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不同P负载量对Co-Mo/γ-Al2O3煤焦油加氢脱硫性能影响的研究

胡乃方 崔海涛 邱泽刚 赵亮富 孟欣欣 赵正权 敖广宇

胡乃方, 崔海涛, 邱泽刚, 赵亮富, 孟欣欣, 赵正权, 敖广宇. 不同P负载量对Co-Mo/γ-Al2O3煤焦油加氢脱硫性能影响的研究[J]. 燃料化学学报, 2016, 44(6): 745-753.
引用本文: 胡乃方, 崔海涛, 邱泽刚, 赵亮富, 孟欣欣, 赵正权, 敖广宇. 不同P负载量对Co-Mo/γ-Al2O3煤焦油加氢脱硫性能影响的研究[J]. 燃料化学学报, 2016, 44(6): 745-753.
HU Nai-fang, CUI Hai-tao, QIU Ze-gang, ZHAO Liang-fu, MENG Xin-xin, ZHAO Zheng-quan, AO Guang-yu. Effect of phosphorus loadings on the performance of Co-Mo/γ-Al2O3 in hydrodesulfurization of coal tar[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 745-753.
Citation: HU Nai-fang, CUI Hai-tao, QIU Ze-gang, ZHAO Liang-fu, MENG Xin-xin, ZHAO Zheng-quan, AO Guang-yu. Effect of phosphorus loadings on the performance of Co-Mo/γ-Al2O3 in hydrodesulfurization of coal tar[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 745-753.

不同P负载量对Co-Mo/γ-Al2O3煤焦油加氢脱硫性能影响的研究

基金项目: 

中国科学院战略性先导科技专项 XDA07020200

中国科学院战略性先导科技专项"天然气" XDA05010302

和鲁奇炉气化煤焦油加氢技术开发 CFBYKJ-JSFW-01-2014

详细信息
  • 中图分类号: TQ519

Effect of phosphorus loadings on the performance of Co-Mo/γ-Al2O3 in hydrodesulfurization of coal tar

More Information
  • 摘要: 以分步浸渍法在固定MoO3、CoO含量 (质量分数) 为13.50%、2.11%的条件下, 通过改变磷酸浓度, 制备了不同P负载量的Co-Mo/γ-Al2O3催化剂。考察了不同的P负载量催化剂对内蒙古赤峰中温煤焦油加氢脱硫性能的影响。并以NH3程序升温脱附 (NH3-TPD)、X射线衍射 (XRD)、X射线光电子能谱 (XPS) 等手段对催化剂的结构性质进行了表征。结果表明, 适宜的P负载量可减弱活性组分与载体间的相互作用, 利于活性组分均匀分散在载体表面, 改善了催化剂的还原、硫化性能和酸性分布, 从而提高了催化剂的加氢脱硫活性。当磷酸质量分数为4%时, 催化剂表现出最佳的加氢脱硫性能, 硫脱除率达到96.98%。不同P负载量Co-Mo/γ-Al2O3催化剂加氢脱硫活性对应的磷酸浓度顺序为:4% >2% >6% >1% >0 >8%。
  • 图  1  催化剂的XRD谱图

    Figure  1  X-ray diffraction of catalysts

    图  2  催化剂的NH3-TPD谱图

    Figure  2  NH3-TPD profiles of catalysts

    图  3  磷酸与γ-Al2O3的表面反应

    Figure  3  Surface reaction of phosphoric acid with γ-Al2O3

    图  4  催化剂的H2-TPR谱图

    Figure  4  H2-TPR profiles of catalysts

    图  5  催化剂的XPS谱图

    Figure  5  XPS patterns of sulfided catalysts

    (a), (b): P0-P8; (c), (d): P4

    图  6  催化剂的HRTEM照片

    Figure  6  HRTEM images of catalysts

    (a): P0; (b): P1; (c): P2; (d): P4; (e): P6; (f): P8

    图  7  不同催化剂的煤焦油HDS性能

    Figure  7  HDS activity of catalysts to coal tar

    t=380℃, p=8.0MPa, LHSV=0.3h-1, H2:oil=1900:1

    表  1  催化剂的组成及含量

    Table  1  Compositions and contents of catalysts

    CatalystContent of component w/%Impregnating solution (aq)
    MoO3CoOP2O5abc
    P013.502.110 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    P113.502.111.04H3PO4 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    P213.502.112.08H3PO4 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    P413.502.114.16H3PO4 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    P613.502.116.44H3PO4 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    P813.502.118.83H3PO4 (NH4)6Mo7O24·4H2OCo (NO3)2·6H2O
    a: the first-step impregnation; b: the second-step impregnation; c: the third-step impregnation
    下载: 导出CSV

    表  2  中温煤焦油的元素组成

    Table  2  Chemical compositions of middle-temperature coal tar

    ElementCHNSO
    Content w/%83.148.340.400.667.46
    下载: 导出CSV

    表  3  催化剂的孔结构

    Table  3  Pore structure parameters of the catalyst

    Catalyst γ-Al2O3P0P1P2P4P6P8
    BET surface area A/(m2·g-1)292.77245.50244.80238.08226.04209.29211.43
    Pore volume v/(cm3·g-1)0.670.500.510.470.500.450.48
    Average pore diameter d/nm9.118.228.288.498.779.039.12
    下载: 导出CSV

    表  4  催化剂的NH3-TPD酸量分析

    Table  4  Acid amount analysis of catalysts by NH3-TPD

    CatalystAcid amount
    weakmediumstrongtotal
    γ-Al2O31.001.001.003.00
    P00.941.110.752.8
    P10.571.070.612.25
    P20.661.100.632.39
    P40.621.270.752.64
    P60.721.220.562.5
    P80.821.080.360.75
    下载: 导出CSV

    表  5  催化剂的硫化度

    Table  5  Sulfuration degree of catalysts

    CatalystP0P1P2P4P6P8
    Mo4+/Mo0.770.740.770.800.780.80
    S/Mo0.060.060.060.070.070.07
    Co-MoS/Co0.290.310.290.290.200.11
    Co-ox/Co0.340.360.440.410.460.49
    下载: 导出CSV

    表  6  煤焦油及加氢产物的GC-MS分析

    Table  6  GC-MS analysis of coal tar and products

    CompositionCoal-tarP0P1P2P4P6P8
    Alkane11.0514.0514.1814.6216.1514.7813.55
    Cycloparaffin024.0423.9324.9625.7124.3619.54
    Benzene25.6721.0422.9224.0723.1024.5825.04
    Naphthalenes16.1022.9123.5522.4321.2723.3725.46
    Phenols28.93000.09000
    Indene4.8110.569.699.288.668.8810.23
    Fluorene3.672.151.61.781.431.431.48
    Organic acids0.110.6700.39000
    Ketones0.9300.460000
    Eneyne2.791.850.881.060.571.01.86
    Aldehydes00000.880.880
    Anthracenes0.350.520.9200.560.560
    Phenanthrenes01.731.571.311.161.661.34
    Furans1.59000000
    Others41.480.30.010.510.21.85
    Total100100100100100100100
    下载: 导出CSV
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  • 收稿日期:  2015-12-16
  • 修回日期:  2016-01-22
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-06-10

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