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Highly effective MFe2O4 (M=Zn, Mg, Cu and Mn) spinel catalysts for Fischer-Tropsch synthesis

WANG Chao CHEN Jiangang ZHU Huaqing ZHANG Wenshao BAI Hongbin ZHANG Juan

王超, 陈建刚, 朱华青, 张文绍, 白洪彬, 张娟. 高效MFe2O4(M=Zn、Mg、Cu和Mn)尖晶石催化剂应用于费托合成[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(23)60406-2
引用本文: 王超, 陈建刚, 朱华青, 张文绍, 白洪彬, 张娟. 高效MFe2O4(M=Zn、Mg、Cu和Mn)尖晶石催化剂应用于费托合成[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(23)60406-2
WANG Chao, CHEN Jiangang, ZHU Huaqing, ZHANG Wenshao, BAI Hongbin, ZHANG Juan. Highly effective MFe2O4 (M=Zn, Mg, Cu and Mn) spinel catalysts for Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60406-2
Citation: WANG Chao, CHEN Jiangang, ZHU Huaqing, ZHANG Wenshao, BAI Hongbin, ZHANG Juan. Highly effective MFe2O4 (M=Zn, Mg, Cu and Mn) spinel catalysts for Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60406-2

高效MFe2O4(M=Zn、Mg、Cu和Mn)尖晶石催化剂应用于费托合成

doi: 10.1016/S1872-5813(23)60406-2
详细信息
  • 中图分类号: TQ511

Highly effective MFe2O4 (M=Zn, Mg, Cu and Mn) spinel catalysts for Fischer-Tropsch synthesis

Funds: This project was supported by the National Natural Science Foundation of China (22072175), the Chinese Academy of Sciences Strategic Pioneer Special Fund (XDA29030402).
More Information
  • 摘要: 一系列尖晶石催化剂,包括 ZnFe2O4、MgFe2O4、CuFe2O4和MnFe2O4被用于费托合成反应(Fischer-Tropsch synthesis, FTS)。Zn、Mg、Cu和Mn很容易与Fe形成尖晶石。其中,在前处理和反应过程中,Zn和Mg能够显著维持尖晶石结构,使得CO转化率较低。在反应过程中,Cu和Mn有利于碳化铁的生成,导致CuFe2O4和MnFe2O4对FTS性能影响显著。ZnFe2O4对烃分布和C2−C4 烯/烷比影响很小。MgFe2O4的C5+选择性较低,同时由于Mg的碱性作用,从而提高了$ {\mathrm{C}}_2^=-{\mathrm{C}}_4^=$选择性和C2−C4烯/烷比。Cu可以促进催化剂的碳化,从而使CuFe2O4具有较高的活性。同时,CuFe2O4可以显著提高C5+选择性。此外,Cu可以促进H2的解离和活化,从而有利于烯烃的二次加氢,降低$ {\mathrm{C}}_2^=-{\mathrm{C}}_4^=$选择性和C2−C4烯/烷比。虽然Mn在反应过程中会促进催化剂的碳化,但MnFe2O4对碳链的长短影响很小。然而,Mn能促进少量ε-Fe2C的生成,这是导致MnFe2O4具有较高$ {\mathrm{C}}_2^=-{\mathrm{C}}_4^=$选择性和C2−C4烯/烷比的原因。同时,所有尖晶石催化剂都具有较低的二氧化碳选择性,符合当前的绿色环保发展要求。
  • Figure  1  SEM images of as-prepared spinel catalysts

    (a): Fe2O3; (b): ZnFe2O4; (c): MgFe2O4; (d): CuFe2O4; (e): MnFe2O4.

    Figure  2  XRD patterns of as-prepared spinel catalysts

    Figure  3  Mössbauer spectra of as-prepared spinel catalysts

    Figure  4  H2-TPR profiles of the as-prepared catalysts

    Figure  5  Mössbauer spectra of the spent spinel catalysts. The blue and green sextets are assigned to A sites and B sites of spinel or Fe3O4, the magenta, olive and violet sextets are assigned to χ-Fe5C2, the cyan sextet is assigned to ε-Fe2C and the yellow doublet is assigned to superparamagnetic Fe2+ and Fe3+

    Figure  6  Raman spectra of spent catalysts

    Figure  7  FTS performance of spinel catalysts

    (a): CO conversion; (b): CO2 selectivity; (c): CH4 selectivity; (d): C2−C4 selectivity; (e): C5+ selectivity.

    Figure  8  (a) $ {\mathrm{C}}_2^=-{\mathrm{C}}_4^=$ selectivity and (b) the O/P ratio of C2−C4 of as-prepared spinel catalysts

    Table  1  Textural properties of the fresh catalysts

    Catalyst SBET/(m2·g−1) vpa/(cm3·g−1) dpb/nm dc/nm
    Fe2O3 58.65 0.15 8.01 30.00
    ZnFe2O4 41.92 0.13 8.20 11.50
    MgFe2O4 86.35 0.13 4.32 6.20
    CuFe2O4 34.29 0.09 7.63 10.00
    MnFe2O4 90.58 0.14 5.25 8.80
    a: BJH adsorption pore volume; b: BJH adsorption average pore size; c: Crystallite size calculated by Scherrer equation according to XRD.
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出版历程
  • 收稿日期:  2023-09-05
  • 修回日期:  2023-11-06
  • 录用日期:  2023-11-06
  • 网络出版日期:  2024-01-18

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