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不同金属含量Ni-W催化剂的煤焦油加氢脱硫脱氮性能研究

孟欣欣 邱泽刚 郭兴梅 李振荣 胡乃方 宋毛宁 赵亮富

孟欣欣, 邱泽刚, 郭兴梅, 李振荣, 胡乃方, 宋毛宁, 赵亮富. 不同金属含量Ni-W催化剂的煤焦油加氢脱硫脱氮性能研究[J]. 燃料化学学报(中英文), 2016, 44(5): 570-578.
引用本文: 孟欣欣, 邱泽刚, 郭兴梅, 李振荣, 胡乃方, 宋毛宁, 赵亮富. 不同金属含量Ni-W催化剂的煤焦油加氢脱硫脱氮性能研究[J]. 燃料化学学报(中英文), 2016, 44(5): 570-578.
MENG Xin-xin, QIU Ze-gang, GUO Xing-mei, LI Zhen-rong, HU Nai-fang, SONG Mao-ning, ZHAO Liang-fu. Hydrodenitrogenation and hydrodesulfurization of coal tar on Ni-W catalysts with different metal loadings[J]. Journal of Fuel Chemistry and Technology, 2016, 44(5): 570-578.
Citation: MENG Xin-xin, QIU Ze-gang, GUO Xing-mei, LI Zhen-rong, HU Nai-fang, SONG Mao-ning, ZHAO Liang-fu. Hydrodenitrogenation and hydrodesulfurization of coal tar on Ni-W catalysts with different metal loadings[J]. Journal of Fuel Chemistry and Technology, 2016, 44(5): 570-578.

不同金属含量Ni-W催化剂的煤焦油加氢脱硫脱氮性能研究

基金项目: 

中国科学院战略性先导科技专项 XDA07020200

鲁奇炉气化煤焦油加氢技术开发 CFBYKJ-JSFW-01-2014

详细信息
    通讯作者:

    郭兴梅, Tel: 0351-6018564, 0351-4041526, E-mail: linyrain@163.com

    赵亮富, E-mail: lfzhao@sxicc.ac.cn

  • 中图分类号: TQ519

Hydrodenitrogenation and hydrodesulfurization of coal tar on Ni-W catalysts with different metal loadings

Funds: 

the Strategic Science and Technology Project of Chinese Academy of Science XDA07020200

the Development of Gasification Coal Tar Hydrogenation in Furnace of Lu Qi CFBYKJ-JSFW-01-2014

  • 摘要:γ-Al2O3为载体, 采用等体积浸渍法制备了五种金属原子比相同而金属负载量不同的Ni-W基催化剂。通过X射线衍射(XRD)、光电子能谱(XPS)、程序升温脱附(NH3-TPD)、氮气吸附、高分辨透射电镜(HRTEM) 等技术对催化剂进行了表征。在固定床反应器中, 以中低温煤焦油为原料, 考察了催化剂的加氢脱氮(HDN) 和加氢脱硫(HDS) 性能。结果表明, 当Ni/W原子比为0.786时, 负载金属后, 催化剂的总酸量减少, 且以中强酸为主。随着金属负载量的增加, 催化剂的硫化程度逐渐增加, HDN活性先增加后降低, 当WO3负载量为24%时达到最优值, 而HDS活性逐渐增强。
  • 图  1  催化剂的XRD谱图

    Figure  1  X-ray diffraction of the catalysts

    图  2  载体及催化剂的孔径分布

    Figure  2  Pore size distributions of the support and catalysts

    图  3  载体及催化剂的NH3-TPD谱图

    Figure  3  NH3-TPD profiles of the support and catalysts

    图  4  硫化态催化剂的W 4f和Ni 2p XPS谱图

    Figure  4  W 4f and Ni 2p XPS patterns of sulfided catalysts

    (a), (b): wide-scan spectra of W 4f and Ni 2p; (c), (d): decomposed peaks of W 4f and Ni 2p

    图  5  催化剂的HRTEM照片

    Figure  5  HRTEM images of the catalysts

    (a): NiW/γ-Al2O3; (b): cat-W16; (c): cat-W20; (d): cat-W24; (e): cat-W28; (f): cat-W32

