Silver modified Cu/SiO2 catalyst for the hydrogenation of methyl acetate to ethanol

doi:10.1016/j.cjche.2020.02.011

中国化学工程学报 ›› 2020, Vol. 28 ›› Issue (6): 1612-1622.DOI: 10.1016/j.cjche.2020.02.011

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol

Zhiheng Ren^1,2,3, Muhammad Naeem Younis³, Hui Zhao³, Chunshan Li^3,4,5, Xiangui Yang^1,2, Erqiang Wang⁶, Gongying Wang^1,2

1 Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China;
2 National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 101408, China;
3 CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, The National Key Laboratory of Clean and Efficient Coking Technology, Beijing Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
4 Zhongke Langfang Institute of Process Engineering, Langfang 065000, China;
5 Zhongke Langfang Institute of Process Engineering, Zhengzhou 450000, China;
6 School of Chemical Science, University of Chinese Academy of Sciences, Beijing 100049, China

收稿日期:2019-07-22 修回日期:2019-12-27 出版日期:2020-06-28 发布日期:2020-07-29
通讯作者: Chunshan Li, Xiangui Yang
基金资助:
We acknowledge Key Research Program of Frontier Sciences, CAS (Grant No. QYZDB -SSW -SLH 022), the National Natural Science Foundation of China -National Research Council of Thailand (NSFC-NRCT,51661145012)and K.C.Wong Education Foundation (GJTD-2582018-04).

Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol

Zhiheng Ren^1,2,3, Muhammad Naeem Younis³, Hui Zhao³, Chunshan Li^3,4,5, Xiangui Yang^1,2, Erqiang Wang⁶, Gongying Wang^1,2

1 Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China;
2 National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 101408, China;
3 CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, The National Key Laboratory of Clean and Efficient Coking Technology, Beijing Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
4 Zhongke Langfang Institute of Process Engineering, Langfang 065000, China;
5 Zhongke Langfang Institute of Process Engineering, Zhengzhou 450000, China;
6 School of Chemical Science, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-07-22 Revised:2019-12-27 Online:2020-06-28 Published:2020-07-29
Contact: Chunshan Li, Xiangui Yang
Supported by:
We acknowledge Key Research Program of Frontier Sciences, CAS (Grant No. QYZDB -SSW -SLH 022), the National Natural Science Foundation of China -National Research Council of Thailand (NSFC-NRCT,51661145012)and K.C.Wong Education Foundation (GJTD-2582018-04).

摘要/Abstract

摘要： A series of silver modified Cu/SiO₂ catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol. The influence of additive ‘Ag’ on the structural evolution of catalyst was systematically studied by several characterization techniques, such as N₂ adsorption-desorption, N₂O titration, PXRD, FTIR, in-situFTIR, H₂-TPR, H₂-TPD, XPS and TEM. Results showed that incorporation of a small amount of Ag could enhance the structural stability, and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu⁺/(Cu⁰ + Cu⁺) ratio, which was proposed to be responsible for the improved catalytic activity. The maximum conversion of MA (94.1%) and selectivity of ethanol (91.3%) over optimized Cu-0.5Ag/SiO₂ and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability.

关键词: Copper, Silver, Hydrogenation, Methyl acetate, Ethanol, Kinetic

Abstract: A series of silver modified Cu/SiO₂ catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol. The influence of additive ‘Ag’ on the structural evolution of catalyst was systematically studied by several characterization techniques, such as N₂ adsorption-desorption, N₂O titration, PXRD, FTIR, in-situFTIR, H₂-TPR, H₂-TPD, XPS and TEM. Results showed that incorporation of a small amount of Ag could enhance the structural stability, and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu⁺/(Cu⁰ + Cu⁺) ratio, which was proposed to be responsible for the improved catalytic activity. The maximum conversion of MA (94.1%) and selectivity of ethanol (91.3%) over optimized Cu-0.5Ag/SiO₂ and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability.

Key words: Copper, Silver, Hydrogenation, Methyl acetate, Ethanol, Kinetic

Zhiheng Ren, Muhammad Naeem Younis, Hui Zhao, Chunshan Li, Xiangui Yang, Erqiang Wang, Gongying Wang. Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol[J]. 中国化学工程学报, 2020, 28(6): 1612-1622.

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Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol

Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol

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