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金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究

张文豪 童乐 冯君锋 潘晖

张文豪, 童乐, 冯君锋, 潘晖. 金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究[J]. 燃料化学学报(中英文), 2024, 52(3): 343-352. doi: 10.19906/j.cnki.JFCT.2023071
引用本文: 张文豪, 童乐, 冯君锋, 潘晖. 金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究[J]. 燃料化学学报(中英文), 2024, 52(3): 343-352. doi: 10.19906/j.cnki.JFCT.2023071
ZHANG Wenhao, TONG Le, FENG Junfeng, PAN Hui. Study on preparation of cyclohexanol from lignin-derived phenolic compounds catalyzed by metal oxide-loaded ruthenium[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 343-352. doi: 10.19906/j.cnki.JFCT.2023071
Citation: ZHANG Wenhao, TONG Le, FENG Junfeng, PAN Hui. Study on preparation of cyclohexanol from lignin-derived phenolic compounds catalyzed by metal oxide-loaded ruthenium[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 343-352. doi: 10.19906/j.cnki.JFCT.2023071

金属氧化物负载钌催化木质素衍生酚类化合物制备环己醇的研究

doi: 10.19906/j.cnki.JFCT.2023071
基金项目: 国家自然科学基金(32101469)和广西林产化学与工程重点实验室(国家民委重点实验室)开放基金课题(GXFK2204)资助
详细信息
    通讯作者:

    Tel: 13770663924 , E-mail: 2018149@njfu.edu.cn

  • 中图分类号: TQ35;TK6

Study on preparation of cyclohexanol from lignin-derived phenolic compounds catalyzed by metal oxide-loaded ruthenium

Funds: The project was supported by National Natural Science Foundation of China (32101469),Guangxi Key Laboratory of Forest Products Chemistry and Engineering (State Ethnic Affairs Commission Key Laboratory) Open Fund Project (GXFK2204)
  • 摘要: 本研究采用初湿浸渍法,制备得到一系列钌负载于金属氧化物载体的催化剂(Ru/CeO2、Ru/Nb2O5、Ru/ZrO2、Ru/Al2O3和Ru/CeOx),用于木质素衍生酚类化合物苯酚提质加氢转化为环己醇的研究。通过采用X射线晶体衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等手段对所制备催化剂进行结构和物化特征的表征,发现Ru/CeOx中含有的氧空位可以很好地吸附带有含氧基团的原料,从而有利于苯酚的高效加氢;同时XPS表明,Ru/CeOx中的有效活性中心RuO2和Ru0是催化加氢的活性位点,因此,氧空位和金属活性位点的共同作用使得催化剂有较好的加氢活性。探究了反应温度、压力、时间对加氢效果的影响,发现催化剂能够在140 ℃下使苯酚完全转化,得到目标产物环己醇得率为90.2%,并对催化剂的循环特性进行考察,发现循环使用四次后催化剂仍表现出优异的加氢活性。同时采用GC-MS检测加氢过程的中间产物,进而推断出苯酚加氢过程的反应路径。
  • FIG. 3013.  FIG. 3013.

    FIG. 3013.  FIG. 3013.

    图  1  (a) 载体CeOx的X射线衍射谱图及(b) 催化剂RuNi/CeOx和Ru/CeOx的X射线衍射谱图

    Figure  1  (a) X-ray diffraction pattern of CeOx support and (b) X-ray diffraction patterns of catalysts RuNi/CeOx and Ru/CeOx

    图  2  CeOx载体和Ru/CeOx催化剂的扫描电镜照片

    Figure  2  SEM of CeOx support and Ru/CeOx catalyst ((a) (10 μm) CeOx, (b) (5 μm) CeOx, (c) (1 μm) CeOx, (d) (10 μm) Ru/CeOx, (e) (5 μm) Ru/CeOx, (f) (1 μm) Ru/CeOx)

    图  3  Ru/CeOx催化剂的HRTEM照片

    Figure  3  HRTEM image of Ru/CeOx catalyst ((a) Ru/CeOx image, (b) Ru particle size distribution diagram, (c) Ru and CeO2 lattice, (d) local enlargement of Ru particles)

    图  4  Ru/CeO2和Ru/CeOx催化剂的XPS谱图

    Figure  4  XPS spectra of Ru/CeO2 catalyst ((a) Ce 3d, (c) Ru 3p, (f) O 1s) and Ru/CeOx catalyst ((b) Ce 3d, (d) Ru 3p, (e) O 1s)

    图  5  催化剂Ru/CeOx和Ru/CeO2的激光拉曼光谱谱图

    Figure  5  Raman spectra of catalysts Ru/CeOx and Ru/CeO2

    图  6  反应时间对催化剂性能的影响

    Figure  6  Effect of reaction time on catalyst performance

    图  7  反应温度对催化剂性能的影响

    Figure  7  Effect of reaction temperature on catalyst performance

    图  8  反应氢气压力对催化剂性能的影响

    Figure  8  Effect of reaction hydrogen pressure on catalyst performance

    图  9  反应后液体产物的GC-MS谱图

    Figure  9  GC-MS spectrum of liquid product after reaction

    图  10  苯酚催化转化的可能反应途径

    Figure  10  Possible reaction pathway of catalytic conversion of phenol

    图  11  Ru/CeOx循环性能

    Figure  11  Ru/CeOx Cyclic experiment

    Reaction conditions: 0.05 g Ru/CeOx, 3 MPa H2, 140 ℃, 3 h.

    图  12  Ru/CeOx催化剂的XPS谱图

    Figure  12  XPS spectra of Ru/CeOx catalyst ((a) not used Ce 3d, (b) used Ce 3d, (c) not used Ru 3p, (d) used Ru 3p)

    表  1  不同催化剂的性能研究

    Table  1  Performance study of different catalysts

    CatalystConversion/%Cyclohexanol yield/%
    Ni/Nb2O531.000.00
    Ni/CeO273.5062.70
    Ru/Nb2O541.7037.50
    Ru/CeO2100.0082.50
    Ru-Ni/CeO290.0080.00
    Ru/ZrO210.000.40
    Ru/Al2O312.500.76
    Ru/CeOx100.0090.20
    Reaction conditions: catalyst 0.05 g, reaction time 3 h, reaction temperature 140 ℃, hydrogen pressure 3 MPa.
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出版历程
  • 收稿日期:  2023-05-12
  • 修回日期:  2023-08-28
  • 录用日期:  2023-09-12
  • 网络出版日期:  2023-09-18
  • 刊出日期:  2024-03-08

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