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稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响

杨淑倩 贺建平 张娜 隋晓伟 张磊 杨占旭

杨淑倩, 贺建平, 张娜, 隋晓伟, 张磊, 杨占旭. 稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响[J]. 燃料化学学报, 2018, 46(2): 179-188.
引用本文: 杨淑倩, 贺建平, 张娜, 隋晓伟, 张磊, 杨占旭. 稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响[J]. 燃料化学学报, 2018, 46(2): 179-188.
YANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu. Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming[J]. Journal of Fuel Chemistry and Technology, 2018, 46(2): 179-188.
Citation: YANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu. Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming[J]. Journal of Fuel Chemistry and Technology, 2018, 46(2): 179-188.

稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响

基金项目: 

国家自然科学基金 21671092

国家自然科学基金 21376237

辽宁省博士科研启动基金 2016013022

详细信息
  • 中图分类号: O643

Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming

Funds: 

the National Natural Science Foundation of China 21671092

the National Natural Science Foundation of China 21376237

the Doctoral Scientific Research Foundation of Liaoning Province 2016013022

More Information
  • 摘要: 采用原位合成法在γ-Al2O3表面合成了锌铝水滑石,再通过顺次浸渍法制备了一系列掺杂稀土改性的MM=Y、La、Ce、Sm、Gd)/Cu/ZnAl催化材料,并将其应用于甲醇水蒸气重整制氢反应。探讨了稀土掺杂改性对Cu/ZnAl催化剂催化性能的影响,并采用XRD、SEM-EDS、BET、H2-TPR、XPS和N2O滴定等手段对催化剂进行了表征。结果表明,催化剂的活性与Cu比表面积和催化剂的还原性质密切相关,Cu比表面积越大,还原温度越低,催化活性越高。稀土Ce、Sm、Gd的引入能改善活性组分Cu的分散度、Cu比表面积以及催化剂的还原性质,进而提高催化剂的催化活性。其中,Ce/Cu/ZnAl催化剂表现出最佳的催化活性,在反应温度为250 ℃时,甲醇转化率达到100%,CO含量为0.39%,相比Cu/ZnAl催化剂,甲醇转化率提高了近40%。
  • 图  1  γ-Al2O3和ZnAl-LDHs/γ-Al2O3的XRD谱图

    Figure  1  XRD patterns of γ-Al2O3 and ZnAl-LDHs/γ-Al2O3

    a: γ-Al2O3; b: ZnAl-LDHs/γ-Al2O3

    图  2  催化剂的XRD谱图

    Figure  2  XRD patterns of various catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  3  γ-Al2O3 和ZnAl-LDHs/γ-Al2O3的SEM照片

    Figure  3  SEM images of γ-Al2O3 (a) and ZnAl-LDHs/γ-Al2O3 (b)

    图  4  掺杂不同稀土助剂催化剂的SEM-EDS照片

    Figure  4  SEM-EDS images of various catalysts

    (a): Y/Cu/ZnAl; (b): La/Cu/ZnAl; (c): Ce/Cu/ZnAl; (d): Sm/Cu/ZnAl; (e): Gd/Cu/ZnAl

    图  5  催化剂的H2-TPR谱图

    Figure  5  H2-TPR profiles of various catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  6  催化剂的Cu 2p XPS谱图

    Figure  6  Cu 2p XPS spectra of the catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  7  催化剂的Cu俄歇谱图

    Figure  7  Cu Auger spectra of the catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  8  催化剂的Zn 2p的XPS谱图

    Figure  8  Zn 2p XPS spectra of various catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  9  催化剂的Al 2p的XPS谱图

    Figure  9  Al 2p XPS spectra of various catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  10  催化剂O 1s的XPS谱图

    Figure  10  O 1s XPS spectra of various catalysts

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl

    图  11  反应温度对催化剂性能的影响

    Figure  11  Activities of various catalysts as a function of the reaction temperature for the methanol steam reforming at a water/methanol molar ratio of 1.2 and GHSV of 800 h-1

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl; g: equil

    图  12  反应温度对催化剂CO浓度的影响

    Figure  12  CO molar concentrations in the gaseous products as a function of the reaction temperature for the methanol steam reforming at a water/methanol molar ratio of 1.2 and GHSV of 800 h-1

    a: Cu/ZnAl; b: Y/Cu/ZnAl; c: La/Cu/ZnAl; d: Ce/Cu/ZnAl; e: Sm/Cu/ZnAl; f: Gd/Cu/ZnAl; g: equil

    表  1  催化剂的物化性质及其催化甲醇水蒸气重整反应中氢气产率

    Table  1  Textural properties of the M/Cn/ZnAl catalysts modified with various rare earth elements and their hydrogen production rate in the methanol steam reforming

    Catalyst ABET
    /(m2·g-1)
    Pore volume
    v/(cm3·g-1)
    CuO crystallite
    size d/nm
    Cu surface area
    A/(m2·g-1)
    Cu dispersion
    /%
    YcH2/
    (mL·kgcat-1·s-1)
    Cu/ZnAl 147.0 0.47 34 5.9 10.32 446.2
    Y/Cu/ZnAl 101.9 0.39 25 5.3 10.15 414.8
    La/Cu/ZnAl 105.5 0.37 24 5.3 10.05 424.4
    Ce/Cu/ZnAl 109.6 0.41 23 6.3 11.49 810.7
    Sm/Cu/ZnAl 106.0 0.37 25 6.1 11.53 568.5
    Gd/Cu/ZnAl 107.6 0.40 24 5.9 11.15 457.3
    note: the Cu surface area was measured by N2O chemisorption and Cu dispersion was determined as the ratio of the surface copper amount to the total copper content in the catalysts; The hydrogen production rate (YH2) was obtained by methanol steam reforming under atmospheric pressure, 240 ℃, water methanol molar ratio of 1.2 and GHSV of 800 h-1; no carrier gas was used
    下载: 导出CSV

    表  2  高斯拟合后还原峰位置

    Table  2  Positions of the reduction peak by a Gauss fit of the H2-TPR profiles

    Catalyst Peak position t/ ℃
    peak 1 peak 2 peak 3
    Cu/ZnAl 266 324 -
    Y/Cu/ZnAl 293 305 315
    La/Cu/ZnAl 279 297 309
    Ce/Cu/ZnAl 242 266 281
    Sm/Cu/ZnAl 266 297 -
    Gd/Cu/ZnAl 266 297 -
    下载: 导出CSV

    表  3  CO的选择性

    Table  3  Selectivity to CO over various catalysts

    Catalyst Methanol conversion
    x/%
    Selectivity to CO
    s/%
    Temperature
    t/ ℃
    Cu/ZnAl 79 1.6 260
    Y/Cu/ZnAl 76 1.1 260
    La/Cu/ZnAl 77 1.2 260
    Ce/Cu/ZnAl 92 0.9 240
    Sm/Cu/ZnAl 83 1.0 250
    Gd/Cu/ZnAl 81 0 260
    下载: 导出CSV
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  • 收稿日期:  2017-08-09
  • 修回日期:  2017-12-13
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2018-02-10

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