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Cu-Ni-Al尖晶石催化甲醇重整制氢:Al含量的影响

刘雅杰,  康荷菲,  侯晓宁,  张磊,  庆绍军,  高志贤,  相宏伟

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文章导航 > 燃料化学学报（中英文）  > 2020 >  48(9): 1112-1121
刘雅杰, 康荷菲, 侯晓宁, 张磊, 庆绍军, 高志贤, 相宏伟. Cu-Ni-Al尖晶石催化甲醇重整制氢:Al含量的影响[J]. 燃料化学学报（中英文）, 2020, 48(9): 1112-1121.
引用本文: 刘雅杰, 康荷菲, 侯晓宁, 张磊, 庆绍军, 高志贤, 相宏伟. Cu-Ni-Al尖晶石催化甲醇重整制氢:Al含量的影响[J]. 燃料化学学报（中英文）, 2020, 48(9): 1112-1121.
shu
LIU Ya-jie, KANG He-fei, HOU Xiao-ning, ZHANG Lei, QING Shao-jun, GAO Zhi-xian, XIANG Hong-wei. Cu-Ni-Al spinel catalyzed methanol steam reforming for hydrogen production: Effect of Al content[J]. Journal of Fuel Chemistry and Technology, 2020, 48(9): 1112-1121.
Citation: LIU Ya-jie, KANG He-fei, HOU Xiao-ning, ZHANG Lei, QING Shao-jun, GAO Zhi-xian, XIANG Hong-wei. Cu-Ni-Al spinel catalyzed methanol steam reforming for hydrogen production: Effect of Al content[J]. Journal of Fuel Chemistry and Technology, 2020, 48(9): 1112-1121.
shu

Cu-Ni-Al尖晶石催化甲醇重整制氢:Al含量的影响

  • 1.

    晋中学院 化学化工学院, 山西 晋中 030619

  • 2.

    中国科学院 山西煤炭化学研究所, 山西 太原 030001

  • 3.

    辽宁石油化工大学 石油化工学院, 辽宁 抚顺 113001

  • 4.

    中国科学院洁净能源创新研究院, 辽宁 大连 116011

基金项目: 

国家自然科学基金面上项目 21673270

山西省高等学校科技创新项目 2019L0880

晋中学院博士科研经费 2019

中国科学院洁净能源创新研究院合作基金项目 DNL201908

详细信息

  • 中图分类号: O643

Cu-Ni-Al spinel catalyzed methanol steam reforming for hydrogen production: Effect of Al content

  • 1.

    College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030619, China

  • 2.

    Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

  • 3.

    School of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China

  • 4.

    Dalian National Laboratory for Clean Energy, Dalian 116011, China

Funds: 

