Advance in the research and development of methanol to aromatic catalysts

doi:10.16085/j.issn.1000-6613.2016.05.024

Abstract

Abstract: The research and development advance in the reaction mechanism of methanol to aromatics(MTA), the influence of active components (zeolite, dehydrogenation component), modifiers, the preparation methods and deactivity of the MTA catalyst for both the reaction and regeneration processes, is reviewed in this paper. Methanol is conversed to aromatics by two approaches, hydrogen shift and dehydrogenation-cyclization, and the latter could have high aromatic selectivity. The bi-functional catalysts consisted of ZSM-5 zeolite with low Si/Al ratio and dehydrogenation Zn component, exhibit excellent performance in MTA process. Modification of the MTA catalysts with La, P and Si components could improve their hydrothermal stability and selectivity to aromatics or p-xylene (PX). The deactivation of MTA catalysts during the reaction and regeneration processes mainly results from carbon deposition, aggregation and reduction of the dehydrogenation components and hydrothermal removal Al or Ga from the molecular sieve framework. In future, the research and development of the MTA catalysts should be directed to improving hydrothermal stability, increasing the selectivity for high added-value aromatics and developing green preparation process for the catalysts.

Key words: methanol, aromatics, molecular sieve, dehydrogenation component, deactivation

摘要： 系统回顾了甲醇制芳烃(MTA)的反应原理、MTA催化剂的活性组分(沸石与脱氢组分)、修饰组分、制备方法以及MTA催化剂反应-失活研究等方面的研究进展。甲醇可通过氢转移与脱氢环化两种途径转化为芳烃,后一途径可获得更高的芳烃选择性。负载具有脱氢功能的Zn组分、低硅铝比的ZSM-5基催化剂为性能优异的MTA催化剂。La、P及Si等组分的修饰可改善MTA催化剂的水热稳定性、提高其芳烃选择性或对二甲苯(PX)选择性。积炭、脱氢组分聚集、还原及分子筛骨架脱Al(或Ga)是导致MTA催化剂失活的重要因素。最后指出,改善催化剂水热稳定性、提高芳烃收率与高附加值芳烃产品的选择性及实现制备过程的绿色化是未来MTA催化剂开发的重要方向。

关键词: 甲醇, 芳烃, 分子筛, 脱氢组分, 失活

CLC Number:

O643.3

WANG Zheming, CHEN Xiqiang, XU Feng, XIAO Jingxian, YANG Weimin. Advance in the research and development of methanol to aromatic catalysts[J]. Chemical Industry and Engineering Progree, 2016, 35(05): 1433-1439.

汪哲明, 陈希强, 许烽, 肖景娴, 杨为民. 甲醇制芳烃催化剂研究进展[J]. 化工进展, 2016, 35(05): 1433-1439.

