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水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响

康玉姝 王丽宝 李永志 白金 张财顺 刘道胜 张磊 高志贤

康玉姝, 王丽宝, 李永志, 白金, 张财顺, 刘道胜, 张磊, 高志贤. 水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022074
引用本文: 康玉姝, 王丽宝, 李永志, 白金, 张财顺, 刘道胜, 张磊, 高志贤. 水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022074
KANG Yu-shu, WANG Li-bao, LI Yong-zhi, BAI Jin, ZHANG Cai-shun, LIU Dao-sheng, ZHANG Lei, GAO Zhi-xian. Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022074
Citation: KANG Yu-shu, WANG Li-bao, LI Yong-zhi, BAI Jin, ZHANG Cai-shun, LIU Dao-sheng, ZHANG Lei, GAO Zhi-xian. Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022074

水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响

doi: 10.19906/j.cnki.JFCT.2022074
基金项目: 国家自然科学基金(21673270)和辽宁省教育厅科学研究经费项目(L2019012)资助
详细信息
    通讯作者:

    E-mail: lnpuzhanglei@163.com

    gaozx@lnpu.edu.cn

  • 中图分类号: O643

Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction

Funds: The project was supported by the National Natural Science Foundation of China (21673270); The Scientific Research Funds project of Education Department of Liaoning Province (L2019012)
  • 摘要: 以硝酸盐为铈、锆原料,以柠檬酸代替碱类沉淀剂,固定n(Zr∶Ce)为2∶8,采用水热法合成Ce-Zr氧化物载体,再通过浸渍法制备Cu/Ce-Zr催化剂。通过XRD、BET、H2-TPR、XPS等手段对载体和催化剂进行表征,研究水热时间对催化剂结构、性质和水气变换反应性能的影响。结果表明,催化活性主要与Cu比表面积、CuO的还原温度以及催化剂表面氧空位含量有关。其中,Cu/Ce-Zr-12催化剂的Cu比表面积较大、CuO的还原温度较低,催化剂表面的氧空位数量较多,表现出较好的催化活性。在320 ℃、水气比(WM)为2,体积空速GHSV=6600 h−1的反应条件下,CO转化率为96.9%,与热力学平衡值97.1%接近。
  • 图  1  Ce-Zr-t载体的XRD谱图

    Figure  1  XRD patterns of Ce-Zr-t

    a:CeO2; b: Ce-Zr-6; c: Ce-Zr-9; d: Ce-Zr-12; e: Ce-Zr-15

    图  2  Cu/Ce-Zr-t催化剂的XRD谱图

    Figure  2  XRD patterns of Cu/Ce-Zr-t

    a: Cu/Ce; b: Cu/Ce-Zr-6; c:Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  3  Cu/Ce-Zr-t催化剂的H2-TPR谱图

    Figure  3  H2-TPR spectra of Cu/Ce-Zr-t catalysts

    a: CeO2; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  4  Cu/Ce-Zr-t催化剂的Ce 3d XPS谱图

    Figure  4  Ce 3d XPS spectra of Cu/Ce-Zr-t catalysts

    a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  5  Cu/Ce-Zr-t催化剂的O 1s XPS谱图

    Figure  5  O 1s XPS spectra of Cu/Ce-Zr-t catalysts

    a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  6  Cu/Ce-Zr-t催化剂的Cu 2p XPS谱图

    Figure  6  Cu 2p XPS spectra of Cu/Ce-Zr-t catalysts

    a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  7  Cu/Ce-Zr-t催化剂的Cu LMM XPS谱图

    Figure  7  Cu LMM XPS spectra of Cu/Ce-Zr-t catalysts

    a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

    图  8  Cu/Ce-Zr-t催化剂的Zr 3d XPS谱图

    Figure  8  Zr 3d XPS spectra of Cu/Ce-Zr-t catalysts

    a: Cu/Ce-Zr-6; b: Cu/Ce-Zr-9; c: Cu/Ce-Zr-12; d: Cu/Ce-Zr-15

    图  9  反应温度对催化活性的影响

    Figure  9  Effect of reaction temperature on catalytic activity (reaction conditions: GHSV=6600 h−1, n(H2O)/n(CO)=2∶1, no carrier gas)

    a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15; f: thermodynamic equilibrium

    表  1  Ce-Zr-t和Cu/Ce-Zr-t的物化性质

    Table  1  Physical and chemical properties of Ce-Zr-t and Cu/Ce-Zr-t

    CatalystCell parameters /nmSBET
    /(m2·g−1)
    Pore volume /(mL·g−1)Cu surface areaa /(m2·g−1)
    CeO20.5407523.90.08--
    Ce-Zr-60.5388171.50.13--
    Ce-Zr-90.5401776.80.14--
    Ce-Zr-120.5387569.20.15--
    Ce-Zr-150.5402661.80.10--
    Cu/Ce0.5407321.20.071.5
    Cu/Ce-Zr-60.5387156.90.113.7
    Cu/Ce-Zr-90.5394460.60.124.9
    Cu/Ce-Zr-120.5373258.80.145.5
    Cu/Ce-Zr-150.5392650.20.093.5
    a: determined by N2O experiments
    下载: 导出CSV

    表  2  CuO还原峰位置

    Table  2  Reduction peak positions of CuO

    CatalystPeak position t/℃
    peak αpeak β
    Cu/Ce-Zr-6156182
    Cu/Ce-Zr-9155181
    Cu/Ce-Zr-12144171
    Cu/Ce-Zr-15157189
    下载: 导出CSV

    表  3  催化剂Ce 3d和O 1s的XPS曲线拟合结果

    Table  3  XPS curve fitting results of catalysts Ce 3d and O 1s

    CatalystCe3+/(Ce3+ + Ce4+)/%Oads/(Olat + Oads)/%
    Cu/Ce24.228.2
    Cu/Ce-Zr-621.926.7
    Cu/Ce-Zr-924.428.7
    Cu/Ce-Zr-1228.631.1
    Cu/Ce-Zr-1518.324.5
    下载: 导出CSV
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  • 收稿日期:  2022-06-10
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