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Ru/固体碱协同催化生物质糠醇水热氢解的研究

翁育靖 孟士航 朱万胜 张明威 孙琦 张玉龙

翁育靖, 孟士航, 朱万胜, 张明威, 孙琦, 张玉龙. Ru/固体碱协同催化生物质糠醇水热氢解的研究[J]. 燃料化学学报(中英文), 2021, 49(12): 1867-1875. doi: 10.1016/S1872-5813(21)60111-1
引用本文: 翁育靖, 孟士航, 朱万胜, 张明威, 孙琦, 张玉龙. Ru/固体碱协同催化生物质糠醇水热氢解的研究[J]. 燃料化学学报(中英文), 2021, 49(12): 1867-1875. doi: 10.1016/S1872-5813(21)60111-1
WENG Yu-jing, MENG Shi-hang, ZHU Wan-sheng, ZHANG Ming-wei, SUN Qi, ZHANG Yu-long. Synergistic hydrogenolysis of biomass furfuryl alcohol over Ru/solid base catalysts in hydrothermal reaction environment[J]. Journal of Fuel Chemistry and Technology, 2021, 49(12): 1867-1875. doi: 10.1016/S1872-5813(21)60111-1
Citation: WENG Yu-jing, MENG Shi-hang, ZHU Wan-sheng, ZHANG Ming-wei, SUN Qi, ZHANG Yu-long. Synergistic hydrogenolysis of biomass furfuryl alcohol over Ru/solid base catalysts in hydrothermal reaction environment[J]. Journal of Fuel Chemistry and Technology, 2021, 49(12): 1867-1875. doi: 10.1016/S1872-5813(21)60111-1

Ru/固体碱协同催化生物质糠醇水热氢解的研究

doi: 10.1016/S1872-5813(21)60111-1
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    Tel:0391-3987810, E-mail:wengyj@hpu.edu.cn

  • 中图分类号: O643

Synergistic hydrogenolysis of biomass furfuryl alcohol over Ru/solid base catalysts in hydrothermal reaction environment

More Information
  • 摘要: 本研究针对生物质糠醇的结构特点,以水相加氢性能优异的Ru催化剂为切入口,通过在催化剂制备工艺和活化条件、反应条件等方面的调控,探索生物质糠醇的直接氢解联产四氢糠醇和1,2-戊二醇的高效催化体系。研究发现,以碱性金属氧化物为载体制备Ru基催化剂可以提高产物中1,2-戊二醇的收率和选择性,其中,Ru/MnO2在最佳反应条件下最高可以得到四氢糠醇(53%)和1,2-戊二醇(32%)总收率85%。实验结合了N2 吸附-脱附、XRD、XPS等表征手段对反应前后催化剂进行分析,并发现反应中催化剂表面会产生碱性基团与活性金属产生协同催化促进反应进行。
  • FIG. 1152.  FIG. 1152.

    FIG. 1152.  FIG. 1152.

    图  1  生物质转化为高价值化学品[10]

    Figure  1  Conversion of biomass to value-added chemicals[10]

    图  2  不同载体的催化剂反应

    Figure  2  Reaction results of catalysts with different support (Furfuryl alcohol 0.5 g, catalyst 0.1 g (4% Ru), H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃)

    图  3  不同溶剂对反应结果的影响

    Figure  3  Effects of solvents on the reaction (a): Furfuryl alcohol 0.5 g, 4% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃. (b): Furfuryl alcohol 0.5 g, 4% Ru/MgO 0.1 g, solvent 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃

    图  4  (a)不同糠醇原料质量浓度,(b)不同原料对反应的影响,(c)产物分布和反应时间的关联图,(d)催化剂稳定性测试

    Figure  4  (a) Effect of raw material concentrations on the reaction (furfuryl alcohol 0.5/0.2/0.1/1 g, 4% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃), (b) Effect of raw material on the reaction (furfuryl alcohol/Furfural 0.5 g, 4% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃), (c) products distribution at different reaction time (Furfuryl alcohol 0.5 g, 4% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 150 ℃) and (d) catalyst reusability test (furfuryl alcohol 0.5 g, 4% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (hydrogen pressure), 4 h, 150 ℃)

    图  5  (a)不同Ru负载量催化剂(b)还原温度对反应的影响

    Figure  5  (a) Effect of Ru loading on the reaction (furfuryl alcohol/furfural 0.5 g, 4% / 2% Ru/MnO2 0.1 g, H2O 10 mL, 600 r/min, 1.5 MPa (H2), 4 h, 150 ℃);(b) effect of reduction conditions on product distribution (Ru/MnO2, 10 mL water, 600 r/min, 1.5 MPa(H2),4 h, 150 ℃)

    图  6  (a)Mg基催化剂和(b)Mn基催化剂的XRD谱图

    Figure  6  XRD patterns of relevant (a) Ru/MgO and (b) Ru/MnO2 catalysts

    图  7  Mn基催化剂N2吸附-脱附曲线

    Figure  7  N2 adsorption-desorption isotherms of Mn-based catalyst

    图  8  Mn基催化剂未还原、还原和反应残渣中O(a)和Mn(b)、(c)元素的XPS谱图

    Figure  8  XPS spectra of Mn based series samples (a): O 1s; (b): Mn 2p; (c): Mn 3s

    表  1  催化剂的比表面积、孔容、孔径

    Table  1  Catalyst specific surface area, pore volume, pore size

    Catalyst (4%)Specific surface area/ (m2·g−1)Pore volume/
    (cm3·g−1)
    Average pore size/nm
    Ru/MnO2
    (Residue)
    41.10.0763.295
    Ru/MnO2
    (Reduced)
    17.20.0834.487
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  • 收稿日期:  2021-03-19
  • 修回日期:  2021-05-08
  • 网络出版日期:  2021-06-09
  • 刊出日期:  2021-12-29

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