References

[1] 刘一心, 杨维军. 芳烃生产技术现状评述[J]. 石油与天然气化工, 2006, 32(1): 23-25.
[2] 祁燕龙, 刘振英, 简书基. 我国对二甲苯产能和市场分析[J]. 河南化工, 2015, 32(4): 7-9.
[3] YI B, WANG Y L, CHEN X, et al. Methanol aromatization over HZSM-5 catalysts modified with different zinc salts[J]. Chin. J. Catal., 2014, 35(10): 1740-1751.
[4] INOUE Y, NAKASHIRO K, ONO Y. Selective conversion of methanol into aromatic hydrocarbons over silver-exchanged ZSM-5 zeolites[J]. Miropor. Mater., 1995, 4(2): 379-383.
[5] ZAIDI H A, PANT K K. Catalytic conversion of methanol to gasoline range hydrocarbons[J]. Catal. Today, 2004, 96(1): 155-160.
[6] 王金英, 李文怀, 胡津仙. ZnHZSM-5上甲醇芳构化反应的研究[J]. 燃料化学学报, 2009, 37(5): 607-612.
[7] ROBERT B, TAMAS B, TIMEA S Z, et al. Aromatization of methanol and methylation of benzene over Mo₂C/ZSM-5 catalysts[J]. J. Catal., 2007, 247(3): 368-378.
[8] 田涛, 骞伟中, 孙玉建, 等. Ag/ZSM-5催化剂上甲醇芳构化过程[J]. 现代化工, 2009, 29(1): 55-58.
[9] 刘维桥, 雷卫宁, 尚通明, 等. Zn对HZSM-5分子筛催化剂甲醇芳构化催化反应性能影响[J]. 化工进展, 2011, 30(9): 1967-1976.
[10] 骞伟中, 魏飞, 魏彤, 等. 一种连续芳构化与催化剂再生的装置及其方法: 101244969A[P]. 2008-08-20.
[11] CONTE M, LOPEZ-SANCHEZ J A, QIAON H, et al. Modified zeolite ZSM-5 for the methanol to aromatics reaction[J]. Catal. Sci. Technol., 2012, 2(1): 105-112.
[12] 李光兴, 李涛, 倪友明, 等. 一种锌同晶取代的纳米分子筛催化剂及其制备方法和应用: 10954291B[P]. 2010-09-26.
[13] 方奕文, 汤吉, 黄晓昌, 等. Zn/H-ZSM-5 催化剂上的二甲醚芳构反应[J]. 催化学报, 2010, 31(3): 264-266.
[14] CHOUDHARY V R, KINAGE A K. Methanol-to-aromatics conversion over H-gallosilicate (MFI): influence of Si/Ga ratio, degree of H⁺ exchange, pretreatment conditions, and poisoning of strong acid sites[J]. Zeolites, 1995, 15: 732-738.
[15] 田涛, 骞伟中, 汤效平, 等. 甲醇芳构化反应中Ag/ZSM-5催化剂的失活特性[J]. 物理化学学报, 2010, 26(12): 3305-3309.
[16] XIN Y B, QI P Y, DUAN X P, et al, Enhanced performance of Zn-Sn/HZSM-5 catalysts for conversion of methanol to aromatics[J]. Catal. Lett., 2013, 143(2): 798-806.
[17] NI Y M, SUN A M, WU X L, et al. Aromatization of methanol over La/Zn/HZSM-5 catalysts[J]. Chin J. Chem. Eng., 2011, 19(3): 439-445.
[18] 高晋升, 张德祥. 甲醇制低碳烯烃的原理及进展[J]. 煤化工, 2006(4): 7-13.
[19] MIKKELSEN Ø, KOLBOE S. The conversion of methanol to hydrocarbons over zeolite H-beta [J]. Micropor. Mesopor. Mater., 1999, 29(2): 173 -184
[20] 钟炳, 罗庆云, 肖有燮, 等. 甲醇在HZSM-5上转化为烃类的催化反应机理[J]. 燃料化学学报, 1986, 14(1): 9-16.
[21] NI Y M, SUN A M, WU X L, et al. The preparation of nano-sized H[Zn, Al]ZSM-5 zeolite and its application in the aromatization of methanol[J]. Micropor. Mesopor. Mater., 2011, 143(2): 435-442.
[22] ROWNAGHI A A, REZAEI F, HEDLUND J. Uniform mesoporous ZSM-5 single crystals catalyst with high resistance to coke formation for methanol deoxygenation[J]. Micropor. Mesopor. Mater., 2012, 151(1): 26-33
[23] BISCARDI J A, MEITZNER G D, IGLESIA E. Structure and density of active Zn species in Zn/H-ZSM5 propane aromatization catalysts[J]. J. Catal., 1998: 179(2): 192-202.
[24] NIU X J, GAO J, MIAO Q, et al. Influence of preparation method on the performance of Zn-containing HZSM-5 catalysts in methanol-to-aromatics[J]. Micropor. Mesopor. Mater., 2014, 197(1): 252-261
[25] WANG F, XIAO W Y, XIAO G M. Atomic layer deposition of zinc oxide on HZSM-5 template and its methanol aromatization performance[J]. Catal. Lett., 2015, 145(2): 860-867.
[26] ZHANG L D, GAO J H, HU J X, et al. Lanthanum oxides-improved catalytic performance of ZSM-5 in toluene alkylationwith methanol[J]. Catal. Lett., 2009, 130(3): 355-361 .
[27] BLASCO T, CORMA A, MARTINEZ-TRIGUERO J. Hydrothermal stabilization of ZSM-5 catalytic-cracking by phosphorus addition[J]. J. Catal., 2006, 237(2)267-277.
[28] LERCHER J A, RUMPLMAYR G. Controlled decrease of acid strength by orthophosphoric acid on ZSM-5[J]. Appl. Catal., 1986, 25(1): 215-222
[29] XUE N H, CHEN X K, NIE L, et al. Understanding the enhancement of catalytic performance for olefin cracking: hydrothermally stable acids in P/HZSM-5[J]. J. Catal., 2007, 248(1): 20-28.
[30] 刘巍, 乔健, 贾臻龙, 等. 磷改性ZSM-5分子筛在甲醇制芳烃反应中催化性能的固体核磁研究[J]. 工业催化, 2012, 21(6): 71-75.
[31] ZHANG J G, QIAN W Z, KONG C Y, et al. Increasing para-xylene selectivity in making aromatics from methanol with a surface-modified Zn/P/ZSM-5 catalyst[J]. ACS Catal., 2015, 5(5): 2982-2988.
[32] MENTZEL U V, HOHJOLT K T, HOLMM S. Conversion of methanol to hydrocarbons over conventional and mesoporous H-ZSM-5 and H-Ga-MFI: major differences in deactivation behavior[J]. Appl. Catal. A: Gen., 2012, 417/418(1): 290-297.