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LiMn2O4/TiO2催化剂上甲烷氧化偶联反应性能的研究

刘玉兰 张泽凯 倪光 刘华彦 陈银飞

刘玉兰, 张泽凯, 倪光, 刘华彦, 陈银飞. LiMn2O4/TiO2催化剂上甲烷氧化偶联反应性能的研究[J]. 燃料化学学报, 2016, 44(6): 703-709.
引用本文: 刘玉兰, 张泽凯, 倪光, 刘华彦, 陈银飞. LiMn2O4/TiO2催化剂上甲烷氧化偶联反应性能的研究[J]. 燃料化学学报, 2016, 44(6): 703-709.
LIU Yu-lan, ZHANG Ze-kai, NI Guang, LIU Hua-yan, CHEN Yin-fei. Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 703-709.
Citation: LIU Yu-lan, ZHANG Ze-kai, NI Guang, LIU Hua-yan, CHEN Yin-fei. Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 703-709.

LiMn2O4/TiO2催化剂上甲烷氧化偶联反应性能的研究

详细信息
    通讯作者:

    E-mail: zzk@zjut.edu.cn

    E-mail: yfchen@zjtu.edu.cn

  • 中图分类号: O643

Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts

  • 摘要: 采用固相反应法制备了具有尖晶石结构的LiMn2O4/TiO2系列催化剂, 探讨了TiO2、Li/TiO2、Mn/TiO2、LiMn2O4及LiMn2O4/TiO2等不同组成催化剂的甲烷氧化偶联反应性能, 采用XRD、XPS、CO2-TPD和H2-TPR等表征方法对该系列催化剂进行了分析。结果表明, 具有尖晶石结构的LiMn2O4化合物具有较高的甲烷氧化偶联催化活性, 在775℃、0.1MPa、7200mL/(h·g), CH4:O2(体积比) 为2.5的条件下, 甲烷转化率可达25.8%, C2选择性可达43.2%。TiO2的存在不仅进一步提高了甲烷转化率和C2选择性, 还有效抑制了甲烷完全氧化形成CO2的过程。负载8% LiMn2O4的LiMn2O4/TiO2催化剂性能达到最优, 此时甲烷转化率达到31.6%, C2选择性为52.4%, CO2选择性降低到26.3%。考察了不同焙烧温度对催化剂活性的影响, 850℃为LiMn2O4/TiO2催化剂的最佳焙烧温度。
  • 图  1  不同组成催化剂的XRD谱图

    Figure  1  XRD patterns of catalysts with different composition

    a: TiO2; b: Li/TiO2; c: Mn/TiO2; d: LiMn2O4;e: LiMn2O4/TiO2; f: Li-Mn/TiO2

    图  2  LiMn2O4、LiMn2O4/TiO2与Li-Mn/TiO2催化剂O 1s的XPS谱图

    Figure  2  X-ray photoelectron spectra for O 1s over LiMn2O4, LiMn2O4/TiO2 and Li-Mn/TiO2 catalysts

    a: LiMn2O4; b: LiMn2O4/TiO2; c: Li-Mn/TiO2

    图  3  不同组成催化剂的CO2-TPD谱图

    Figure  3  CO2-TPD profiles of catalysts with different composition

    a: LiMn2O4; b: Li/TiO2; c: Mn/TiO2;d: LiMn2O4/TiO2; e: Li-Mn/TiO2

    图  4  不同组成催化剂的H2-TPR谱图

    Figure  4  H2-TPR profiles of catalysts with different composition

    a: LiMn2O4; b: Li/TiO2;c: Mn/TiO2; d: LiMn2O4/TiO2;e: Li-Mn/TiO2

    表  1  不同组成催化剂的催化性能

    Table  1  Catalytic performance of different catalysts

    CatalystConversion of CH4 x/%Selectivity s/% Yield w/% C2H4/C2H6
    C2COCO2 C2
    TiO222.31.676.122.30.41.0
    0.3%Li/TiO225.110.981.97.22.70.9
    5%Mn/TiO223.121.120.858.14.91.0
    LiMn2O425.843.28.148.711.11.7
    LiMn2O4/TiO230.549.721.129.215.22.1
    Li-Mn/TiO231.451.519.828.716.22.0
    notes: C2 includes ethylene and ethane; the same content of Li and Mn are included in the LiMn2O4/TiO2 and Li-Mn/TiO2 catalysts, respectively 0.3%, 5%(mass fraction); reaction conditions: t=775℃,CH4:O2 (volume ratio)=2.5,GHSV=7200mL/(h·g)
    下载: 导出CSV

    表  2  不同负载量LiMn2O4/TiO2催化剂的催化性能

    Table  2  Catalytic activity of LiMn2O4/TiO2 catalysts with different loadings

    CatalystConversion of CH4 x/%Selectivity s/% Yield w/% C2H4/C2H6
    C2COCO2 C2
    4%LiMn2O4/TiO228.946.218.735.113.42.1
    6%LiMn2O4/TiO229.747.625.427.014.22.1
    8%LiMn2O4/TiO231.652.421.326.316.62.3
    10%LiMn2O4/TiO230.850.219.929.915.51.9
    12%LiMn2O4/TiO228.147.915.536.613.51.8
    下载: 导出CSV

    表  3  不同焙烧温度对LiMn2O4/TiO2催化剂性能的影响

    Table  3  Influence of calcination temperature on performance of LiMn2O4/TiO2catalysts

    CatalystConversion of CH4 x/%Selectivity s/% Yield w/% C2H4/C2H6
    C2COCO2 C2
    LiMn2O4/TiO2(500℃)29.730.555.414.19.12.1
    LiMn2O4/TiO2(850℃)30.549.721.129.215.22.1
    LiMn2O4/TiO2 (1000℃)27.931.933.035.18.91.8
    下载: 导出CSV

    表  4  通过O 1s谱图得LiMn2O4/TiO2与Li-Mn/TiO2催化剂表面活性氧物种的组成

    Table  4  Surface composition of LiMn2O4/TiO2 and Li-Mn/TiO2 catalysts obtained using O 1s photoelectron spectroscopy

    CatalystO22- O- O2- $\frac{\text{O}_{2}^{2-}+{{\text{O}}^{-}}}{{{\text{O}}^{2-}}}$
    E/eVwatom/% E/eVwatom/% E/eVwatom/%
    LiMn2O4/TiO2530.741.3530.16.1528.952.6 0.90
    Li-Mn/TiO2531.143.0 530.19.9528.947.1 1.12
    LiMn2O4530.632.9532.1(CO32-)8.8528.958.3 0.56
    下载: 导出CSV

    表  5  H2-TPR谱图半定量分析

    Table  5  Semi-quantitative analysis of H2-TPR profiles

    CatalystArea of peaksH2 consumption
    /(mmol·g-1)
    LiMn2O436214.015.80
    Li/TiO2514.480.08
    Mn/TiO21642.040.26
    LiMn2O4/TiO21710.780.27
    Li-Mn/TiO21763.710.28
    下载: 导出CSV
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  • 收稿日期:  2015-12-21
  • 修回日期:  2016-03-23
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-06-10

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