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煤直接液化催化剂预硫化过程中氢的作用研究

代浩杉 田磊 熊严坤 冯富祥 杨勇 马智 郭强 刘源

代浩杉, 田磊, 熊严坤, 冯富祥, 杨勇, 马智, 郭强, 刘源. 煤直接液化催化剂预硫化过程中氢的作用研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60008-2
引用本文: 代浩杉, 田磊, 熊严坤, 冯富祥, 杨勇, 马智, 郭强, 刘源. 煤直接液化催化剂预硫化过程中氢的作用研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60008-2
DAI Hao-shan, TIAN Lei, XIONG Yan-kun, FENG Fu-xiang, YANG Yong, MA Zhi, GUO Qiang, LIU Yuan. Research of hydrogen action during pre-sulfidation of direct coal liquefaction catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60008-2
Citation: DAI Hao-shan, TIAN Lei, XIONG Yan-kun, FENG Fu-xiang, YANG Yong, MA Zhi, GUO Qiang, LIU Yuan. Research of hydrogen action during pre-sulfidation of direct coal liquefaction catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60008-2

煤直接液化催化剂预硫化过程中氢的作用研究

doi: 10.1016/S1872-5813(22)60008-2
基金项目: 国家重点研发计划(2017YFB0602401)和国家自然科学基金面上项目(22178368)资助
详细信息
    通讯作者:

    yuanliu@tju.edu.cn, guoqiang@synfuelschina.com.cn

  • 中图分类号: TQ426;TQ529

Research of hydrogen action during pre-sulfidation of direct coal liquefaction catalyst

Funds: National Key Research and Development Program of China, 2017YFB0602401; General Program of National Natural Science Foundation of China, 22178368;
  • 摘要: 在不同温度、不同氢气分压下预硫化制备了系列硫铁催化剂,并在5MPa 1% H2S-H2气氛、360 ℃下研究了其催化萘加氢活性。借助XRD、MES、SEM-EDS、ICP和GC-MS等表征手段,研究了不同温度下氢气在预硫化过程中的作用。结果表明,预硫化过程中氢气的引入有利于硫的传递,从而促进了硫化。在不同温度下均有利于活性相Fe1-xS生成,但不同预硫化温度下氢气的作用有所不同。50 ℃预硫化时,氢气的引入可以有利于硫的传递,使得催化活性有所上升,但该温度下依然存在大量单质Fe和单质S;150 ℃预硫化时催化活性最好,单质Fe含量下降没有单质S生成,随着氢气分压的增大,萘加氢转化率由60.6%增加至69.1%;300 ℃预硫化时氢气将催化剂表面的硫还原至低价态,不利于硫的传递,在催化剂颗粒内部观察到晶态的Fe3O4,进而催化活性有不同程度的下降。
  • 图  1  催化剂活性评价示意图

    Figure  1  Schematic diagram of catalyst activity evaluation

    图  2  催化剂前驱体的程序升温硫化(TPS)

    Figure  2  Temperature programmed sulfidation (TPS) results of catalyst precursor

    图  3  催化剂前驱体的H2-TPR谱图

    Figure  3  Results of H2-TPR of catalyst precursor

    图  4  不同温度和不同氢气分压预硫化的萘加氢

    Figure  4  Results of naphthalene hydrogenation at different hydrogen partial pressures of 50, 150 and 300 ℃ (5 MPa, 1% H2S-H2, 360 ℃, 1 h)

    图  5  Cat-50-p系列催化剂的XRD谱图

    Figure  5  XRD patterns of CAT-50-p series catalysts

    图  6  Cat-50-p经THF溶解后上清液的GC-MS谱图

    Figure  6  GC-MS results of supernatant of dissolved by THF

    图  7  硫化过程及硫化催化剂颗粒结构

    Figure  7  Pre-sulfuration process and particle structure of presulfidation catalyst

