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钴基FT合成催化剂中原子碳物种的作用研究

杨胜龙 王俊刚 马中义 陈从标 刘岩 张伟 解启龙 侯博

杨胜龙, 王俊刚, 马中义, 陈从标, 刘岩, 张伟, 解启龙, 侯博. 钴基FT合成催化剂中原子碳物种的作用研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024017
引用本文: 杨胜龙, 王俊刚, 马中义, 陈从标, 刘岩, 张伟, 解启龙, 侯博. 钴基FT合成催化剂中原子碳物种的作用研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024017
YANG Shenglong, WANG Jungang, MA Zhongyi, CHEN Congbiao, LIU Yan, ZHANG Wei, XIE Qilong, HOU Bo. Study on the role of atomic carbon species in cobalt-based FT synthesis catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024017
Citation: YANG Shenglong, WANG Jungang, MA Zhongyi, CHEN Congbiao, LIU Yan, ZHANG Wei, XIE Qilong, HOU Bo. Study on the role of atomic carbon species in cobalt-based FT synthesis catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024017

钴基FT合成催化剂中原子碳物种的作用研究

doi: 10.19906/j.cnki.JFCT.2024017
基金项目: 山西省研究计划(202103021224444,202102090301003)和国家自然科学基金(22179136,22279155,22208361)资助
详细信息
    通讯作者:

    Tel: 13934595876, E-mail: wangjg@sxicc.ac.cn

  • 中图分类号: O643

Study on the role of atomic carbon species in cobalt-based FT synthesis catalyst

Funds: The project was supported by the Research Program of Shanxi Province(202103021224444, 202102090301003) and National Natural Science Foundation of China(22179136, 22279155, 22208361).
  • 摘要: 费托合成是将合成气催化转化为长链重质烃的工艺过程。在此过程中,CO活化、歧化反应以及烃类脱氢反应都可以在催化剂表面形成碳物种,而碳物种对费托反应的作用一直存在争议。本工作通过对主要暴露面为HCP-Co(10-11)的单晶钴进行不同条件的预处理,成功构建了具有不同含量原子碳物种的模型催化剂,并采用程序升温加氢、拉曼光谱和红外光谱等表征手段对催化剂中的原子碳物种含量和存在形式进行分析。结果表明,在引入原子碳物种后,钴基催化剂的活性和CH4选择性与原子碳物种数量和存在形式密切相关。含碳量为5.72%的P-Co-C3催化剂具有较高的CO转化率,可达72.2%;而含碳量为3.01%的P-Co-C2催化剂具有较低的CH4选择性,仅为4.2%。此外,表征结果进一步证明该原子碳物种是以C(无定形碳)和CxHy两种形式共存,其在反应过程中可能参与了FT反应,进而提升其反应性能。
  • 图  1  不同含碳量催化剂的FT反应性能

    Figure  1  FT reaction performance of catalyst with different carbon content

    (a): CO conversion and methane selectivity at the same temperature; (b): Methane selectivity and reaction temperature at 30−40%CO conversion.

    图  2  催化剂的XRD谱图

    Figure  2  XRD patterns of catalysts

    图  3  不同含碳量催化剂的TPH谱图

    Figure  3  TPH spectra of catalysts with different carbon content

    图  4  不同含碳量催化剂的漫反射红外光谱谱图

    Figure  4  Diffuse reflection infrared spectra of catalysts with different carbon content

    图  5  合成气(H2/CO=2)下P-Co催化剂的原位拉曼谱图

    Figure  5  In-situ Raman spectra of P-Co catalyst in syngas (H2/CO=2) atmosphere

    图  6  不同含碳量P-Co催化剂的C 1s XPS谱图

    Figure  6  C 1s XPS spectra of P-Co catalysts with different carbon content

    图  7  不同处理时间下的TPH-MS谱图

    Figure  7  TPH-MS spectra of catalysts with different treatment times

    图  8  C−Co和C−Co−C催化剂的XRD谱图

    Figure  8  XRD spectra of pretreated catalysts C−Co and C−Co−C

    图  9  C−Co−C催化剂的TPH谱图

    Figure  9  TPH profiles for the C−Co−C catalyst

    图  10  C−Co和C−Co−C催化剂的FT反应性能比较:30%−40%CO转化率下的CH4选择性和反应温度

    Figure  10  Comparison of FT reaction properties of C−Co and C−CO−C catalysts: CH4 selectivity and reaction temperature at 30%−40% CO conversion

    表  1  催化剂的费托反应性能

    Table  1  FT reaction performance of catalyst

    Catalyst C/% Temperature/℃ CO conversion/% Product selectivity/%
    CH4 C2-C4 C5+
    P-Co 0.00 220 28.0 9.8 13.1 77.2
    P-Co-C1 2.76 220 36.0 8.1 25.3 66.6
    P-Co-C2 3.01 220 45.7 6.0 18.7 75.3
    P-Co-C3 5.72 220 72.2 13.0 23.7 63.4
    P-Co-C4 14.12 220 29.5 14.7 34.4 50.9
    Reaction conditions:H2/CO=2, p=2 MPa, GHSV=1000 h−1, TOS=48 h.
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出版历程
  • 收稿日期:  2024-02-27
  • 修回日期:  2024-03-30
  • 录用日期:  2024-04-01
  • 网络出版日期:  2024-05-10

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