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过硫酸铵氧化耦合过渡金属氧化物改性炭基催化剂低温SCR性能增强机制研究

肖岭 黄妍 乔淑芳 赵令葵 李思密

肖岭, 黄妍, 乔淑芳, 赵令葵, 李思密. 过硫酸铵氧化耦合过渡金属氧化物改性炭基催化剂低温SCR性能增强机制研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024006
引用本文: 肖岭, 黄妍, 乔淑芳, 赵令葵, 李思密. 过硫酸铵氧化耦合过渡金属氧化物改性炭基催化剂低温SCR性能增强机制研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024006
XIAO Ling, HUANG Yan, QIAO Shufang, ZHAO Lingkui, LI Simi. Study on the enhancement mechanism of low-temperature SCR performance of ammonium persulfate coupled transition metal oxides modified carbon-based catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024006
Citation: XIAO Ling, HUANG Yan, QIAO Shufang, ZHAO Lingkui, LI Simi. Study on the enhancement mechanism of low-temperature SCR performance of ammonium persulfate coupled transition metal oxides modified carbon-based catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024006

过硫酸铵氧化耦合过渡金属氧化物改性炭基催化剂低温SCR性能增强机制研究

doi: 10.19906/j.cnki.JFCT.2024006
基金项目: 湖南省教育厅科研项目(22A0129)和湖南省研究生科研创新项目(CX20230668)资助
详细信息
    通讯作者:

    E-mail: xtuhy@163.com

  • 中图分类号: X701

Study on the enhancement mechanism of low-temperature SCR performance of ammonium persulfate coupled transition metal oxides modified carbon-based catalysts

Funds: The project was supported by Scientific Research Fund of Hunan Provincial Education Department (22A0129) and Postgraduate Scientific Research Innovation Project of Hunan Province (CX20230668).
  • 摘要: 本工作中利用过硫酸铵氧化耦合过渡金属氧化物改性制备V/OAC、Fe/OAC、Mn/OAC、Cu/OAC炭基催化剂,并通过催化活性测试和物理吸附、FT-IR、XPS、NH3-TPD、H2-TPR、EPR等表征手段探究改性炭基催化剂的低温SCR性能增强机制。结果表明,过硫酸铵氧化可向活性炭载体表面引入大量酸性含氧官能团,促进过渡金属氧化物中的氧空位形成,从而提升炭基催化剂的表面酸度和氧化还原性能,进而提升了炭基催化剂低温NH3-SCR性能。本工作发现,过硫酸铵氧化可诱导过渡金属元素(V、Fe、Mn、Cu)的低价态形成。因此,过硫酸铵氧化改性后,活性组分中低价态金属利于NH3-SCR反应的V/OAC、Fe/OAC催化剂性能提升显著,VOx/OAC和FeOx/OAC催化剂在100 ℃下的NO转化率分别从18.2%提升到34.8%和从34.2%提升到55.6%;而活性组分中高价态金属有利NH3-SCR反应的Mn/OAC和Cu/OAC催化剂性能提升有限,100 ℃下的NO转化率仅从61.4%提升到70.4%和61.3%提升到69.7%。本工作总结了过硫酸铵氧化改性对炭基催化剂表面金属价态的调控作用,有助于深入认识过硫酸铵氧化改性对炭基催化剂物化性质的调控规律,为高效炭基脱硝催化剂的开发提供指导和参考。
  • 图  1  MOx/AC和MOx/OAC(M=V、Fe、Mn、Cu)NH3-SCR脱硝性能

    Figure  1  MOx/AC and MOx/OAC (M=V, Fe, Mn, Cu) NH3-SCR denitration performance test Reaction Conditions: 0.05%NO, 0.05%NH3, 5%O2, 5%H2O ,N2 as balance, flow rate=360 mL/min, GHSV=24000 h−1.

    图  2  M/AC和M/OAC(M=V、Fe、Mn、Cu)NH3-SCR的抗硫抗水性能

    Figure  2  Test of sulfur and water resistance of M/AC and M/OAC (M=V, Fe, Mn, Cu) NH3-SCR Reaction Conditions: 0.05%NO, 0.05%NH3, 5%O2, 5%H2O, 0.02%SO2, N2 as balance, flow rate=360 mL/min, GHSV=24000 h−1.

    图  3  AC和OAC的(a) FT-IR光谱图 (b) XPS总谱图 (c) XPS的C 1s谱图

    Figure  3  (a) FT-IR spectra (b) XPS total spectra (c) C 1s spectra of XPS of AC and OAC

    图  4  催化剂的XPS谱图(a)V 2p (b)Fe 2p (c)Mn 2p (d)Cu 2p

    Figure  4  (a)V 2p(b)Fe 2p(c)Mn 2p(d)Cu 2p spectrum of catalyst XPS

    图  5  催化剂的XPS O 1s谱图

    Figure  5  O 1s spectrum of catalyst XPS

    图  6  催化剂的EPR谱图

    Figure  6  EPR spectrum of catalyst

    图  7  催化剂的NH3-TPD谱图(a)和H2-TPR谱图(b)

    Figure  7  NH3-TPD spectra (a) and H2-TPR spectra (b) of catalysts

    表  1  催化剂的比表面积以及孔容和孔径

    Table  1  Catalyst specific surface area and pore volume aperture

    Sample BET surface area/(m2·g−1) Cumulitive pore volume/(cm3·g−1) Pore size/
    nm
    VOx/AC 824 0.45 2.18
    VOx/OAC 760 0.42 2.22
    FeOx/AC 689 0.30 3.83
    FeOx/OAC 602 0.29 3.81
    MnOx/AC 803 0.44 2.53
    MnOx/OAC 635 0.34 2.49
    CuOx/AC 811 0.44 2.62
    CuOx/OAC 657 0.36 2.52
    下载: 导出CSV

    表  2  催化剂的总酸量

    Table  2  Total acid content of catalyst

    Sample V/AC V/OAC Fe/AC Fe/OAC Mn/AC Mn/OAC Cu/AC Cu/OAC
    Total acid
    (μmol·g−1)
    379.2 577.6 523.7 746.3 1190.7 1478.8 1325.3 1721.4
    下载: 导出CSV
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  • 收稿日期:  2023-12-29
  • 修回日期:  2024-02-28
  • 录用日期:  2024-02-29
  • 网络出版日期:  2024-04-01

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