Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

doi:10.1016/j.cjche.2014.06.009

Chinese Journal of Chemical Engineering ›› 2014, Vol. 22 ›› Issue (8): 921-929.DOI: 10.1016/j.cjche.2014.06.009

• 第四届整体式结构化催剂与反应器国际会议专栏 • 上一篇下一篇

Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Wei Deng¹, Xuan He¹, Chao Zhang¹, Yunyi Gao¹, Xuedong Zhu¹, Kake Zhu¹, Qisheng Huo², Zhijie Zhou³

1. College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China;
3. Key Laboratory of Coal Gasification, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

收稿日期:2013-12-24 修回日期:2014-02-21 出版日期:2014-08-28 发布日期:2014-11-04
通讯作者: Kake Zhu
基金资助:
Supported by the National Natural Science Foundation of China (21006024), the CNPC Innovation Foundation (2011D-5006-0507), the Shanghai Pujiang Program (11PJ1402600), the New Century Excellent Talents in University (NCET-11-0644), and the Fundamental Research Funds for the Central Universities (WB1213004-1).

Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Wei Deng¹, Xuan He¹, Chao Zhang¹, Yunyi Gao¹, Xuedong Zhu¹, Kake Zhu¹, Qisheng Huo², Zhijie Zhou³

1. College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China;
3. Key Laboratory of Coal Gasification, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Received:2013-12-24 Revised:2014-02-21 Online:2014-08-28 Published:2014-11-04
Supported by:
Supported by the National Natural Science Foundation of China (21006024), the CNPC Innovation Foundation (2011D-5006-0507), the Shanghai Pujiang Program (11PJ1402600), the New Century Excellent Talents in University (NCET-11-0644), and the Fundamental Research Funds for the Central Universities (WB1213004-1).

摘要/Abstract

摘要： Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assistedcrystallization method is used to synthesize hierarchically porous zeolite ZSM-5 with varied Si/Al malar ratios. X-ray diffraction (XRD), N₂ physisorption, NH₃-temperature programmed desorption (TPD), scanning electronic microscopic (SEM) measurement and Fourier transforminfrared (FT-IR) are employed to characterize the structure and acidity of both hierarchically porous zeolites and their conventional counterparts. The method is found to be applicable to ZSM-5 with molar ratios of Si/Al from 20 to 180. The ZSM-5 zeolites are used as catalysts for benzene methylation at 460℃ to investigate the effect of additional porosity and Si/Al ratios. At low Si/Al ratios, the benzene conversions over conventional and hierarchical ZSM-5 are close, and selectivity to toluene is high over hierarchical ZSM-5. It is found that hierarchical porositymarkedly enhances the utility of zeolite and the selectivity towards xylenes via improved mass transport at higher Si/Al ratios. Under an optimized hierarchical ZSM-5 catalyst, xylene selectivity reaches 34.9% at a Si/Al ratio of 180.

关键词: Hierarchical zeolite, Benzene, Methanol, Methylation, ZSM-5, Process intensification

Abstract: Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assistedcrystallization method is used to synthesize hierarchically porous zeolite ZSM-5 with varied Si/Al malar ratios. X-ray diffraction (XRD), N₂ physisorption, NH₃-temperature programmed desorption (TPD), scanning electronic microscopic (SEM) measurement and Fourier transforminfrared (FT-IR) are employed to characterize the structure and acidity of both hierarchically porous zeolites and their conventional counterparts. The method is found to be applicable to ZSM-5 with molar ratios of Si/Al from 20 to 180. The ZSM-5 zeolites are used as catalysts for benzene methylation at 460℃ to investigate the effect of additional porosity and Si/Al ratios. At low Si/Al ratios, the benzene conversions over conventional and hierarchical ZSM-5 are close, and selectivity to toluene is high over hierarchical ZSM-5. It is found that hierarchical porositymarkedly enhances the utility of zeolite and the selectivity towards xylenes via improved mass transport at higher Si/Al ratios. Under an optimized hierarchical ZSM-5 catalyst, xylene selectivity reaches 34.9% at a Si/Al ratio of 180.

Key words: Hierarchical zeolite, Benzene, Methanol, Methylation, ZSM-5, Process intensification

Wei Deng, Xuan He, Chao Zhang, Yunyi Gao, Xuedong Zhu, Kake Zhu, Qisheng Huo, Zhijie Zhou. Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route[J]. Chinese Journal of Chemical Engineering, 2014, 22(8): 921-929.

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Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

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