多级孔道ZSM-5分子筛的合成及其催化应用

doi:10.16085/j.issn.1000-6613.2015.09.016

摘要/Abstract

摘要： 多级孔道ZSM-5分子筛具有微孔沸石分子筛良好的择形催化性能和介孔材料优异的传质扩散性能,在催化领域显示出良好的应用前景。本文综述了近年来多级孔道ZSM-5分子筛的研究进展,重点介绍了多级孔道ZSM-5分子筛的不同合成方法,包括后处理法、硬模板法和软模板法等,同时介绍了不同方法得到的多级孔道ZSM-5分子筛在催化反应中的应用,分析表明多级孔道ZSM-5分子筛以其良好的扩散性能和适宜的酸性提高了反应转化率和目标产物选择性。最后对多级孔道ZSM-5分子筛的发展方向进行了展望,指出研发简单、经济和环保的新合成路线是多级孔道ZSM-5分子筛发展中的重大挑战,深入研究多级孔道分子筛中介孔的形成机理和开发具有多级孔道整体式催化剂以及负载型多级孔道ZSM-5分子筛是今后的研究重点。

关键词: 多级孔道分子筛, ZSM-5, 后处理, 硬模板, 软模板

Abstract: Due to high shape selectivity of microporous zeolite and the excellent mass transport of the mesoporous material,the hierarchical ZSM-5 zeolite has potential applications in catalytic field. The synthesis methods and application progress of hierarchical ZSM-5 zeolite in recent years are reviewed in this paper. Various approaches of hierarchical ZSM-5 zeolite synthesis were introduced,including post-treatment method,hard templating method and soft templating method. In addition,the catalytic applications of the as-synthesized zeolites were discussed. It was demonstrated that the reaction conversion and selectivity of target products were improved due to the excellent mass transport and appropriate acidity of the hierarchical ZSM-5 zeolite. This paper also forecasted the development of the hierarchical ZSM-5 zeolite in chemical industry. It was pointed out that the development of facile,economic and green routes towards the synthesis of hierarchical ZSM-5 zeolite would be a challenge in modern industrial catalysis. Research should focus on the mechanism of the mesopore formation,the development of the hierarchical ZSM-5 monolith zeolite as well as the supported hierarchical ZSM-5 zeolites.

Key words: hierarchical zeolite, ZSM-5, post-treatment, hard template, soft template

中图分类号:

TQ424.25

崔生航, 张君涛, 申志兵. 多级孔道ZSM-5分子筛的合成及其催化应用[J]. 化工进展, 2015, 34(09): 3311-3316,3336.

CUI Shenghang, ZHANG Juntao, SHEN Zhibing. Hierarchical ZSM-5 zeolite: Synthesis and catalytic applications[J]. Chemical Industry and Engineering Progree, 2015, 34(09): 3311-3316,3336.

参考文献

[1] Silaghi Marius-Christian,Chizallet Céline,Raybaud Pascal. Challenges on molecular aspects of dealumination and desilication of zeolites[J]. Microporous and Mesoporous Materials,2014,191:82-96.

[2] Zhang Yicheng,Zhu Kake,Duan Xuezhi,et al. Synthesis of hierarchical ZSM-5 zeolite using CTAB interacting with carboxyl-ended organosilane as a mesotemplate[J]. RSC Adv.,2014,4:14471-14474.

[3] Groen J C,Peffer L A A,Moulijn J A,et al. Mesoporosity development in ZSM-5 zeolite upon optimized desilication conditions in alkaline medium[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2004,241:53-58.

[4] Fathi Sohrab,Sohrabi Morteza,Falamaki Cavus. Improvement of HZSM-5 performance by alkaline treatments:Comparative catalytic study in the MTG reactions[J]. Fuel,2014,116:529-537.

[5] Kumar S,Sinha A K,Hegde S G,et al. Influence of mild dealumination on physicochemical,acidicand catalytic properties of H-ZSM-5[J]. Journal of Molecular Catalysis A:Chemical,2000,154:115-120.

[6] Yuan Enhui,Tang Zhicheng,Mo Zunli,et al. A new method to construct hierarchical ZSM-5 zeolites with excellent catalytic activity[J]. J. Porous Mater.,2014,21:957-965.

[7] Xin Hongchuan,Li Xiangping,Fang Yuan,et al. Catalytic dehydration of ethanol over post-treated ZSM-5 zeolites[J]. Journal of Catalysis,2014,312:204-215.

[8] Schmidt Iver,Madsen Claus,Jacobsen Claus J H. Confined space synthesis:A novel route to nanosized zeolites[J]. Inorg. Chem.,2000,39:2279-2283.

[9] Tao Yousheng,Kanoh H,Hanzawa Y,et al. Template synthesis and characterization of mesoporous zeolites[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2004,241:75-80.

[10] Tao Yousheng,Kanoh Hirofumi,Kaneko Katsumi,et al. ZSM-5 monolith of uniform mesoporous channels[J]. J. Am. Chem. Soc.,2003,125:6044-6045.

