sec-butylbenzene, tert-butylbenzene, 2,2-dimethylbutanoic acid, tridecafluoroheptanoic acid, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1-chloro-2-propanol[J]. Journal of Chemical & Engineering Data, 2002, 47(4):648-666.
[30]	Bateman L, Gee G. Determination of absolute rate constants for olefinic oxidations by measurement of photochemical pre-and after-effects(Ⅰ):At "high" oxygen pressures[J]. Transactions of the Faraday Society, 1951, 47:155-164.