the National Natural Science Foundation of China 21673270

Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi 2019L0880

Ph. D. Research Funding of Jinzhong University 2019

DNL Cooperation Fund DNL201908

More Information

    摘要
  • 摘要: 采用固相球磨法制备了Al含量不等的Cu-Ni-Al三元尖晶石固溶体催化剂，通过BET、XRD、H2-TPR、XPS表征和催化性能评价，研究了Al含量对Cu-Ni-Al尖晶石的物化性质和甲醇制氢缓释催化性能的影响。结果表明，恒定Cu：Ni（molar ratio）=0.95：0.05，增加Al含量时（Al=2、3、4），所得催化剂的比表面积和孔体积都明显增大，且尖晶石晶胞常数和晶粒尺寸均减小，催化剂也变得难以还原。进一步研究发现，随着Al含量增加，尖晶石Ni2+含量略微增加，但尖晶石Cu2+含量大幅降低，因此，尖晶石结构中Cu2+和Ni2+的总量降低，表明Ni2+的存在抑制了Cu2+进入尖晶石结构。表面分析结果证实，Al含量增加导致催化剂表面由富Cu转变为富Al，表层尖晶石Cu2+含量降低，但仍高于体相含量。评价结果显示，随着Al含量增加，反应初始活性增大，CO选择性降低，但Al过量太多时催化稳定性降低，综合来说，Al=3的催化剂表现出较好的催化性能。结果表明，对于Cu-Ni-Al尖晶石缓释催化剂，存在最佳Al含量，对催化稳定性起到关键作用。
    Abstract: Cu-Ni-Al ternary spinel solid solution catalysts with different Al content are prepared by the solid-phase ball milling method. The characterizations with XRD, H2-TPR, BET and XPS, and catalytic performance testing are carried out to study the effects of Al content on the physicochemical properties of the Cu-Ni-Al spinels and their sustained release catalytic performances in methanol steam reforming for hydrogen production. Characterization results show a significant increase in the specific surface area and pore volume of the catalysts with increasing the Al content (Al = 2, 3, 4) at a constant Cu/Ni molar ratio of 0.95:0.05. At the same time, both the cell parameters and crystallite sizes of Cu-Ni-Al spinel solid solutions decrease, and the catalysts become difficult to be reduced. Furthermore, the content of spinel Ni2+ increases slightly while the spinel Cu2+ decreases significantly, leading to a declined total content of spinel Cu2+ plus Ni2+. The results also indicate that the presence of Ni2+ inhibits the formation of spinel Cu2+. Surface analysis results show that the increase of Al content transforms the catalyst surface composition from Cu-rich to Al-rich, and the surface spinel Cu2+ decreases, but it is still higher than the spinel bulk. The catalyst testing results show that as the Al content in the catalysts increases, the initial activity increases notably, and the CO selectivity decreases, but too much Al results in an inferior catalytic stability. In general, the catalyst with an Al = 3 shows a better catalytic performance in terms of activity and stability. The results of this paper demonstrate that there is an optimal Al content for the Cu-Ni-Al spinel solid solutions used as the sustained release catalysts, playing a crucial role in obtaining high catalytic stability.
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    图  1  催化剂C0.95N0.05Ax(x = 2、3、4)的吸附等温曲线

    Figure  1  Adsorption-desorption isotherms of C0.95N0.05Ax(x = 2, 3, 4) catalysts

    下载: 全尺寸图片 幻灯片

    图  2  催化剂C0.95N0.05Ax(x = 2、3、4)的孔径分布

    Figure  2  Pore size distributions of C0.95N0.05Ax(x = 2, 3, 4) catalysts

    下载: 全尺寸图片 幻灯片

    图  3  C0.95N0.05Ax(x = 2、3、4)及对比样的XRD谱图

    Figure  3  XRD patterns of C0.95N0.05Ax(x = 2, 3, 4) and the reference samples

    a: CA2; b: C0.95N0.05A2; c: C0.95N0.05A3; d: C0.95N0.05A4; e: NA2; f: CuAl2O4

    下载: 全尺寸图片 幻灯片

    图  4  C0.95N0.05Ax(x = 2、3、4)及对比样中尖晶石440晶面的XRD放大谱图

    Figure  4  Enlarged XRD peaks of spinel 440 plane in C0.95N0.05Ax (x = 2, 3, 4) and the reference samples

    a: CA2; b: C0.95N0.05A2; c: C0.95N0.05A3; d: C0.95N0.05A4; e: NA2; f: CuAl2O4; g: γ-Al2O3

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    图  5  C0.95N0.05Ax(x = 2、3、4)及对比样的H2-TPR谱图

    Figure  5  H2-TPR profiles of C0.95N0.05Ax(x = 2, 3, 4) and the reference samples

    a: CA2; b: C0.95N0.05A2; c: C0.95N0.05A3; d: C0.95N0.05A4; e: NA2

    下载: 全尺寸图片 幻灯片

    图  6  C0.95N0.05Ax(x = 2、3、4)及对比样的还原程度

    Figure  6  Reduction degree profiles of C0.95N0.05Ax(x = 2, 3, 4) and the reference samples

    a: CA2; b: C0.95N0.05A2; c: C0.95N0.05A3; d: C0.95N0.05A4; e: NA2

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    图  7  催化剂C0.95N0.05Ax(x = 2、3、4)的XPS谱图

    Figure  7  XPS spectra of the C0.95N0.05Ax(x = 2, 3, 4) catalysts

    (a) Cu 2p3/2; (b) Al 2p; (c) Ni 2p3/2; a: C0.95N0.05A2; b: C0.95N0.05A3; c: C0.95N0.05A4

