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镧改性Cu/SiO2催化剂的乙酸甲酯高效加氢催化性能研究

张传明 李伟杰 康金灿 林丽娜 李昌鑫 李林才 邹昊宇 朱红平

张传明, 李伟杰, 康金灿, 林丽娜, 李昌鑫, 李林才, 邹昊宇, 朱红平. 镧改性Cu/SiO2催化剂的乙酸甲酯高效加氢催化性能研究[J]. 燃料化学学报(中英文), 2024, 52(2): 131-139. doi: 10.1016/S1872-5813(23)60382-2
引用本文: 张传明, 李伟杰, 康金灿, 林丽娜, 李昌鑫, 李林才, 邹昊宇, 朱红平. 镧改性Cu/SiO2催化剂的乙酸甲酯高效加氢催化性能研究[J]. 燃料化学学报(中英文), 2024, 52(2): 131-139. doi: 10.1016/S1872-5813(23)60382-2
ZHANG Chuanming, LI Weijie, KANG Jincan, LIN Lina, LI Changxin, LI Lincai, ZOU Haoyu, ZHU Hongping. Catalytic performance of La-modified Cu/SiO2 in the hydrogenation of methyl acetate[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 131-139. doi: 10.1016/S1872-5813(23)60382-2
Citation: ZHANG Chuanming, LI Weijie, KANG Jincan, LIN Lina, LI Changxin, LI Lincai, ZOU Haoyu, ZHU Hongping. Catalytic performance of La-modified Cu/SiO2 in the hydrogenation of methyl acetate[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 131-139. doi: 10.1016/S1872-5813(23)60382-2

镧改性Cu/SiO2催化剂的乙酸甲酯高效加氢催化性能研究

doi: 10.1016/S1872-5813(23)60382-2
基金项目: 国家自然科学基金(21972112,22172123)和福建省高校产学合作项目(2021H6002)资助
详细信息
    通讯作者:

    E-mail: kangjc@xmu.edu.cn

    hpzhu@xmu.edu.cn

  • 中图分类号: O643.38

Catalytic performance of La-modified Cu/SiO2 in the hydrogenation of methyl acetate

Funds: The project was supported by National Natural Science Foundation of China (21972112, 22172123) and Productive and Researching Foundation of Fujian Province (2021H6002).
  • 摘要: 采用蒸氨法制备了镧(La)改性的负载型铜硅(Cu/SiO2)催化剂,并对其乙酸甲酯(MeOAc)气相加氢制乙醇(EtOH)的催化性能进行了研究。采用N2吸附-脱附(N2 adsorption-desorption)、X射线粉末衍射(XRD)、电感耦合等离子体发射光谱(ICP-OES)、氢气程序升温还原(H2-TPR)、傅里叶红外光谱(FT-IR)、高分辨透射电镜(HRTEM)、光电子能谱(XPS)和原子发射光谱仪(AES)等手段对催化剂进行了的表征,发现La物种的加入产生了较多的层状硅酸铜,增强了Cu和La物种之间的相互作用。La物种的加入在结构方面提高了催化剂的比表面积,降低了铜物种的粒径,提高了铜物种的分散度;在电子还原调控方面提高了Cu+的含量,增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO2催化剂相比,镧改性后Cu/SiO2催化剂的乙酸甲酯加氢性能得到大幅提升;其中La掺杂量0.5%的Cu/SiO2催化剂表现出最佳的催化性能,乙酸甲酯转化率达98.5%,乙醇的总收率为97.0%。
  • FIG. 2922.  FIG. 2922.

    FIG. 2922.  FIG. 2922.

