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液相体系Ru-Co3O4催化CO2加氢制甲烷过程中的溶剂效应研究

宋英健 崔晓静 邓天昇 秦张峰 樊卫斌

宋英健, 崔晓静, 邓天昇, 秦张峰, 樊卫斌. 液相体系Ru-Co3O4催化CO2加氢制甲烷过程中的溶剂效应研究[J]. 燃料化学学报, 2021, 49(2): 178-185. doi: 10.1016/S1872-5813(21)60013-0
引用本文: 宋英健, 崔晓静, 邓天昇, 秦张峰, 樊卫斌. 液相体系Ru-Co3O4催化CO2加氢制甲烷过程中的溶剂效应研究[J]. 燃料化学学报, 2021, 49(2): 178-185. doi: 10.1016/S1872-5813(21)60013-0
SONG Ying-jian, CUI Xiao-jing, DENG Tian-sheng, QIN Zhang-feng, FAN Wei-bin. Solvent effect on the activity of Ru-Co3O4 catalyst for liquid-phase hydrogenation of CO2 into methane[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 178-185. doi: 10.1016/S1872-5813(21)60013-0
Citation: SONG Ying-jian, CUI Xiao-jing, DENG Tian-sheng, QIN Zhang-feng, FAN Wei-bin. Solvent effect on the activity of Ru-Co3O4 catalyst for liquid-phase hydrogenation of CO2 into methane[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 178-185. doi: 10.1016/S1872-5813(21)60013-0

液相体系Ru-Co3O4催化CO2加氢制甲烷过程中的溶剂效应研究

doi: 10.1016/S1872-5813(21)60013-0
基金项目: 国家自然科学基金(U1910203, 21972159)资助
详细信息
    通讯作者:

    E-mail:cuixj@sxicc.ac.cn

    fanwb@sxicc.ac.cn

  • 中图分类号: O643.36; X773

Solvent effect on the activity of Ru-Co3O4 catalyst for liquid-phase hydrogenation of CO2 into methane

Funds: The project was supported by National Natural Science Foundation of China (U1910203, 21972159)
  • 摘要: 采用共沉淀法制备了Ru-Co3O4催化剂,考察了其在液相体系的CO2加氢制甲烷催化性能,并与浸渍法制备的Ru基催化剂(Ru/SiO2、Ru/CeO2、Ru/ZrO2、Ru/TiO2)进行了对比,探讨了不同溶剂(水、正丁醇、1, 4-丁内酯、DMF、十氢萘、环己烷、异辛烷)对催化性能的影响规律。发现Ru-Co3O4具有较高的加氢催化活性和产物选择性,十氢萘和异辛烷作溶剂显示出良好的催化性能。在200 °C及H2/CO2 = 3∶1(v/v, 4 MPa)条件下,CO2转化率达45.6%,CH4的选择性约97%。同位素标记实验和原位漫反射红外光谱结果表明,十氢萘和异辛烷中的叔碳离子可以起到较强的供氢作用,从而提高了催化活性。
  • 图  1  Ru-Co3O4的SEM((a)、(b))和TEM照片(c)

    Figure  1  SEM images ((a), (b)) and TEM images (c) of Ru-Co3O4

    图  2  不同焙烧样品的XRD谱图

    1: Co3O4; 2: SiO2; 3: Ru; 4: CeO2; 5, 6: the characteristic peaks of TiO2 with different crystal forms (5 is auatase and 6 is rutile); 7: ZrO2

    Figure  2  XRD patterns of calcined catalysts (a): Co3O4; (b): Ru-Co3O4; (c): Ru-SiO2; (d): Ru-CeO2; (e): Ru-ZrO2; (f): Ru-TiO2

    图  3  异辛烷标样(a)和氘代异辛烷(b)的核磁共振色谱

    Figure  3  Nuclear magnetic resonance chromatograms of standard isooctane (a) and of deuterated isooctane (b)

    图  4  室温下不同样品吸附十氢萘的漫反射红外吸附谱图

    Figure  4  DRIFTS spectra for adsorption of decalin on the surfaces of various samples at room temperature

    图  5  Ru-Co3O4催化剂表面CO2加氢的漫反射红外谱图:(a) 200 °C; (b) 不同温度下

    Figure  5  DRIFTS spectra of CO2 hydrogenation to CH4 at 200 oC on Ru-Co3O4 in CO2, decalin, (CO2+decalin), and DRIFTS spectrum of standard CH4 (from the bottom to the top direction) (a); and DRIFTS spectra of CO2 hydrogenation to CH4 at 200 oC on Ru-Co3O4 in (CO2+decalin) at different reaction temperatures (b)

    图  6  催化剂的H2-TPR谱图

    Figure  6  H2-TPR profiles of catalyst

    图  7  十氢萘溶剂中Ru-Co3O4表面CO2加氢生成甲烷的反应路径

    Figure  7  Schematic presentation for catalytic mechanism of CO2 hydrogenation to CH4 over Ru-Co3O4 in decalin solvent

    表  1  不同Ru-基催化剂液相CO2加氢制甲烷的催化性能

    Table  1  Catalytic results of various supported Ru catalysts for liquid-phase hydrogenation of CO2 to CH4

    EntryCatalystCO2
    conversion
    /%
    Selectivity of
    hydrocarbons/mol%
    CH4C2−5CO
    1Ru/SiO22.397.12.90
    2Ru/CeO25.498.81.20
    3Ru/ZrO211.397.92.10
    4Ru/TiO215.297.12.90
    5Ru-Co3O445.697.02.90.1
    6Co3O434.097.72.20.1
    reaction conditions: 100 mg of catalyst, 5 g decalin, 200 °C, initial pressure: 4 MPa of H2/CO2 gas (v/v = 3∶1), 1 h
    下载: 导出CSV

    表  2  不同溶剂中Ru-Co3O4催化剂上CO2液相加氢制甲烷性能的影响a

    Table  2  Catalytic results of Ru-Co3O4 for liquid-phase hydrogenation of CO2 to CH4 in different solventsa

    SolventCO2 conversion/%Product selectivity/%Solubility b/(mmol·L−1)
    CH4C2−5
    Water8.388.711.028.9
    Butyl alcohol21.488.711.187.2
    1,4- butyrolactone26.295.74.242.6
    DMF31.089.410.443.2
    n-Nonane31.998.51.593.5
    Decalin45.697.03.067.5
    Cyclohexane34.098.81.2
    Isooctane42.098.21.7
    a: reaction conditions: 100 mg of 1% Ru-Co3O4,5 g of solvent,200 °C,initial pressure: 4 MPa of H2/CO2 gas (v/v=3/1), 1 h; b: calculated by considering H2 filled in the reactor as standard gas
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-08-14
  • 修回日期:  2020-11-02
  • 网络出版日期:  2021-02-25
  • 刊出日期:  2021-02-08

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