ZSM-11分子筛的碱处理及其正十二烷催化裂解性能

摘要

研究了碱处理对ZSM-11分子筛的微观结构、酸性质和催化裂解性能的影响。采用不同浓度的氢氧化钠对ZSM-11分子筛进行碱处理,得到了级孔ZSM-11分子筛。用XRD,SEM,TEM, NH₃-TPD,N₂低温吸附-脱附等手段对碱处理后的分子筛进行了表征。以正十二烷为模型燃料,在550 ℃、4 MPa的条件下评价了分子筛的催化裂解性能。结果表明,碱处理导致HZSM-11分子筛晶粒内形成介孔、比表面积和酸量增加。碱处理的ZSM-11分子筛表现出较高的催化裂解活性。其中,用浓度为0.1 mol/L的氢氧化钠溶液处理的HZSM-11分子筛,催化活性最高。与未处理的HZSM-11分子筛相比,正十二烷的平均转化率提高了约58%。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	濮思菁
	郝江鸽
	刘国柱
	王莅

关键词： ZSM-11；碱处理；催化裂解

Abstract：

In this paper the effects of alkaline treatment on texture, acid properties and catalytic cracking performance of ZSM-11 zeolites have been studied. Hierarchical ZSM-11 zeolites were prepared by alkali treatment with the different concentration of NaOH solutions. The resulting zeolites were characterized by XRD, SEM, TEM, NH₃-TPD, N₂-adsorpotion/desorpotion and their catalytic performances were evaluated by using catalytic cracking of n-dodecane at 4 MPa and 550 ℃. It is found that alkali treatment on ZSM-11 induced the formation of mesopores in crystals, and increased in the specific surface area and the amount of acid, resulting in the improvement of the conversion of n-dodecane catalytic cracking. The HZSM-11 catalyst obtained by alkaline treatment with 1.0 mol/L NaOH solution exhibited the highest catalytic activity with the enhancement of ca. 58% in the average conversion compared to the untreated HZSM-11zeolite.

Keywords： ZSM-11zeolite； alkaline treatment； catalytic cracking

Received 2014-03-10;

Fund:

国家自然科学基金(90916022和91116001)。

Corresponding Authors: 王莅,E-mail: wlytj@tju.edu.cn。 Email: wlytj@tju.edu.cn

About author: 濮思菁(1989-),女,硕士研究生,从事催化剂制备以及裂解烃类研究。

引用本文:

濮思菁, 郝江鸽, 刘国柱, 王莅.ZSM-11分子筛的碱处理及其正十二烷催化裂解性能[J]. 化学工业与工程, 2015,32(4): 13-18

Pu Sijing, Hao Jiangge, Liu Guozhu, Wang Li.Alkali Treatment of ZSM-11 Zeolite and Performance for Catalytic Cracking of n-Dodecane[J]. Chemcial Industry and Engineering, 2015,32(4): 13-18

[1] 孟凡旭, 赵海龙, 张香文, 等. Pd/HZSM-5涂层催化剂及正十二烷的裂解[J]. 化学工业与工程, 2007, 24 (5): 385-388 Meng Fanxu, Zhao Hailong, Zhang Xiangwen, et al. Preparation of Pd/HZSM-5 film catalyst for cracking of n-dodecane[J]. Chemical Industry and Engineering, 2007, 24(5): 385-388(in Chinese)
[2] Huang H, Spadaccini L J, Sobel D R. Fuel-Cooled thermal management for advanced aeroengines[J]. Journal of Engineering for Gas Turbines and Power, 2004, 126: 284-289
[3] 王莹, 刘国柱, 陈晨, 等. n(硅):n(铝)对HZSM-5分子筛膜催化裂解性能的影响[J]. 化学工业与工程, 2012, 29(5): 1-5 Wang Ying, Liu Guozhu, Chen Chen, et al. Influence of Si/Al ratio on catalytic cracking of n-dodecane over HZSM-5 membranes[J]. Chemical Industry and Engineering, 2012, 29(5): 1-5(in Chinese)
[4] 杨军, 刘秀凤. MFI 型分子筛膜的修复[J]. 化学工业与工程, 2013, 30(6): 1-4 Yang Jun, Liu Xiufeng. Defect healing of MFI zeolite membranes[J]. Chemical Industry and Engineering, 2013, 30(6):1-4(in Chinese)
[5] Na K, Choi M, Ryoo R. Recent advances in the synthesis of hierarchically nanoporous zeolites[J]. Microporous and Mesoporous Materials, 2013, 166: 3-19
[6] Jung J S, Park J W, Seo G. Catalytic cracking of n-octane over alkali-treated MFI zeolites[J]. Applied Catalysis A: General, 2005, 288(1): 149-157
[7] Zhang L, Qu S, Wang L, et al. Preparation and performance of hierarchical HZSM-5 coatings on stainless-steeled microchannels for catalytic cracking of hydrocarbons[J]. Catalysis Today, 2013, 216: 64-70
[8] Yu Q, Cui C, Zhang Q, et al. Hierarchical ZSM-11 with intergrowth structures: Synthesis, characterization and catalytic properties[J]. Journal of Energy Chemistry, 2013, 22(5): 761-768
[9] Na J, Liu G, Zhou T, et al. Synthesis and catalytic performance of ZSM-5/MCM-41 zeolites with varying mesopore size by surfactant-directed recrystallization[J]. Catalysis Letters, 2013, 143(3): 267-275
[10] Kustova M Y, Rasmuusen S B, Kustov A L, et al. Direct NO decomposition over conventional and mesoporous Cu-ZSM-5 and Cu-ZSM-11 catalysts: Improved performance with hierarchical zeolites[J]. Applied Catalysis B: Environmental, 2006, 67(1/2): 60-67
[11] 金文清, 赵国良, 腾加伟, 等. 氢氧化钠改性ZSM-5分子筛的碳四烯烃催化裂解性能[J]. 化学反应工程与工艺, 2007, 23(3): 193-199 Jin Wenqing, Zhao Guoliang, Teng Jiawei, et al. Catalytic performance of ZSM-5 catalyst modified by sodium hydroxide for C₄-olefin cracking[J]. Chemical Reaction Enigineering and Technology, 2007, 23(3): 193-199 (in Chinese)
[12] 张旭, 马新宾. NaY分子筛的脱铝改性[J]. 化学工业与工程, 2007, 24(2): 145-149 Zhang Xu, Ma Xinbin. Dealumination of NaY zeolite[J]. Chemical Industry and Engineering, 2007, 24(2): 145-149 (in Chinese)
[13] Song Y, Zhu X, Song Y, et al. An effective method to enhance the stability on-stream of butene aromatization: Post-treatment of ZSM-5 by alkali solution of sodium hydroxide[J]. Applied Catalysis A: General, 2006, 302(1): 69-77
[14] Meusinger J, Corma A. Influence of zeolite composition and structure on hydrogen transfer reactions from hydrocarbons and from hydrogen[J]. Journal of Catalysis, 1996, 159(2): 353-360
[15] Corma A, Fornes V, Martnez-Triguero J, et al. Delaminated zeolites: Combining the benefits of zeolites and mesoporous materials for catalytic uses[J]. Journal of Catalysis, 1999, 186(1): 57-63