原料中水含量对甲苯歧化与烷基转移催化剂性能的影响

摘要/Abstract

摘要： 甲苯歧化与烷基转移反应在芳烃资源结构调整以及劣质资源再利用等环节中起着非常重要的作用。该反应原料中水含量易受到上游装置以及下游储存环境等因素的影响，其波动范围较大。本研究采用Ni改性的沸石分子筛催化剂，考察了原料中水含量对甲苯歧化与烷基转移反应性能的影响。研究表明，在实验测试范围内[w(H2O)<200μg/g]，原料中水含量对甲苯歧化反应以及甲苯与重芳烃烷基转移反应性能影响较小。但是，原料中水分子能降低催化剂中加氢组分催化活性，抑制重芳烃侧链加氢脱烷基反应，从而降低反应的重芳烃处理能力和整体转化效率。与此同时，受抑制的加氢活性同样会降低芳环加氢副反应，进而提高苯产品质量。

关键词: 甲苯歧化, 烷基转移, 脱烷基, 重芳烃, 加氢, 催化

Abstract: Toluene disproportionation and transalkylation reactions play an important role in the adjustment of aromatic resources and the reuse of inferior resources. The water content in feed affects the reactions significantly, however, it depends upon the upstream device and downstream storage environment with a large fluctuation range. The effect of water content on toluene disproportionation and transalkylation reaction was studied by using Ni modified zeolite catalyst. The results showed that within the testing range [w(H2O)<200 μg/g], the content of water had little influence on toluene disproportionation and transalkylation reaction of toluene and heavy aromatics. However, the water in the raw materials could reduce the metal reduction degree of the Ni hydrogenation active center, thereby reducing the hydrogenation activity of the catalyst and inhibiting the hydrodealkylation reaction of the side chain of heavy aromatics, thus reducing the processing capacity and overall conversion efficiency of the heavy aromatics. The inhibited hydrogenation activity would also reduce the hydrogenation of aromatic ring, so as to improve the quality of benzene product.

Key words: toluene disproportionation, transalkylation, dealkylation, heavy aromatics, hydrogenation, catalysis

中图分类号:

李华英石张平李经球孔德金. 原料中水含量对甲苯歧化与烷基转移催化剂性能的影响[J]. 石油炼制与化工, 2020, 51(4): 28-32.

