HZSM-5/SAPO-11复合分子筛的制备、 表征及在异丁烷芳构化反应中的催化性能

doi:10.7503/cjcu20160369

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (1): 126.doi: 10.7503/cjcu20160369

HZSM-5/SAPO-11复合分子筛的制备、表征及在异丁烷芳构化反应中的催化性能

张瑞珍^1,²(), 温少波^1,², 邢普^1,², 赵欣^1,², 王志翔^1,², 韩培德^1,², 赵亮富³

1. 太原理工大学材料科学与工程学院
2. 新材料界面科学与工程教育部重点实验室, 太原 030024
3. 中国科学院山西煤炭化学研究所, 太原 030001

收稿日期:2016-05-23 出版日期:2017-01-10 发布日期:2016-12-13
作者简介:联系人简介: 张瑞珍, 女, 博士, 副教授, 主要从事微-介孔材料的制备、表征及催化方面的研究. E-mail: zhangruizhen@tyut.edu.cn
基金资助:
国家自然科学基金(批准号: 51371123)和山西省基础研究项目(批准号: 2014011002-1)资助.

Preparation and Characterization of HZSM-5/SAPO-11 Composite Molecular Sieves and Their Catalytic Properties in Isobutane Aromatization^†

ZHANG Ruizhen^1,^2,^*(), WEN Shaobo^1,², XING Pu^1,², ZHAO Xin^1,², WANG Zhixiang^1,², HAN Peide^1,², ZHAO Liangfu³

1. College of Materials Science and Engineering
2. Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education,Taiyuan University of Technology, Taiyuan 030024, China
3. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Received:2016-05-23 Online:2017-01-10 Published:2016-12-13
Contact: ZHANG Ruizhen E-mail:zhangruizhen@tyut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51371123) and the Basic Research Projects of Shanxi Province, China(No.2014011002-1).

摘要/Abstract

摘要：

将经聚二烯丙基二甲基氯化铵(PDDA)预处理的HZSM-5分子筛置于SAPO-11分子筛的合成母液中, 在水热体系中原位制备了一系列HZSM-5/SAPO-11复合分子筛, 并对分子筛的结构、形貌及酸性进行了表征, 考察了其在异丁烷芳构化反应中的催化性能. 结果表明, 所得复合分子筛由HZSM-5表面包覆约20 nm的SAPO-11微晶组成, 且通过调变SAPO-11的Si含量可以有效调变复合分子筛的酸性, 提高芳构化强弱酸协同催化作用, 有效抑制裂解副反应. 结合异丁烷芳构化转化率及液体收率结果可知, 当SAPO-11合成溶胶中硅铝摩尔比为0.6时, HZSM-5/SAPO-11复合分子筛的芳构化活性及稳定性最佳.

关键词: HZSM-5/SAPO-11复合分子筛, 异丁烷, 芳构化

Abstract:

HZSM-5/SAPO-11 composite molecular sieves with different silicon contents were synthesized hydrothermally via in situ overgrowth of SAPO-11 on ZSM-5 pretreated by polydiallyldimethylammonium chloride(PDDA), and were characterized by means of XRD, SEM, TEM, FTIR and NH₃-TPD. The catalytic activity, stability and BTEX(benzene, toluene, ethylbenzene and xylenes) selectivity of HZSM-5/SAPO-11 in isobutane aromatization were also investigated. All the results were compared with those of ZSM-5, SAPO-11, and the mechanical mixtures of ZSM-5 and SAPO-11 and showed that the ZSM-5/SAPO-11 composites were composed of ZSM-5 covered by about 20 nm SAPO-11 round crystals, that modulation of ZSM-5/SAPO-11 acidity by altering Si content could effectively enhance the synergetic aromatization effect between strong and weak acids and restrain the cracking of iso-butane and the generation of C9⁺, thus the liquid yield and stability of aromatization were superior to HZSM-5 and mechanical mixtures when the Si content reaches 0.6 significantly.

Key words: HZSM-5/SAPO-11 Composite molecular sieve, Isobutane, Aromatization

中图分类号:

O643

TrendMD:

张瑞珍, 温少波, 邢普, 赵欣, 王志翔, 韩培德, 赵亮富. HZSM-5/SAPO-11复合分子筛的制备、表征及在异丁烷芳构化反应中的催化性能. 高等学校化学学报, 2017, 38(1): 126.

ZHANG Ruizhen, WEN Shaobo, XING Pu, ZHAO Xin, WANG Zhixiang, HAN Peide, ZHAO Liangfu. Preparation and Characterization of HZSM-5/SAPO-11 Composite Molecular Sieves and Their Catalytic Properties in Isobutane Aromatization^†. Chem. J. Chinese Universities, 2017, 38(1): 126.

图/表 8

Fig.1 XRD patterns(A) and micro-region XRD patterns(B) of different catalysts a. HZSM-5; b. SAPO-11-0.6; c. MZS-0.6; d. CZS-0.2; e. CZS-0.4; f. CZS-0.6; g. CZS-0.8.

Fig.2 FTIR spectra of different catalystsa. HZSM-5; b. MZS-0.6; c. CZS-0.6; d. SAPO-11-0.6.

Fig.3 SEM[(A)—(D)] and TEM[(E), (F)] images and EDS analysis[(G), (H)] of molecular sieves HZSM-5(A), SAPO-11-0.6(B) and CZS-0.6(C—H)

Fig.4 NH3-TPD spectra of different catalysts(A) a. HZSM-5; b. SAPO-11; c. CZS-0.6; d. MZS-0.6. (B) a. SAPO-11-0.2; b. SAPO-11-0.4; c. SAPO-11-0.8; d. SAPO-11-0.6. (C) a. CZS-0.2; b. CZS-0.4; c. CZS-0.8; d. CZS-0.6.

Fig.5 Isobutane conversions(A) and average liquid yields(B) over different catalysts for 8 h a. HZSM-5; b. CZS-0.2; c. CZS-0.4; d. CZS-0.6; e. CZS-0.8; f. MZS-0.6.

Fig.6 Selectivity of C1, C2 alkanes in the gas hydrocarbon and C5—C9+ in liquid aromatics a. MZS-0.6; b. HZSM-5; c. CZS-0.2; d. CZS-0.4; e. CZS-0.6; f. CZS-0.8.

Fig.7 Conversions of iso-butane aromatization over different catalysts for 32 h(A) a. HZSM-5; b. MZS-0.6; c. CZS-0.6. (B) a. HZSM-5; b. CZS-0.2; c. CZS-0.4; d. CZS-0.6; e. CZS-0.8.

Fig.8 Liquid yields of iso-butane aromatization over different catalysts for 32 h(A) a. HZSM-5; b. MZS-0.6; c. CZS-0.6. (B) a. HZSM-5; b. CZS-0.2; c. CZS-0.4; d. CZS-0.6; e. CZS-0.8.

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HZSM-5/SAPO-11复合分子筛的制备、表征及在异丁烷芳构化反应中的催化性能

Preparation and Characterization of HZSM-5/SAPO-11 Composite Molecular Sieves and Their Catalytic Properties in Isobutane Aromatization^†

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