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    图  8  C0.95N0.05Ax(x = 2、3、4)催化剂上的甲醇转化速率

    Figure  8  CH3OH conversion rate in MSR over C0.95N0.05Ax(x = 2, 3, 4) catalysts

    下载: 全尺寸图片 幻灯片

    图  9  催化剂C0.95N0.05Ax(x = 2、3、4)在甲醇重整制氢反应中的CO选择性

    Figure  9  CO selectivity in MSR over C0.95N0.05Ax(x = 2, 3, 4) catalysts

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    图  10  C0.95N0.05A2及其再生催化剂C0.95N0.05A2-R的甲醇转化率对比

    Figure  10  Comparison of CH3OH conversion in MSR between the C0.95N0.05A2 and regenerated catalyst C0.95N0.05A2-R

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    图  11  C0.95N0.05A2及其再生催化剂C0.95N0.05A2-R的CO选择性对比

    Figure  11  Comparison of CO selectivity in MSR between the C0.95N0.05A2 and regenerated catalyst C0.95N0.05A2-R

    下载: 全尺寸图片 幻灯片

    表  1  催化剂C0.95N0.05Ax(x = 2、3、4)的织构性质

    Table  1  Texture properties of C0.95N0.05Ax(x = 2, 3, 4) catalysts

    Sample C0.95N0.05A2 C0.95N0.05A3 C0.95N0.05A4
    S /(m2·g-1)[a] 30.9 42.2 69.0
    v/(cm2·g-1)[b] 0.223 0.291 0.386
    d/nm[c] 28.9 27.6 22.4
    [a]: catalyst surface areas; [b]: catalyst volumes; [c]: average pore sizes
    下载: 导出CSV

    表  2  C0.95N0.05Ax(x = 2、3、4)及对比样的物化性质

    Table  2  Physicochemical properties of C0.95N0.05Ax(x = 2, 3, 4) and the reference samples

    Sample CA2 C0.95N0.05A2 C0.95N0.05A3 C0.95N0.05A4 NA2
    a/nm[a] 0.8065 0.8063 0.8049 0.8040 0.8045
    dspinel/nm[b] 17.1 22.8 11.0 9.0 8.2
    X(spinel Cu2+)/%[c] 81.2 77.4 75.8 67.4 -
    X(non-spinel Cu2+)/%[c] 18.8 17.6 19.2 27.6 -
    X(spinel Ni2+)/%[c] - 3.5 3.6 4.3 72.4
    X(non-spinel Ni2+)/%[c] - 1.5 1.4 0.7 27.6
    X(spinel Cu2+ and Ni2+)/%[c] 81.2 80.9 79.4 71.7 72.4
    X(hardly-reducible spinel Cu2+)/%[d] 7.2 4.7 18.8 27.0 -
    [a]: the cell parameters of spinel phases; [b]: the crystallite sizes of spinel phases; [c]: the molar ratio of reducible metal species in catalysts, calculated by peak integrating analysis with H2-TPR profiles; [d]: the hard-reducible spinel Cu2+ species in catalysts
    下载: 导出CSV

    表  3  催化剂C0.95N0.05Ax(x = 2、3、4)的表面性质

    Table  3  Surface properties of C0.95N0.05Ax(x = 2, 3, 4) catalysts

    Sample C0.95N0.05A2 C0.95N0.05A3 C0.95N0.05A4
    Cu/Al (surface)[a] 0.511 0.304 0.202
    Cu/Al (bulk)[a] 0.475 0.317 0.238
    Cu(s)/Al (spinel surface)[b] 0.477 0.280 0.182
    Cu(s)/Al (spinel bulk)[b] 0.387 0.253 0.169
    [a]: Cu/Al atomic ratio in the catalyst surface (XPS results) or catalyst bulk (precursors); [b]: Cu(s)/Al atomic ratio in the spinel surface (XPS results) or spinel bulk (H2-TPR results)
    下载: 导出CSV
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  • 收稿日期:  2020-08-06
  • 修回日期:  2020-08-27
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2020-09-10

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