SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2024, Vol. 66 ›› Issue (2): 273-284.DOI: 10.1016/j.cjche.2023.09.012

• Full Length Article • 上一篇    下一篇

Pre-reduction of WO3–Co3O4 by H2–C2H4 in a fluidized bed

Huijun Shang1,2, Hengli Li1,3, Weijun Li3, Feng Pan1,4, Zhan Du5   

  1. 1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences (CAS), Beijing 100190, China;
    2. College of Chemical Engineering, Nanjing Technology University, Nanjing 211816, China;
    3. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
    4. College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
    5. Chinalco Environmental Protection and Energy Conservation Group Co., Ltd., Xiong’an 071700, China
  • 收稿日期:2023-01-17 修回日期:2023-08-26 出版日期:2024-02-28 发布日期:2024-04-20
  • 通讯作者: Feng Pan,E-mail:fpan@ipe.ac.cn;Zhan Du,E-mail:duyinyi2008823@126.com
  • 基金资助:
    The authors wish to gratefully acknowledge financial support from the National Natural Science Foundation of China (22078326, 21878305 and 21908227).

Pre-reduction of WO3–Co3O4 by H2–C2H4 in a fluidized bed

Huijun Shang1,2, Hengli Li1,3, Weijun Li3, Feng Pan1,4, Zhan Du5   

  1. 1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences (CAS), Beijing 100190, China;
    2. College of Chemical Engineering, Nanjing Technology University, Nanjing 211816, China;
    3. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
    4. College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
    5. Chinalco Environmental Protection and Energy Conservation Group Co., Ltd., Xiong’an 071700, China
  • Received:2023-01-17 Revised:2023-08-26 Online:2024-02-28 Published:2024-04-20
  • Contact: Feng Pan,E-mail:fpan@ipe.ac.cn;Zhan Du,E-mail:duyinyi2008823@126.com
  • Supported by:
    The authors wish to gratefully acknowledge financial support from the National Natural Science Foundation of China (22078326, 21878305 and 21908227).

摘要: In order to avoid the formation of η phase (W6Co6C or W3Co3C) that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder, a technical route of pre-reduction of WO3–Co3O4 to WO2–Co and then deep reduction carbonization to WC-Co powder has been proposed. This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO3–Co3O4 under a mixed atmosphere of H2–C2H4–Ar at 600°Cand establishes the kinetic equations of pre-reduction and carbon evolution. The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO3 to WO2. High carbon content can be generated by the deposition of C2H4, and it hinders the diffusion of the reducing gas; WO3 still cannot be completely reduced to WO2 as the partial pressure of C2H4 increases to 60 %. For the carbon evolution of C2H4, the carbon amount is positively related to the H2 partial pressure, but it shows the highest amount and evolution rate when the ethylene partial pressure is 20 %. Based on the reduction rate curves of WO3 and carbon evolution rate curves of C2H4, the rate equations of pre-reduction and carbon evolution of WO3–Co3O4 system at 600°C are established. The pre-reduction reaction belongs to the first-order reaction, and its equation is expressed as follows:The carbon deposition rate equation of C2H4 can be expressed as follows:

关键词: Fluidization, WO3–Co3O4, Reduction, Carbon deposition, Rate equation

Abstract: In order to avoid the formation of η phase (W6Co6C or W3Co3C) that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder, a technical route of pre-reduction of WO3–Co3O4 to WO2–Co and then deep reduction carbonization to WC-Co powder has been proposed. This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO3–Co3O4 under a mixed atmosphere of H2–C2H4–Ar at 600°Cand establishes the kinetic equations of pre-reduction and carbon evolution. The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO3 to WO2. High carbon content can be generated by the deposition of C2H4, and it hinders the diffusion of the reducing gas; WO3 still cannot be completely reduced to WO2 as the partial pressure of C2H4 increases to 60 %. For the carbon evolution of C2H4, the carbon amount is positively related to the H2 partial pressure, but it shows the highest amount and evolution rate when the ethylene partial pressure is 20 %. Based on the reduction rate curves of WO3 and carbon evolution rate curves of C2H4, the rate equations of pre-reduction and carbon evolution of WO3–Co3O4 system at 600°C are established. The pre-reduction reaction belongs to the first-order reaction, and its equation is expressed as follows:The carbon deposition rate equation of C2H4 can be expressed as follows:

Key words: Fluidization, WO3–Co3O4, Reduction, Carbon deposition, Rate equation