SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2018, Vol. 26 ›› Issue (4): 768-774.DOI: 10.1016/j.cjche.2017.10.014

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

Influence of Zr, Ce, and La on Co3O4 catalyst for CO2 methanation at low temperature

Yuwen Zhou1, Yuexiu Jiang1, Zuzeng Qin1,2, Qinruo Xie3, Hongbing Ji1,2   

  1. 1 School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004, China;
    2 School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China;
    3 School of Biology and Chemical Engineering, Guangxi University of Science and Technology, Liuzhou 545006, China
  • 收稿日期:2017-07-30 修回日期:2017-07-30 出版日期:2018-04-28 发布日期:2018-05-19
  • 通讯作者: Zuzeng Qin,E-mail addresses:qinzuzeng@gmail.com,qinzuzeng@gxu.edu.cn;Hongbing Ji,E-mail addresses:jihb@mail.sysu.edu.cn
  • 基金资助:

    Supported by the National Natural Science Foundation of China (21366004), Guangxi Natural Science Foundation (2016GXNSFFA380015), the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2016Z003).

Influence of Zr, Ce, and La on Co3O4 catalyst for CO2 methanation at low temperature

Yuwen Zhou1, Yuexiu Jiang1, Zuzeng Qin1,2, Qinruo Xie3, Hongbing Ji1,2   

  1. 1 School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004, China;
    2 School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China;
    3 School of Biology and Chemical Engineering, Guangxi University of Science and Technology, Liuzhou 545006, China
  • Received:2017-07-30 Revised:2017-07-30 Online:2018-04-28 Published:2018-05-19
  • Contact: Zuzeng Qin,E-mail addresses:qinzuzeng@gmail.com,qinzuzeng@gxu.edu.cn;Hongbing Ji,E-mail addresses:jihb@mail.sysu.edu.cn
  • Supported by:

    Supported by the National Natural Science Foundation of China (21366004), Guangxi Natural Science Foundation (2016GXNSFFA380015), the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2016Z003).

摘要: The Co3O4 and Zr-, Ce-, and La-Co3O4catalysts were prepared, characterized, and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140-220℃. The results indicated that the addition of Zr, Ce, or La to the Co3O4 decreased the crystallite sizes of Co and the outer-shell electron density of Co3+, and increased the specific surface area, which would provide more active sites for the CO2 methanation. Especially, the addition of Zr also changed the reducing state of Co3O4 via an obvious change in the interaction between Co3O4 and ZrO2. Furthermore, Zr doped into the Co3O4 increased the basic intensity of the weak and medium basic sites, as well as the amount of Lewis acid sites, and Brønsted acid sites were also found on the Zr-Co3O4 surface. The introduction of Zr, Ce, or La favored the production of CH4, and the Zr-Co3O4 catalyst exhibited the highest CO2 conversion (58.2%) and CH4 selectivity (100%) at 200℃, and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·gcat-1·h-1, and the catalytic activity of CO2 methanation for the Zr-, Ce-, and La-Co3O4 exhibited more stable than Co3O4 in a 20-h reaction.

关键词: CO2 hydrogenation, Methanation, Co3O4 catalyst, Cobalt-zirconium interaction, Basic sites

Abstract: The Co3O4 and Zr-, Ce-, and La-Co3O4catalysts were prepared, characterized, and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140-220℃. The results indicated that the addition of Zr, Ce, or La to the Co3O4 decreased the crystallite sizes of Co and the outer-shell electron density of Co3+, and increased the specific surface area, which would provide more active sites for the CO2 methanation. Especially, the addition of Zr also changed the reducing state of Co3O4 via an obvious change in the interaction between Co3O4 and ZrO2. Furthermore, Zr doped into the Co3O4 increased the basic intensity of the weak and medium basic sites, as well as the amount of Lewis acid sites, and Brønsted acid sites were also found on the Zr-Co3O4 surface. The introduction of Zr, Ce, or La favored the production of CH4, and the Zr-Co3O4 catalyst exhibited the highest CO2 conversion (58.2%) and CH4 selectivity (100%) at 200℃, and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·gcat-1·h-1, and the catalytic activity of CO2 methanation for the Zr-, Ce-, and La-Co3O4 exhibited more stable than Co3O4 in a 20-h reaction.

Key words: CO2 hydrogenation, Methanation, Co3O4 catalyst, Cobalt-zirconium interaction, Basic sites