Research on the mechanism of benzene alkylation with short-chain olefins on zeolite by quantum chemistry

doi:10.16085/j.issn.1000-6613.2015.03.004

Abstract

Abstract: Methods of quantum mechanics and their research applications on the mechanism of benzene alkylation with short-chain olefins in recent years were reviewed. Software based on quantum mechanics and their applications were also introduced. The controversial concerted and stepwise mechanism on the alkylation between benzene and short-chain olefins was elaborated by different model sizes and variable computational methods. The future of computational method for research on the mechanism of benzene alkylation with short-chain was also discussed. The hybrid QM/MM (quantum mechanics/molecular mechanics) approach that combines the strengths of the QM (accuracy) and MM (speed) approaches will be a more effective way to study chemical reaction mechanism.

Key words: quantum mechanics, benzene, short-chain olefins, alkylation, reaction, model

摘要： 对近年来基于量子化学方法研究苯与短链烯烃烷基化反应机理的进展进行了综述。简要介绍了量子化学方法的相关软件及其应用。对于苯与短链烯烃发生烷基化时存在争议的协同机理和分步机理, 详细阐述了采用大小不同模型和计算方法对其进行研究的进展;由此可以展望量子力学/分子动力学(QM/MM)组合方法综合了量子化学理论和分子动力学理论的优点, 将成为研究化学反应机理的更有效方法。

关键词: 量子化学, 苯, 短链烯烃, 烷基化反应, 反应, 模型

CLC Number:

O643.1

SUN Xiaoyan, QIANG Long, XIANG Shuguang. Research on the mechanism of benzene alkylation with short-chain olefins on zeolite by quantum chemistry[J]. Chemical Industry and Engineering Progree, 2015, 34(3): 624-627,637.

孙晓岩, 强龙, 项曙光. 量子化学方法应用于分子筛上苯与短链烯烃反应机理的研究进展[J]. 化工进展, 2015, 34(3): 624-627,637.

References

[1] 程国香.固体酸烷基化工艺发展现状[J].石化技术, 1998, 5(3):182-187.

[2] Berna T.Alkylation of aromatic hydrocarbons.US, 5l57158[P].1992.

[3] Subawalla H, Fair J R.Design guidelines for solid-catalyzed reactive distillation systems[J].Ind.Eng.Chem.Res., 1999, 38(10):3696-3709.

[4] 刘庆辉, 詹宏昌, 汤敏擘.固体酸催化剂的分类以及研究近况[J].广州化工, 2008, 36(2):14-17.

[5] 赵亮, 高金森, 徐春明.分子计算理论方法及在化工计算中的应用[J].计算机与应用化学, 2004, 21(5):764-772.

[6] 杨振, 徐志军, 杨晓宁.基于密度泛函理论研究二元排斥Yukawa流体的表面结构性质[J].物理化学学报, 2006, 22(12):1460-1465.

[7] 陈念陔, 高坡, 乐征宇.量子化学理论基础[M].哈尔滨:哈尔滨工业大学出版社, 2002.

[8] Flego C, Kiricsi I, Perego C, et al.Adsorption of propene, benzene, their mixtures and cumene on H-beta zeolites studied by IR and UV-VIS spectroscopy[J].Stud.Surf.Sci.Catal., 1995, 94:405-412.

[9] 潘纲, 刘媛媛.MEA-Langmuir-Hinshelwood光催化降解动力学方程[J].环境化学, 2006, 25(1):1-4.

[10] Wojciechowski B W.The reaction mechanism of catalytic cracking:Quantifying activity, selectivity, and catalyst decay[J].Catal.Rev.Sci.Eng., 1998, 40(3):209-328.

[11] Venuto P, Landis P.Organic reactions catalyzed by crystalline aluminosilicates II.Alkylation reactions:Mechanistic and aging considerations[J].J.Catal., 1966, 5(3):484-493.

[12] You Hongjun, Long Wenyu, Pan Yi.The mechanism and kinetics for the alkylation of benzene with ethylene[J].Pet.Sci.Technol., 2006, 24(9):1079-1088.

[13] Vos Ann M, Robert A, Schoonheydt, et al.Reactivity descriptors and rate constants for acid zeolite catalyzed ethylation and isopropylation of benzene[J].J.Phys.Chem.B, 2003, 107(9):2001-2008.

[14] Arstad Bjørnar, Kolboe Stein, Swang Ole.Theoretical investigation of arene alkylation by ethene and propene over acidic zeolites[J].J.Phys.Chem.B, 2004, 108(7):2300-2308

[15] 张达, 孙晓岩, 项曙光.DFT方法研究酸性沸石上苯与乙烯烷基化反应的机理[J].化学研究, 2013, 24(2):189-194.

[16] Namuangruk Supawadee, Pantu Piboon, Limtrakul Jumras.Alkylation of benzene with ethylene over faujasite zeolite investigated by the ONIOM method[J].J.Catal., 2004, 225(2):523-530.

[17] Niels Hansen, Till Brüggemann, Alexis T Bell, et al.Theoretical investigation of benzene alkylation with ethene over H-ZSM-5[J].J.Phy.Chem.C, 2008, 112(39):15402-15411.

[18] Boronat M, Zircovich-Wilson C M, Pedro Viruela, et al.Influence of the local geometry of zeolite active sites and olefin size on the stability of alkoxide intermediates[J].J.Phys.Chem.B, 2001, 105(45):11169-11177.

[19] Rozanska X, Demuth Th, Hutschka F, et al.A periodic structure density functional theory study of propylene chemisorption in acidic chabazite:Effect of zeolite structure relaxation[J].J.Phys.Chem.B, 2002, 106(12):3248-3254.

[20] Zhang Zhou, Liu Hui, Zhu Jiqin, et al.Molecular simulations of asoption and diffusion behaviors of benzene molecules in NaY zeolite[J].Chinese J.Chem.Eng., 2009, 17(4):618-624.

[21] 聂小娃, 刘新, 宋春山, 等.H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应的理论研究[J].催化学报, 2009, 30(5):453-455.

[22] 莫亦荣, Cristobal A, 高加力.量子化学和分子力学组合方法及其应用[J].化学学报, 2000, 58(12):1504-1510.

[23] Warshel A, Levitt M.Theoretical studies of enzymic reactions:Dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme[M].J.Mol.Biol., 1976, 103(3):227-249.