参考文献

[1] Al‐Khattaf S, Ali M. A, ?ejka J. Recent development in transformations of aromatic hydrocarbons over zeolites[J]. Zeolites and Catalysis: Synthesis, Reactions and Applications, 2010, 2, 623-648.
[2] Krej?í A, Al-Khattaf S, Ali M. A, Bejblová M., ?ejka J. Transalkylation of toluene with trimethylbenzenes over large-pore zeolites[J]. Applied Catalysis A: General, 2010, 377, 99-106.
[3] Ali S. A, Ali M. A, Al-Nawad K, Ercan C, Wang Y. Parametric study of dealkylation–transalkylation reactions over mordenite-based bi-functional catalysts[J]. Applied Catalysis A: General, 2011, 393 (2011) 96-108.
[4] Al-Khattaf S. S, Ali S. A, Osman M. S, Aitani A. M. Influence of toluene-tetramethylbenzene transalkylation on heavy aromatics conversion to xylenes[J]. Journal of Industrial and Engineering Chemistry, 2015, 21, 1077-1088.
[5] Almulla F. M, Zholobenko V. I, Hill P. I, Chansai S, Garforth A. A. Transalkylation of Toluene with 1, 2, 4-Trimethylbenzene over Large Pore Zeolites[J]. Industrial & Engineering Chemistry Research, 2017, 56, 9799-9808.
[6] Kong D, Qi X, Zhu Z, Yang W, Xie Z. Technological advances in conversion of heavy aromatics to light aromatics[J]. Chemical Industry and Engineering Progress, 2006, 25, 983-987.
[7] Mokoena K, Scurrell M. S. Alkyl transfer reactions on solid acids. The disproportionation of ethylbenzene and toluene on H-mordenite and HY zeolites[J]. Petroleum Science and Technology, 2018, 36, 1208-1215.
[8] Odedairo T, Balasamy R. J, Al-Khattaf S. Toluene Disproportionation and Methylation over Zeolites TNU-9, SSZ-33, ZSM-5, and Mordenite Using Different Reactor Systems[J]. Industrial & Engineering Chemistry Research, 2011, 50, 3169-3183.
[9] 郑均林, 徐旋, 祁晓岚, 孔德金. 劣质重芳烃资源及其化工产品转化技术[J]. 化工进展, 2017, 36, 3665-3673.
[10] 戴厚良. 芳烃技术[M]. 北京: 中国石化出版社, 2017.
[11] 徐爱莲. 重整C10+重芳烃的综合利用[J]. 石化技术, 2004, 4, 14.
[12] Shi D, Zhao Z, Xu C, Duan A, Liu J, Dou T. Characterization and catalytic performances of supported chromia catalysts for C10+ heavy aromatics hydrodealkylation[J]. Journal of Molecular Catalysis A: Chemical, 2006, 245, 106-113.
[13] Tsai T C, Liu S B, Wang I. Metal supported zeolite for heavy aromatics transalkylation process[J]. Catalysis surveys from Asia, 2009, 13(2): 94-103.
[14] Chen, Q, Chen X, Mao L, Cheng, W. Recent advances in R and D of commercial catalysts for acrylonitrile synthesis, styrene production and toluene disproportionation processes[J]. Catalysis today, 1999, 51, 141-146.
[15] Dooley K. M, Brignac S. D, Price G. L. Kinetics of zeolite-catalyzed toluene disproportionation[J]. Industrial & engineering chemistry research, 1990, 29, 789-795.
[16] 邓澄浩, 祁晓岚, 郑均林, 孔德金, 唐颐. 贵金属/分子筛催化芳烃转化的研究进展[J]. 化工进展, 2017, 36, 1711-1718.
[17] Thakur R, Barman S, Gupta, R. K. Kinetic Investigation in Transalkylation of 1, 2, 4 Trimethylbenzene with Toluene over Rare Earth Metal-Modified Large Pore Zeolite[J]. Chemical Engineering Communications, 2017, 204, 254-264.
[18] Al-Khattaf S. S, Ali S. A, Aitani A. M, Al-Nawad K. J, Chiu C. H, Tsai T. C. Catalysis of metal supported zeolites for dealkylation–transalkylation of alkyl-aromatics[J]. Applied Catalysis A: General, 2016, 514, 154-163.
[19] Bernal S., Calvino J. J, Cauqui M. A, Gatica J. M, Cartes C. L, Omil J. P, Pintado, J. M. Some contributions of electron microscopy to the characterisation of the strong metal–support interaction effect[J]. Catalysis Today, 2003, 77, 385-406.
[20] Liu D, Quek X. Y, Cheo W. N. E, Lau R, Borgna A, Yang Y. MCM-41 supported nickel-based bimetallic catalysts with superior stability during carbon dioxide reforming of methane: Effect of strong metal–support interaction[J]. Journal of Catalysis, 2009, 266, 380-390.
[21] Liu, X, Liu M. H, Luo Y. C, Mou C. Y, Lin S. D, Cheng H, Lin, T. S. Strong metal–support interactions between gold nanoparticles and ZnO nanorods in CO oxidation[J]. Journal of the American Chemical Society, 2012, 134(24), 10251-10258.
[22] Michel C, Zaffran J, Ruppert A. M, Matras-Michalska J, J?drzejczyk M, Grams J, Sautet P. Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone[J]. Chemical Communications, 2014, 50, 12450-12453.
[23] Wolffenbuttel B. M. A, Nijhuis T. A, Stankiewicz A, Moulijn J. A. Influence of water on fast hydrogenation reactions with monolithic and slurry catalysts[J]. Catalysis Today, 2001, 69, 265-273.
[24] Wang W. J, Qiao M. H, Li H. X, Dai W. L, Deng, J. F. Study on the deactivation of amorphous NiB/SiO2 catalyst during the selective hydrogenation of cyclopentadiene to cyclopentene[J]. Applied Catalysis A: General, 1998, 168, 151-157.
[25] Wu Z, Zhang M, Li W, Mu S, Tao K. Study on the deactivation of supported amorphous Ni-B catalyst in hydrogenation[J]. Journal of Molecular Catalysis A: Chemical, 2007, 273, 277-283.