SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2022, Vol. 43 ›› Issue (3): 77-85.DOI: 10.1016/j.cjche.2022.01.017

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Highly dispersed nickel boosts catalysis by Cu/SiO2 in the hydrogenation of CO2-derived ethylene carbonate to methanol and ethylene glycol

Youwei Yang1, Jingyu Zhang1, Yueqi Gao1, Busha Assaba Fayisa1, Antai Li1, Shouying Huang1,2, Jing Lv1, Yue Wang1,2, Xinbin Ma1,2   

  1. 1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
    2. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China
  • Received:2021-09-04 Revised:2022-01-13 Online:2022-04-28 Published:2022-03-28
  • Contact: Jing Lv,E-mail:muddylj@tju.edu.cn
  • Supported by:
    We are grateful for the supports from the National Natural Science Foundation of China (22022811, U21B2096 and 21938008) and the National Key Research & Development Program of China (2018YFB0605803).

Highly dispersed nickel boosts catalysis by Cu/SiO2 in the hydrogenation of CO2-derived ethylene carbonate to methanol and ethylene glycol

Youwei Yang1, Jingyu Zhang1, Yueqi Gao1, Busha Assaba Fayisa1, Antai Li1, Shouying Huang1,2, Jing Lv1, Yue Wang1,2, Xinbin Ma1,2   

  1. 1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
    2. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China
  • 通讯作者: Jing Lv,E-mail:muddylj@tju.edu.cn
  • 基金资助:
    We are grateful for the supports from the National Natural Science Foundation of China (22022811, U21B2096 and 21938008) and the National Key Research & Development Program of China (2018YFB0605803).

Abstract: The efficient hydrogenation of CO2-derived ethylene carbonate (EC) to yield methanol (MeOH) and ethylene glycol (EG) is a key process for indirect conversion of CO2 to MeOH. However, a high H2/EC molar ratio during the hydrogenation process (usually as 180–300) is generally required to achieve good catalytic performance, resulting in high cost and energy consumption for H2 circulation in the promising industrial application. Here, we prepared a series of Ni-modified Cu/SiO2 catalysts and explored the effects of synthesis methods and Ni contents on catalytic performance under different H2/EC molar ratios. The Cu/SiO2 catalyst with 0.2% (mass) Ni loading prepared by co-ammonia evaporation method exhibited above 99% conversion of EC, 91% and 98% selectivity to MeOH and EG respectively at H2/EC ratio of 60. And no significant deactivation was observed within 140 h at a lower H2/EC of 40. It is demonstrated that a few of Ni addition could not only promote Cu dispersion and increase surface Cu+ species due to the strong interaction between Cu and Ni species, but also form uniformly-dispersed CuNi alloy species and thus enhance the adsorption and dissociation of H2. But the excess Ni species would aggregate and segregate to cover partial surface of Cu nanoparticles, leading to a significantly drop of catalytic performance in EC hydrogenation. These insights may provide guidance for further design of catalysts for the ester hydrogenation reactions.

Key words: Cu-based catalyst, Ethylene carbonate, Methanol, Hydrogenation, Carbon dioxide

摘要: The efficient hydrogenation of CO2-derived ethylene carbonate (EC) to yield methanol (MeOH) and ethylene glycol (EG) is a key process for indirect conversion of CO2 to MeOH. However, a high H2/EC molar ratio during the hydrogenation process (usually as 180–300) is generally required to achieve good catalytic performance, resulting in high cost and energy consumption for H2 circulation in the promising industrial application. Here, we prepared a series of Ni-modified Cu/SiO2 catalysts and explored the effects of synthesis methods and Ni contents on catalytic performance under different H2/EC molar ratios. The Cu/SiO2 catalyst with 0.2% (mass) Ni loading prepared by co-ammonia evaporation method exhibited above 99% conversion of EC, 91% and 98% selectivity to MeOH and EG respectively at H2/EC ratio of 60. And no significant deactivation was observed within 140 h at a lower H2/EC of 40. It is demonstrated that a few of Ni addition could not only promote Cu dispersion and increase surface Cu+ species due to the strong interaction between Cu and Ni species, but also form uniformly-dispersed CuNi alloy species and thus enhance the adsorption and dissociation of H2. But the excess Ni species would aggregate and segregate to cover partial surface of Cu nanoparticles, leading to a significantly drop of catalytic performance in EC hydrogenation. These insights may provide guidance for further design of catalysts for the ester hydrogenation reactions.

关键词: Cu-based catalyst, Ethylene carbonate, Methanol, Hydrogenation, Carbon dioxide