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N掺杂Mo/HZSM-5催化剂制备及对甲烷无氧芳构化催化性能影响

韩运达 张新庄 吴保强 张浩 黄帆 马晓迅

韩运达, 张新庄, 吴保强, 张浩, 黄帆, 马晓迅. N掺杂Mo/HZSM-5催化剂制备及对甲烷无氧芳构化催化性能影响[J]. 燃料化学学报, 2021, 49(4): 475-482. doi: 10.19906/j.cnki.JFCT.2021035
引用本文: 韩运达, 张新庄, 吴保强, 张浩, 黄帆, 马晓迅. N掺杂Mo/HZSM-5催化剂制备及对甲烷无氧芳构化催化性能影响[J]. 燃料化学学报, 2021, 49(4): 475-482. doi: 10.19906/j.cnki.JFCT.2021035
HAN Yun-da, ZHANG Xin-zhuang, WU Bao-qiang, ZHANG Hao, HUANG Fan, MA Xiao-xun. Preparation of N-doped Mo/HZSM-5 catalyst and its effect on performance of non-oxidative methane aromatization reaction[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 475-482. doi: 10.19906/j.cnki.JFCT.2021035
Citation: HAN Yun-da, ZHANG Xin-zhuang, WU Bao-qiang, ZHANG Hao, HUANG Fan, MA Xiao-xun. Preparation of N-doped Mo/HZSM-5 catalyst and its effect on performance of non-oxidative methane aromatization reaction[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 475-482. doi: 10.19906/j.cnki.JFCT.2021035

N掺杂Mo/HZSM-5催化剂制备及对甲烷无氧芳构化催化性能影响

doi: 10.19906/j.cnki.JFCT.2021035
基金项目: 国家重点研发计划项目(2018YFB0604603),国家自然科学基金(21536009)和陕西省重点研发计划项目(2017ZDCXL-GY-10-03,2018ZDXM-GY-167)资助
详细信息
    通讯作者:

    Tel: 13772424852, E-mail: maxym@nwu.edu.cn

  • 中图分类号: TE646

Preparation of N-doped Mo/HZSM-5 catalyst and its effect on performance of non-oxidative methane aromatization reaction

Funds: The project was supported by the National Key Research and Development Program (2018YFB0604603), the National Natural Science Foundation of China (21536009) and the Shaanxi Provincial Key Research and Development Program (2017ZDCXL-GY-10-03, 2018ZDXMGY-167)
  • 摘要: 采用三聚氰胺作为N源,N掺杂改性HZSM-5沸石分子筛后负载Mo活性金属组分,制备了一种用于甲烷无氧芳构化反应(MDA)的催化剂。采用XPS、N2吸附-脱附、XRD、H2-TPR、TEM和NH3-TPD对催化剂性质和Mo金属组分状态进行了分析表征,并考察了催化剂的甲烷无氧芳构化反应催化性能。结果表明,HZSM-5经过N掺杂改性后,会在分子筛表面生成一层含氮基团,有序调控了分子筛的酸性位点;同时会诱导Mo金属组分在催化剂表面更好的锚定落位。此方法制备的Mo/HZSM-5-CN催化剂能有效提高MDA反应的甲烷转化率和芳烃选择性,减缓了积炭的生成,展现出更优良的催化性能。
  • FIG. 611.  FIG. 611.

    FIG. 611..  FIG. 611.

    图  1  催化剂MDA催化性能评价装置

    Figure  1.  Catalytic performance evaluation device of MDA

    1: single phase valve; 2: mass flow controller; 3: four-way valve; 4: distribution board; 5: U shaped quartz tube reactor; 6: reaction heating furnace; 7: pipeline with temperature control; 8: ten way valve; 9: online chromatography

    图  2  改性前后催化剂XPS的N 1s和Mo 3d谱图

    Figure  2.  XPS spectra of N 1s and Mo 3d for the catalysts before and after modification

    图  3  改性前后催化剂的N2吸附-脱附等温曲线

    Figure  3.  N2-adsorption-desorption of catalysts before and after modification

    图  4  改性前后催化剂的XRD谱图

    Figure  4.  XRD patterns of the catalysts before and after modification

    图  5  Mo/HZSM-5和Mo/HZSM-5-CN的H2-TPR谱图

    Figure  5.  H2-TPR spectra of Mo/HZSM-5 and Mo/HZSM-5-CN

    图  6  Mo/HZSM-5和Mo/HZSM-5-CN的TEM照片

    Figure  6.  TEM images of Mo/HZSM-5 and Mo/HZSM-5-CN

    ((a1), (a2)): Mo/HZSM-5; ((b1), (b2)): Mo/HZSM-5-CN

    图  7  改性前后催化剂的NH3-TPD谱图

    Figure  7.  NH3-TPD spectra of the catalysts before and after modification

    图  8  改性前后甲烷转化率及芳烃选择性

    Figure  8.  Methane conversion rate and aromatics selectivity before and after modification

    图  9  反应后催化剂的积炭

    Figure  9.  Carbon deposit of spent catalysts

    表  1  改性前后催化剂的比表面积和孔道结构分布

    Table  1.   Surface area and pore structure distribution of the catalysts before and after modification

    CatalystSurface area
    A/(m2·g−1
    Pore volume
    v/(cm3·g−1
    totalmicroporeexternaltotalmicropore
    HZSM-5367328390.1980.139
    HZSM-5-CN318279380.1800.118
    Mo/HZSM-5293246470.1790.112
    Mo/HZSM-5-CN300255450.1670.114
    下载: 导出CSV

    表  2  改性前后催化剂的酸量分布

    Table  2.   Amounts of acid sites of the catalysts before and after modification

    CatalystWeak
    acid/
    (mmol·g−1)
    Medium
    acid/
    (mmol·g−1)
    Strong
    acid/
    (mmol·g−1)
    Total/
    (mmol·g−1)
    HZSM-50.5340.1090.3881.031
    HZSM-5-CN0.4650.1050.2150.785
    Mo/HZSM-50.3910.1220.1160.629
    Mo/HZSM-5-CN0.3620.1920.1470.701
    下载: 导出CSV

    表  3  催化剂MDA反应中不同时间点活性与积炭

    Table  3.   Analysis of catalyst activity and carbon deposition in MDA reaction

    CatalystTime/
    min
    Conversion/
    %
    Selectivity/
    %
    Carbon
    depostion/
    %
    Mo/HZSM-52018.6569.5412.8
    4013.5463.88
    609.7956.81
    807.6341.60
    Mo/HZSM-5-CN2021.6781.7510.9
    4018.0382.10
    6015.1077.50
    8010.6350.64
    下载: 导出CSV
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  • 收稿日期:  2020-12-02
  • 修回日期:  2021-01-14
  • 网络出版日期:  2021-03-30
  • 刊出日期:  2021-04-10

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