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Ce改性对CuLDH催化CO2加氢制甲醇性能的影响

刘昊然 于志庆 黄文斌 魏强 姜鹏 周亚松

刘昊然, 于志庆, 黄文斌, 魏强, 姜鹏, 周亚松. Ce改性对CuLDH催化CO2加氢制甲醇性能的影响[J]. 燃料化学学报(中英文), 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5
引用本文: 刘昊然, 于志庆, 黄文斌, 魏强, 姜鹏, 周亚松. Ce改性对CuLDH催化CO2加氢制甲醇性能的影响[J]. 燃料化学学报(中英文), 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5
LIU Haoran, YU Zhiqing, HUANG Wenbin, WEI Qiang, JIANG Peng, ZHOU Yasong. Effect of Ce modification on the performance of CuLDH catalyst for CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5
Citation: LIU Haoran, YU Zhiqing, HUANG Wenbin, WEI Qiang, JIANG Peng, ZHOU Yasong. Effect of Ce modification on the performance of CuLDH catalyst for CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5

Ce改性对CuLDH催化CO2加氢制甲醇性能的影响

doi: 10.1016/S1872-5813(23)60392-5
基金项目: 国家自然科学基金(22078360)资助
详细信息
    通讯作者:

    E-mail: zhouyasong2011@163.com

  • 中图分类号: O643

Effect of Ce modification on the performance of CuLDH catalyst for CO2 hydrogenation to methanol

Funds: The project was supported by National Natural Science Foundation of China (22078360).
  • 摘要: 通过向CuMgAl水滑石(CuLDH)催化剂中添加不同量的Ce,合成了一系列Ce改性的CuLDH-Cex催化剂。采用X射线衍射(XRD)、N2吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等分析手段对催化剂的理化性质进行表征。结果表明,添加Ce会改变Cu-LDH催化剂的水滑石结构,适量的Ce会增大催化剂的比表面积,改善了Cu颗粒的分散度。同时,适量的Ce有利于增加催化剂表面强碱性位点的密度和氧空位的数量,促进了CO2的吸附和转化。Ce有利于调变催化剂表面的Cu+/Cu0比例,较高的Cu+/Cu0比例有利于甲醇的生成。当Ce/Cu比例为0.3时,在空速为9000 mL/(g·h),温度为240 ℃,压力为2.5 MPa的条件下,催化剂的CO2的转化率为7.5%,甲醇选择性为78.4%,甲醇的时空收率最高可达362.8 g/(kg·h)。通过原位红外光谱(in-situ DRIFTS)证明CuLDH-Ce0.3催化剂在CO2加氢合成甲醇过程中遵循HCOO*反应路径。
  • FIG. 2925.  FIG. 2925.

    FIG. 2925.  FIG. 2925.

    图  1  CuLDH-Cex催化剂前驱体的XRD谱图

    Figure  1  XRD patterns of CuLDH-Cex catalysts precursors

    图  2  CuLDH-Cex催化剂煅烧后的XRD谱图

    Figure  2  XRD patterns of CuLDH-Cex catalysts after calcination

    图  3  CuLDH-Cex 催化剂煅烧后的SEM图片

    Figure  3  SEM images of CuLDH-Cex catalysts after calcination

    (a): CuLDO-Ce0; (b): CuLDO-Ce0.1; (c): CuLDO-Ce0.3; (d): CuLDO-Ce0.5; (e): CuLDO-Ce0.7.

    图  4  CuLDH-Cex催化剂的(a)N2吸附-脱附等温线和(b)孔径分布

    Figure  4  (a) N2 adsorption-desorption isotherm and (b) pore size distribution of CuLDH-Cex catalysts

    图  5  CuLDH-Cex 催化剂还原后的TEM图和CuLDO-Ce0.3 的EDX元素图

    Figure  5  TEM images of CuLDH-Cex catalysts after reduction and EDX elemental mapping of CuLDO-Ce0.3 (a): CuLDO-Ce0; (b): CuLDO-Ce0.1; (c): CuLDO-Ce0.3; (d): CuLDO-Ce0.5; (e): CuLDO-Ce0.7.

    图  6  CuLDH-Cex催化剂还原后的XPS谱图

    Figure  6  XPS spectra of CuLDH-Cex catalysts after reduction

    图  7  CuLDH-Cex催化剂的H2-TPR谱图

    Figure  7  H2-TPR profiles of CuLDH-Cex catalysts

    图  8  CuLDH-Cex催化剂的CO2-TPD谱图

    Figure  8  CO2-TPD profiles of CuLDH-Cex catalysts

    图  9  CuLDH-Cex催化剂的催化活性

    Figure  9  Catalytic performance of CuLDH-Cex catalysts Reaction condition: 240 ℃, 2.5 MPa, 9000 mL/(g·h).

    图  10  CuLDH-Ce0.3催化剂的催化性能随时间的变化(a), 反应前后的XRD谱图 (b)和反应后的TEM图(c)

    Figure  10  Catalytic performance of CuLDH-Ce0.3 catalyst over time (a), XRD patterns before and after reaction (b), and TEM images after reaction (c) Reaction condition: 240 ℃, 2.5 MPa, 9000 mL/(g·h).

    图  11  CuLDH-Ce0.3催化剂在CO2加氢过程中中间物种浓度的原位红外光谱谱图

    Figure  11  In-situ infrared spectra of intermediate species concentration during CO2 hydrogenation on CuLDH-Ce0.3 catalyst

    表  1  CuLDH-Cex催化剂的物理化学性质

    Table  1  Physical and chemical properties of CuLDH-Cex catalysts

    CatalystMolar ratio Cu/Mg/Al/CeaSBETb/
    (m2·g−1)
    vpb/
    (cm3·g−1)
    dpb/
    nm
    dCu c/
    nm
    dCud /
    %
    SCud/
    (m2·g−1)
    CuLDH-Ce09.9/29.7/10.4/0199.50.41
    6.2
    4.9
    23.5
    32.1
    CuLDH-Ce0.110.2./29.9/9.8/1.1208.40.477.33.726.335.4
    CuLDH-Ce0.310.1/30.3/9.7/2.9205.60.43
    6.5
    4.5
    24.2
    33.2
    CuLDH-Ce0.59.8/29.8/10.2/5.2194.90.35
    5.3
    5.2
    20.4
    29.6
    CuLDO-Ce0.710.3/29.7/9.9/7.1182.30.314.47.218.125.3
    a: Measured by ICP; b: Calculated by BET and BJH equations; c: Measured by TEM; d: Measured by N2O titration.
    下载: 导出CSV

    表  2  CuLDH-Cex催化剂碱性位点密度

    Table  2  The basic sites density of CuLDH-Cex catalysts

    CatalystTotal basic
    sites/
    (μmol·g−1)
    Weakly basic
    sites/
    (μmol·g−1)
    Moderately basic
    sites/
    (μmol·g−1)
    Density of moderately
    basic site/
    (μmol·m2)
    CuLDH-Ce0232.855.7177.10.89
    CuLDH-Ce0.1256.523.2233.31.12
    CuLDH-Ce0.3297.234.5262.71.28
    CuLDH-Ce0.5210.348.8161.50.83
    CuLDO-Ce0.7198.664.3134.30.74
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-08-18
  • 修回日期:  2023-09-21
  • 录用日期:  2023-09-21
  • 网络出版日期:  2023-11-10
  • 刊出日期:  2024-02-02

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