    图  1  不同La掺杂量催化剂的沉淀前驱体FT-IR谱图

    Figure  1  FT-IR spectra of the pre-calcined 30Cu- nLa/SiO2 samples ( n=0, 0.5, 1, and 2)

    图  2  不同La掺杂量催化剂的N2吸附-脱附等温线(a)和孔径分布(b)

    Figure  2  N2 adsorption-desorption isotherms (a) and pore distribution curves (b) of the 30Cu-nLa/SiO2 catalysts with different La loadings

    图  3  不同La掺杂量的催化剂的XRD谱图

    Figure  3  XRD patterns of the calcined (a) and reduced (b) 30Cu-nLa/SiO2 catalysts with different La loadings

    图  4  不同La掺杂量催化剂的H2-TPR谱图

    Figure  4  H2-TPR profiles of the 30Cu-nLa/SiO2 catalysts with different La loadings

    图  5  不同La掺杂量的催化剂H2还原后的Cu 2p(a)和La 3d(b) XPS谱图

    Figure  5  Cu 2p (a) and La 3d (b) XPS spectra of the reduced 30Cu-nLa/SiO2 catalysts with different La loadings

    图  6  不同La掺杂量的催化剂还原后的Cu LMM XAES谱图

    Figure  6  Cu LMM XAES spectra of the reduced 30Cu-nLa/SiO2 catalysts with different La loadings

    图  7  不同La掺杂量的还原后催化剂的TEM照片和粒径统计分布

    Figure  7  TEM images of the reduced 30Cu- nLa/SiO2 catalysts with different La loadings ((a) 30Cu/SiO2, (b) 30Cu-0.5La/SiO2, (c) 30Cu-1La/SiO2, and (d) 30Cu-2La/SiO2, where the insets display the particle size distribution) and (e) HRTEM image of 30Cu-0.5La/SiO2

    表  1  30Cu-nLa/SiO2、30Cu/SiO2、2La/SiO2、SiO2催化乙酸甲酯加氢反应制乙醇的性能

    Table  1  Catalytic reaction test results for the hydrogenation of MeOAc to EtOH

    CatalystMeOAc
    conversion/
    %
    EtOH
    selectivity/
    %
    EtOAc
    selectivity/
    %
    EtOH
    yield/
    %
    30Cu/SiO285.677.322.766.2
    30Cu-0.5La/SiO298.598.51.597.0
    30Cu-1La/SiO294.892.67.487.8
    30Cu-2La/SiO281.573.426.659.8
    2La/SiO21.4068.731.31.0
    SiO20.10
    Reaction conditions: 230 ℃, 2 MPa, LHSV=2 h−1, and H2/MeOAc=20.
    下载: 导出CSV

    表  2  不同La掺杂量的催化剂的组织结构特征

    Table  2  Textural properties of the 30Cu-nLa/SiO2 catalysts with different La loadings

    CatalystCu loading w/%La loading w/%SBET/(m2·g−1)dpore/(cm3·g−1)vpore/(cm3·g−1)dCu-XRD /nmdCu-TEM /nm
    30Cu/SiO229.60.0295.36.00.445.45.4
    30Cu-0.5La/SiO229.00.47350.44.90.434.84.5
    30Cu-1La/SiO227.91.01336.25.40.455.75.5
    30Cu-2La/SiO228.91.91323.75.90.496.25.8
    Note: Cu and Cu loadings were measured by ICP-OES; Specific surface area (SBET), averaged pore diameter (dpore), and averaged pore volume (vpore) are determined by N2 sorption; dCu-XRD and dCu-TEM for the Cu particle sizes are obtained from XRD using the Debye-Scherrer formula and TEM measurement, respectively.
    下载: 导出CSV

    表  3  不同La掺杂量的催化剂还原后的XPS和Cu LMM XAES反卷积结果

    Table  3  Summary of the Cu XPS and Cu-LMM results

    CatalystBinding energy/eVKinetic energy/eVxCu+/%
    Cu 2p1/2Cu 2p3/2Cu+Cu0
    30Cu952.3932.2914.0918.038.2
    30Cu-0.5La952.1932.5914.0918.049.4
    30Cu-1La952.3932.6914.0918.046.7
    30Cu-2La952.8933.0914.0918.044.8
    下载: 导出CSV
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  • 收稿日期:  2022-07-03
  • 修回日期:  2022-08-04
  • 录用日期:  2023-08-02
  • 网络出版日期:  2023-09-18
  • 刊出日期:  2024-02-02

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