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钙铈基催化剂上碳酸丙烯酯和甲醇制备碳酸二甲酯的研究

郭炯 杨金海 史依琳 赵宁 肖福魁 姜新东

郭炯, 杨金海, 史依琳, 赵宁, 肖福魁, 姜新东. 钙铈基催化剂上碳酸丙烯酯和甲醇制备碳酸二甲酯的研究[J]. 燃料化学学报(中英文), 2024, 52(4): 545-552. doi: 10.1016/S1872-5813(23)60394-9
引用本文: 郭炯, 杨金海, 史依琳, 赵宁, 肖福魁, 姜新东. 钙铈基催化剂上碳酸丙烯酯和甲醇制备碳酸二甲酯的研究[J]. 燃料化学学报(中英文), 2024, 52(4): 545-552. doi: 10.1016/S1872-5813(23)60394-9
GUO Jiong, YANG Jinhai, SHI Yilin, ZHAO Ning, XIAO Fukui, JIANG Xindong. Investigation on production of dimethyl carbonate from propylene carbonate and methanol on calcium cerium-based catalysts[J]. Journal of Fuel Chemistry and Technology, 2024, 52(4): 545-552. doi: 10.1016/S1872-5813(23)60394-9
Citation: GUO Jiong, YANG Jinhai, SHI Yilin, ZHAO Ning, XIAO Fukui, JIANG Xindong. Investigation on production of dimethyl carbonate from propylene carbonate and methanol on calcium cerium-based catalysts[J]. Journal of Fuel Chemistry and Technology, 2024, 52(4): 545-552. doi: 10.1016/S1872-5813(23)60394-9

钙铈基催化剂上碳酸丙烯酯和甲醇制备碳酸二甲酯的研究

doi: 10.1016/S1872-5813(23)60394-9
基金项目: 山西省基础研究计划(202203021221303),国家自然科学基金—面上项目(22078201),国家自然科学基金—辽宁联合基金(U1908202),山西省重点研发计划(202005D121002)和中央引导地方科技发展项目(2020SW26)资助
详细信息
    通讯作者:

    Tel:13935170768, 13403457648, 13889207608, E-mail: zhaoning@sxicc.ac.cn

    xiaofk@sxicc.ac.cn

    xdjiang@syuct.edu.cn

  • 中图分类号: TQ225

Investigation on production of dimethyl carbonate from propylene carbonate and methanol on calcium cerium-based catalysts

Funds: The project was supported by Fundamental Research Program of Shanxi Province (202203021221303), National Natural Science Foundation of China (22078201), Joint Funds of the National Natural Science Foundation of China (U1908202), Science and Technology Major Project of Shanxi Province (202005D121002), The Central Project Guide Local Science and Technology for Development (2020SW26).
  • 摘要: 采用溶胶凝胶法制备了不同比例的钙铈基催化剂,并研究了其对于碳酸丙烯酯和甲醇制备碳酸二甲酯的酯交换反应性能。结果表明, Ca∶Ce=9的催化剂在反应时间2 h,温度40 ℃,甲醇与碳酸丙烯酯物质的量比为15∶1,催化剂用量为碳酸丙烯酯用量4%的条件下,碳酸丙烯酯转化率达到91.1%,碳酸二甲酯选择性达到91.7%。采用XRD、N2吸附-脱附、FT-IR、XPS和CO2-TPD对催化剂进行了表征。结果表明,催化剂表面的氧空穴越多,中等碱性位数量越多,越有利于甲醇的活化,催化剂的活性越好。
  • FIG. 3078.  FIG. 3078.

    FIG. 3078.  FIG. 3078.

    图  1  不同比例钙铈基催化剂的XRD谱图

    Figure  1  XRD patterns of the catalysts with different Ca∶Ce molar ratio

    图  2  不同比例钙铈基催化剂的N2吸附-解吸等温线和孔径分布

    Figure  2  N2 adsorption-desorption isotherms and pore size distribution of CaxCe1−xOz with different Ca∶Ce molar ratio

    图  3  不同比例钙铈基催化剂的红外光谱谱图

    Figure  3  FT-IR spectra of the catalysts with different Ca:Ce molar ratio

    图  4  不同比例钙铈基催化剂的XPS谱图

    Figure  4  XPS spectra of the catalysts with different Ca∶Ce molar ratio

    图  5  不同比例钙铈基催化剂的CO2-TPD谱图

    Figure  5  CO2-TPD profiles of the catalysts with different Ca∶Ce molar ratio

    图  6  0.9CaCe催化剂反应条件优化及循环使用性能

    Figure  6  Optimization of reaction conditions and recyclability for 0.9CaCe catalyst

    图  7  氧空穴占比与PC转化率的关系(a),中强碱性位点占比与PC转化率的关系(b)

    Figure  7  Relationship between oxygen defect proportion and PC conversion (a); Relationship between medium-strong basic site proportion and PC conversion (b)

    表  1  不同比例钙铈基催化剂的织构参数

    Table  1  Textural parameters of the catalysts with different Ca∶Ce molar ratio

    CatalystSBET/
    (m2·g−1)
    Pore volumea/
    (cm3·g−1)
    Average pore
    sizeb/nm
    0.9CaCe10.90.0313.0
    0.7CaCe1.80.0260.1
    0.5CaCe5.90.0226.9
    0.3CaCe1.60.0148.7
    0.1CaCe0.70.0139.4
    a: Measured at p/p0=0.99; b: Calculated from isothermal desorption branches using the BJH method.
    下载: 导出CSV

    表  2  催化剂中Ca和O的结合能值

    Table  2  Binding energy values of the catalysts

    CatalystBinding energy/eV
    Ca 2pO 1s
    0.9CaCe346.86, 350.41528.89, 531.3, 532.42
    0.7CaCe346.64, 350.2528.77, 531.13, 532.07
    0.5CaCe346.58, 350.13528.61, 531.03, 532.25
    0.3CaCe346.64, 350.19528.69, 531.14, 532.87
    0.1CaCe346.51, 350.1528.51, 531.01, 532.42
    下载: 导出CSV

    表  3  催化剂表面氧物种的相对含量

    Table  3  Relative content of oxygen species of the catalysts

    CatalystO 1s/%
    O1O2O3
    0.9CaCe5.9280.3013.79
    0.7CaCe20.0163.0416.95
    0.5CaCe31.3457.3311.33
    0.3CaCe41.6152.326.07
    0.1CaCe51.9040.337.76
    下载: 导出CSV

    表  4  催化剂的总碱位数量和各碱性位点所占比例

    Table  4  The total number and the proportion of each basic site of the catalysts

    Catalystα peak/%β peak/%Total basicity/(mmol·g−1)
    0.9CaCe3.9696.041.85
    0.7CaCe22.7677.240.35
    0.5CaCe23.9876.020.52
    0.3CaCe44.8155.190.12
    0.1CaCe53.3146.690.04
    下载: 导出CSV

    表  5  钙铈基催化剂的反应性能评价

    Table  5  Catalytic performance of the catalysts

    CatalystReaction conditionsPC
    conv./%
    DMC
    sel./%
    temp./℃time/hCH3OH/PCmcat./mPC
    /%
    0.1CaCe60215432.06.3
    0.3CaCe60215461.345.7
    0.5CaCe60215474.387.5
    0.7CaCe60215488.987.4
    0.9CaCe60215489.487.4
    CeO260215443.70.0
    下载: 导出CSV
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  • 收稿日期:  2023-09-06
  • 修回日期:  2023-10-13
  • 录用日期:  2023-10-18
  • 网络出版日期:  2023-11-10
  • 刊出日期:  2024-04-03

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