    图  8  Cat-150-p系列催化剂的XRD谱图

    Figure  8  XRD patterns of CAT-150-p series catalysts

    图  9  Cat-300-p系列催化剂的XRD谱图

    Figure  9  XRD patterns of CAT-300-p series catalysts

    图  10  Cat-300-95切割后SEM照片

    Figure  10  SEM results of CAT-300-95 after cutting

    表  1  Mössbauer谱的拟合参数

    Table  1  Parameters of Mössbauer spectrum

    NameSiteIS/(mm·s−1)QS/(mm·s−1)H(T)
    Hexagonal pyrrhotite10.740.0133.01
    20.720.0230.44
    30.710.0228.18
    40.740.0125.63
    Monoclinic pyrrhotite10.85(1)−0.035(4)33.4(1)
    20.86(2)0.084(10)31.4(2)
    30.81(1)−0.086(10)27.1(1)
    4a0.83(1)0.084(15)24.4(2)
    4b0.82(1)0.166(15)20.7(2)
    Greigiteoctahedral0.66-32.7
    tetrahedral0.38-31.9
    Troilite-0.89−0.1432.8
    Pyrite-0.43(1)0.66(1)-
    Maghemitex0.47−0.0151.0
    y0.34−0.0348.1
    MagnetiteA0.420.0651.6
    B0.990.8951.0
    Highly dispersed Fe[-0.02−0.0325.0
    α-Fe-0.090.0433.8
    下载: 导出CSV

    表  2  Cat-50-p的Mössbauer谱解析

    Table  2  Mössbauer spectrum results of Cat-50-p

    pFeS2Fe3S4Fe1-xSFeSFe2O3Fe3O4FeFe3+
    (spm)
    Fe2+
    (spm)
    00.03.715.17.640.022.18.72.01.0
    50.06.421.74.037.216.510.62.31.2
    200.08.425.51.628.015.416.73.50.9
    450.08.525.50.432.613.215.83.10.9
    900.017.831.63.217.64.320.03.91.8
    950.016.331.75.112.72.624.95.31.4
    下载: 导出CSV

    表  3  Cat-50-p的(S/Fe)atom和单质硫质量

    Table  3  (S/Fe) atom and elemental sulfur quality results for CAT-50-p

    p0520459095
    S/Fe0.870.880.890.961.141.16
    S质量/g/gcat0.01550.01250.00940.00790.00680.0056
    下载: 导出CSV

    表  4  Cat-50-p的XPS拟合

    Table  4  XPS fitting results of CAT-50-p

    Fe(0)Fe(Ⅱ)-SFe(Ⅲ)-SFe(Ⅱ)-OFe(Ⅲ)-OS22−S2−S/S8
    Cat-50-00.0%2.3%0.9%6.4%90.4%7.1%78.9%14.0%
    Cat-50-200.0%7.9%7.5%7.7%76.9%16.7%80.5%2.8%
    Cat-50-450.0%16.5%18.4%10.1%55.1%32.1%67.9%0.0%
    Cat-50-950.0%22.7%32.6%15.2%29.5%33.9%66.1%0.0%
    下载: 导出CSV

    表  5  Cat-150-p的Mössbauer谱解析

    Table  5  Mössbauer spectrum results of Cat-150-p

    pFeS2Fe3S4Fe1-xSFeSFe2O3Fe3O4Fe
    021.614.423.90.024.211.05.0
    518.916.022.73.421.912.64.5
    2016.516.525.83.225.37.45.3
    4514.822.428.60.316.57.69.8
    9015.219.042.62.72.16.312.2
    9515.620.643.82.52.84.310.4
    下载: 导出CSV

    表  6  Cat-150-p的(S/Fe)atom

    Table  6  (S/Fe) atom results for CAT-150-p

    p0520459095
    S/Fe0.920.940.961.031.191.23
    下载: 导出CSV

    表  7  Cat-150-p的XPS拟合结果

    Table  7  XPS fitting results of CAT-150-p

    Fe(0)Fe(Ⅱ)-SFe(Ⅲ)-SFe(Ⅱ)-OFe(Ⅲ)-OS22−S2−S/S8
    Cat-150-00.0%25.2%5.3%22.1%47.4%38.6%60.2%1.3%
    Cat-150-200.0%24.3%15.1%21.3%39.3%36.0%64.0%0.0%
    Cat-150-450.0%24.7%11.7%18.6%45.0%31.6%68.4%0.0%
    Cat-150-950.0%28.5%23.5%21.7%26.3%37.9%62.1%0.0%
    下载: 导出CSV

