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

doi:10.1016/j.cjche.2023.09.012

Chinese Journal of Chemical Engineering ›› 2024, Vol. 66 ›› Issue (2): 273-284.DOI: 10.1016/j.cjche.2023.09.012

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

Huijun Shang^1,2, Hengli Li^1,3, Weijun Li³, Feng Pan^1,4, Zhan Du⁵

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:2024-04-20 Published:2024-02-28
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).

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

Huijun Shang^1,2, Hengli Li^1,3, Weijun Li³, Feng Pan^1,4, Zhan Du⁵

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

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).

Abstract

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

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

Huijun Shang, Hengli Li, Weijun Li, Feng Pan, Zhan Du. Pre-reduction of WO₃–Co₃O₄ by H₂–C₂H₄ in a fluidized bed[J]. Chinese Journal of Chemical Engineering, 2024, 66(2): 273-284.

Huijun Shang, Hengli Li, Weijun Li, Feng Pan, Zhan Du. Pre-reduction of WO₃–Co₃O₄ by H₂–C₂H₄ in a fluidized bed[J]. 中国化学工程学报, 2024, 66(2): 273-284.

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

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

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