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Cerium-modified copper/hexagonal mesoporous silica catalyst for efficient dimethyl oxalate hydrogenation to ethylene glycol under moderate reaction conditions

WU Di ZHANG Juan HUANG Zhi-jun CHEN Jian-gang

吴迪, 张娟, 黄志军, 陈建刚. 铈改性的铜/六方介孔二氧化硅催化剂在温和反应条件下高效地将草酸二甲酯氢化为乙二醇[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60042-2
引用本文: 吴迪, 张娟, 黄志军, 陈建刚. 铈改性的铜/六方介孔二氧化硅催化剂在温和反应条件下高效地将草酸二甲酯氢化为乙二醇[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60042-2
WU Di, ZHANG Juan, HUANG Zhi-jun, CHEN Jian-gang. Cerium-modified copper/hexagonal mesoporous silica catalyst for efficient dimethyl oxalate hydrogenation to ethylene glycol under moderate reaction conditions[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60042-2
Citation: WU Di, ZHANG Juan, HUANG Zhi-jun, CHEN Jian-gang. Cerium-modified copper/hexagonal mesoporous silica catalyst for efficient dimethyl oxalate hydrogenation to ethylene glycol under moderate reaction conditions[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60042-2

铈改性的铜/六方介孔二氧化硅催化剂在温和反应条件下高效地将草酸二甲酯氢化为乙二醇

doi: 10.1016/S1872-5813(22)60042-2

Cerium-modified copper/hexagonal mesoporous silica catalyst for efficient dimethyl oxalate hydrogenation to ethylene glycol under moderate reaction conditions

Funds: The project was supported by the National Natural Science Foundation of China (22072175).
More Information
  • 摘要: 采用蒸氨法制备了一种高效的铈改性铜/六方介孔二氧化硅(xCe-Cu/HMS)催化剂,用于草酸二甲酯(DMO)气相化学选择性氢化成乙二醇(EG)。铈助剂可以显著提高催化剂的性能,在引入1.2 wt%的铈后,催化剂的性能最好。在温和的条件下(200 ℃,2.0 MPa,H2/DMO = 100,LHSVDMO = 1.2 h−1),DMO转化率和EG选择性分别达到了前所未有的99.6%和96.3%。表征结果显示,Ce修饰的Cu/HMS可以增强Cu与载体之间的相互作用,改善Cu的分散性,并保持适当的Cu+/(Cu+ + Cu0)的比例。本研究采用简单、低成本的路线,合成了具有优良催化性能的Ce改性的Cu-HMS催化剂,实现了在温和的条件下DMO向EG的高选择性转化。
  • Figure  1  Nitrogen adsorption and desorption isotherms and pore size distribution of the catalysts

    Figure  2  X-ray diffraction patterns of the (a) fresh catalysts and (b) used Cu/HMS and 1.2Ce-Cu/HMS catalysts

    Figure  3  TEM images with the corresponding Cu particles size distribution diagrams of Cu/HMS (a: fresh; b: used) and1.2Ce-Cu/HMS (c: fresh; d: used)

    Figure  4  H2-TPR patterns of the calcined catalysts

    Figure  5  FFT-IR spectra of the calcined catalysts

    Figure  6  XPS spectra of the fresh catalysts

    Figure  7  Cu LMM XAES spectra of the reduced catalysts: (a) Cu/HMS, (b) 0.8Ce-Cu/HMS, (c) 1.0Ce-Cu/HMS, (d) 1.2Ce-Cu/HMS, (e) 1.5Ce-Cu/HMS and (f) 2.0Ce-Cu/HMS

    Figure  8  Catalytic performance of the xCe-Cu/HMS catalysts in DMO hydrogenation reaction. Reaction conditions: 200 °C, 2.0 MPa and H2/DMO = 100

    Figure  9  Catalytic performance of 1.2Ce-Cu/HMS as a function of reaction time. Reaction conditions: 200 °C, 2.0 MPa, H2/DMO =100 and LHSVDMO = 1.2 h−1

    Table  1  Structural properties and chemical compositions of synthesized catalysts

    SampleSBET(m2·g−1)aVp(cm3·g−1)bDp (nm)cDCu (%)dSACu(m2·gcat−1)edvsCu(nm)fCe loading(wt%)g
    HMS 1117 0.98 2.68
    Cu/HMS 349 0.51 4.47 31.8 43.1 3.1
    0.8Ce-Cu/HMS 310 0.47 4.95 39.0 52.8 2.6 0.83
    1.0Ce-Cu/HMS 264 0.41 4.93 42.3 57.3 2.4 1.01
    1.2Ce-Cu/HMS 308 0.48 5.08 45.5 61.5 2.2 1.44
    1.5Ce-Cu/HMS 299 0.54 5.60 32.1 43.5 3.1 1.54
    2.0Ce-Cu/HMS 299 0.53 5.58 21.1 28.5 4.7 1.96
    a BET specific surface area
    b Total pore volume obtained from N2 physisorption
    c Average pore size obtained from N2 physisorption
    d Cu dispersion determined by N2O titration
    e Cu surface area per gram of catalyst determined by N2O titration
    f Cu average volume-surface area diameter determined by N2O titration
    g Determined by ICP-AES
    下载: 导出CSV

    Table  2  Catalytic performance of several catalysts under different reaction conditions

    CatalystxDMO/%sEG/%p/MPat/℃H2/DMOLHSV/h−1Ref.
    CuZnZr-0.210092.03.02201500.3[2]
    Cu@CNTs-35099.487.42.52702000.2[34]
    15Ag/SiO210096.02.52801000.2[35]
    CuZnAl-LDH10094.72.52201600.3[36]
    10%Cu-Co/HMS100>95.03.02201501.2[37]
    Cu3Ni/HMS100>95.02.52001001.0[13]
    1.2Ce-Cu/HMS99.696.32.02001001.2This work
    下载: 导出CSV
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  • 收稿日期:  2022-03-14
  • 录用日期:  2022-04-24
  • 修回日期:  2022-04-23
  • 网络出版日期:  2022-06-23

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