[11] Nandan Devaki,Saxena Sandeep K,Viswanadham Nagabhatla. Synthesis of hierarchical ZSM-5 using glucose as a templating precursor[J]. J. Mater. Chem. A,2014,2:1054-1059.

[12] Li Bin,Hu Zhijie,Kong Biao,et al. Hierarchically tetramodal-porous zeolite ZSM-5 monoliths with template-free-derived intracrystalline mesopores[J]. Chem. Sci.,2014,5:1565-1573.

[13] Chu Linlin,Liu Gang,Xiao Qiang. Direct construction of hierarchical ZSM-5 microspheres aided by 3-glycidoxypropyltrimethoxysilane[J]. Materials Research Bulletin,2014,60:746-751.

[14] Serrano D P,Aguado J,Escola J M,et al. Catalytic properties in polyolefin cracking of hierarchical nanocrystalline HZSM-5 samples prepared according to different strategies [J]. Journal of Catalysis,2010,276:152-160.

[15] 王莉,徐义明,陈英才. 3-氨丙基三乙氧基硅烷作用下合成多级孔道ZSM-5分子筛[J]. 工业催化,2014,22(5):346-351.

[16] Zhu Yan,Hua Zile,Zhou Jian,et al. Hierarchical mesoporous zeolites:Direct self-assembly synthesis in a conventional surfactant solution by kinetic control over the zeolite seed formation[J]. Chem. Eur. J.,2011,17:14618-14627.

[17] Zhang Yicheng,Zhu Kake,Duan Xuezhi,et al. Synthesis of hierarchical ZSM-5 zeolite using CTAB interacting with carboxyl-ended organosilane as a mesotemplate[J]. RSC Adv.,2014,4:14471-14474.

[18] Zhang Yicheng,Zhu Kake,Duan Xuezhi,et al. The templating effect of an easily available cationic polymer with widely separated charge centers on the synthesis of a hierarchical ZSM-5 zeolite[J]. J. Mater. Chem. A,2014,2:18666-18676.

[19] Wang Lifeng,Yin Chengyang,Shan Zhichao,et al. Bread-template synthesis of hierarchical mesoporous ZSM-5 zeolite with hydrothermally stable mesoporosity[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2009,340:126-130.

[20] Yin Chengyang,Wei Yijun,Wang Fengwu,et al. Introduction of mesopority in zeolite ZSM-5 using resin as templates[J]. Materials Letters,2013,98:194-196.

[21] Kong Jie,Sheng Xiaoli,Zhou Yuming,et al. Ultrasound-assisted synthesis of nanosized hierarchical ZSM-5 and its catalytic performance as the support for heteropolyacid[J]. J. Porous Mater.,2014,21:241-249.

[22] Yue Yuanyuan,Liu Haiyan,Yuan Pei,et al. From natural aluminosilicate minerals to hierarchical ZSM-5 zeolites:A nanoscale depolymerization-reorganization approach[J]. Journal of Catalysis,2014,319:200-210.

[23] Wang Chunlei,Li Jianfen,Yan Juntao,et al. Investigation on the morphology of hierarchical mesoporous ZSM-5 zeolite prepared by the CO₂-in-water microemulsion method[J]. Korean J. Chem. Eng.,2014,31(9):1547-1552.

[24] 姚军康,陈明高,岳祥龙. 泡沫结构多级孔ZSM-5分子筛的制备与表征[J]. 石油加工:石油学报,2014,30(1):145-150.

[25] Liu Lijia,Wang Hongbin,Wang Runwei,et al. N-Methyl-2-pyrrolidone assisted synthesis of hierarchical ZSM-5 with house-of-cards-like structure[J]. RSC Adv.,2014,4:21301-21305.

[26] Botas J A,Serrano D P,García A,et al. Catalytic conversion of rapeseed oil for the production of raw chemicals,fuels and carbon nanotubes over Ni-modified nanocrystalline and hierarchical ZSM-5[J]. Applied Catalysis B:Environmental,2014,145:205-215.

[27] Schmidt Franz,Lohe Martin R,Büchner Bernd,et al. Improved catalytic performance of hierarchical ZSM-5 synthesized by desilication with surfactants[J]. Microporous and Mesoporous Materials,2013,165:148-157.

[28] Xiao Qiang,Yao Qiongsi,Zhuang Jin,et al. A localized crystallization to hierarchical ZSM-5 microspheres aided by silane coupling agent[J]. Journal of Colloid and Interface Science,2013,394:604-610.

[29] Tao Haixiang,Yang Hong,Liu Xiaohui,et al. Highly stable hierarchical ZSM-5 zeolite with intra-and inter-crystalline porous structures[J]. Chemical Engineering Journal,2013,225:686-694.

[30] Yang Qi,Zhang Haitao,Kong Meng,et al. Hierarchical mesoporous ZSM-5 for the dehydration of methanol to dimethyl ether[J]. Chinese Journal of Catalysis,2013,31:1576-1582.