    表  8  Cat-300-p的Mossbauer谱解析

    Table  8  Mössbauer spectrum results of Cat-300-p

    pFeS2Fe3S4Fe1-xSFeSFe2O3Fe3O4Fe
    020.99.426.20.028.212.92.4
    55.710.840.24.224.914.20.0
    202.24.755.54.116.614.12.8
    453.09.757.31.39.815.23.8
    901.76.963.45.88.810.52.9
    956.77.953.25.813.29.33.9
    下载: 导出CSV

    表  9  Cat-300-p的(S/Fe)atom结果

    Table  9  (S/Fe) atom results for CAT-300-p

    p0520459095
    S/Fe0.950.870.840.900.900.91
    下载: 导出CSV

    表  10  Cat-300-95的SEM-EDS的(O/S)wt

    Table  10  (O/S) wt results of SEM-EDS of CAT-300-95

    Site 1Site 2Site 3Site 4Site 5
    a0.590.650.790.700.61
    b0.680.600.711.440.66
    c0.740.770.940.920.88
    d0.220.343.520.470.69
    下载: 导出CSV

    表  11  Cat-300-p的XPS拟合

    Table  11  XPS fitting results of CAT-300-p

    Fe(0)Fe(Ⅱ)-SFe(Ⅲ)-SFe(Ⅱ)-OFe(Ⅲ)-OS22−S2−S/S8
    Cat-300-00.0%23.7%13.1%13.3%49.9%45.3%54.7%0.0%
    Cat-300-200.0%23.7%11.9%18.8%45.6%31.6%68.4%0.0%
    Cat-300-450.0%26.0%24.0%22.2%27.9%20.6%79.4%0.0%
    Cat-300-950.0%29.8%25.2%21.5%23.5%19.5%80.5%0.0%
    下载: 导出CSV

    表  12  不同温度分压为0和95时的Mössbauer谱解析

    Table  12  Mössbauer spectrum results of 0 and 95 in different temperature

    FeS2Fe3S4Fe1-xSFeSFe2O3Fe3O4FeFe3+
    (spm)
    Fe2+
    (spm)
    Cat-50-00.03.715.17.640.022.18.72.01.0
    Cat-50-950.016.331.75.112.72.624.95.31.4
    Cat-150-021.614.423.90.024.211.05.0--
    Cat-150-9515.620.643.82.52.84.310.4--
    Cat-300-020.99.426.20.028.212.92.4--
    Cat-300-956.77.953.25.813.29.33.9--
    下载: 导出CSV

    表  13  不同温度分压为0和95时的(S/Fe)atom结果

    Table  13  (S/Fe) atom results for 0 and 95 in different temperature

    Cat-50-0Cat-50-95Cat-150-0Cat-150-95Cat-300-0Cat-300-95
    S/Fe0.871.160.821.230.950.91
    下载: 导出CSV

    表  14  不同温度下分压为0和95时的XPS拟合

    Table  14  XPS fitting results of 0 and 95 in different temperature

    Fe(0)Fe(Ⅱ)-SFe(Ⅲ)-SFe(Ⅱ)-OFe(Ⅲ)-OS22−S2−S/S8
    Cat-50-00.0%2.3%0.9%6.4%90.4%7.1%78.9%14.0%
    Cat-50-950.0%22.7%32.6%15.2%29.5%33.9%66.1%0.0%
    Cat-150-00.0%25.2%5.3%22.1%47.4%38.6%60.2%1.3%
    Cat-150-950.0%28.5%23.5%21.7%26.3%37.9%62.1%0.0%
    Cat-300-00.0%23.7%13.1%13.3%49.9%45.3%54.7%0.0%
    Cat-300-950.0%29.8%25.2%21.5%23.5%19.5%80.5%0.0%
    下载: 导出CSV
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  • 收稿日期:  2022-02-16
  • 录用日期:  2022-03-17
  • 修回日期:  2022-03-11
  • 网络出版日期:  2022-03-29

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