    图  6  硫化后催化剂中WS2(a) 长度和层数(b) 的分布

    Figure  6  Distributions in WS2 length (a) and layers (b) of the catalysts after sulfidation

    图  7  催化剂对煤焦油的HDN和HDS活性

    Figure  7  HDN and HDS activity of the catalysts for coal tar reaction conditions: t=380 ℃, p=8.0 MPa, LHSV=0.3 h-1, H2/oil=1 500

    表  1  催化剂的金属含量及配比

    Table  1  Metal content and atomic ratio of the catalysts

    WO3 w/% NiO w/% Ni/W Ni/(Ni+W)
    Cat-W16 16 4.05 0.786 0.44
    Cat-W20 20 5.06 0.786 0.44
    Cat-W24 24 6.07 0.786 0.44
    Cat-W28 28 7.09 0.786 0.44
    Cat-W32 32 8.10 0.786 0.44
    下载: 导出CSV

    表  2  中低温煤焦油的元素分析

    Table  2  Chemical compositions of low and middle-temperature coal tar

    Contentw/%
    C H N S O*
    83.05 8.81 0.88 0.27 6.99
    *: the oxygen content was calculated by the subtraction method
    下载: 导出CSV

    表  3  载体及催化剂的孔结构

    Table  3  Pore structure parameters of the support and catalysts

    Catalyst Al2O3 cat-W16 cat-W20 cat-W24 cat-W28 cat-W32
    BET surface Area A/(m2·g-1) 256.86 208.46 193.04 182.34 164.56 147.38
    Pore volume v/(cm3·g-1) 0.62 0.48 0.44 0.41 0.36 0.33
    Average pore diameter d/nm 9.71 9.14 9.04 8.92 8.82 7.81
    下载: 导出CSV

    表  4  载体及催化剂的BJH孔结构分析

    Table  4  Pore size distributions of the support and catalysts

    d/nm Al2O3 cat-W16 cat-W20 cat-W24 cat-W28 cat-W32
    V/cm3 w/% V/cm3 w/% V/cm3 w/% V/cm3 w/% V/cm3 w/% V/cm3 w/%
    >20 0.126 19.968 0.097 20.083 0.089 20.045 0.085 20.531 0.075 20.270 0.070 21.148
    13-20 0.067 10.618 0.053 10.973 0.050 11.261 0.046 11.111 0.041 11.081 0.037 11.178
    10-13 0.097 15.372 0.067 13.872 0.057 12.838 0.057 13.768 0.041 11.081 0.035 10.574
    7-10 0.163 25.832 0.122 25.259 0.106 23.874 0.095 22.947 0.086 23.243 0.076 22.961
    4-7 0.129 20.444 0.097 20.083 0.097 21.847 0.086 20.773 0.086 23.243 0.077 23.263
    2-4 0.047 7.448 0.044 9.110 0.042 9.459 0.042 10.097 0.038 10.270 0.034 10.272
    <2 0.002 0.317 0.003 0.621 0.003 0.676 0.003 0.725 0.003 0.811 0.002 0.604
    下载: 导出CSV

    表  5  载体及催化剂的酸性分布

    Table  5  Acid distributions of the support and catalysts

    Catalyst 100-200 ℃ w/% Relative content 200-350 ℃ w/% Relative content 350-550 ℃ w/% Relative content Total relative content
    Al2O3 4.74 1 43.67 1 51.58 1 1
    Cat-W16 7.08 1.18 56.71 1.03 36.21 0.56 0.79
    Cat-W20 5.77 0.77 60.42 0.87 33.81 0.41 0.63
    Cat-W24 3.25 0.44 55.19 0.81 41.56 0.52 0.64
    Cat-W28 5.61 0.58 57.49 0.80 36.90 0.45 0.61
    Cat-W32 4.51 0.72 48.27 0.83 47.22 0.69 0.75
    下载: 导出CSV

    表  6  硫化态催化剂W和Ni的结合能和硫化程度

    Table  6  Binding energy and sulfidation degree of W and Ni of the catalysts after sulfidation

    Catalyst cat-W16 cat-W20 cat-W24 cat-W28 cat-W32
    WS2 EB 4f7/2/eV 32.50 32.50 32.50 32.50 32.50
    relative content w/% 34.51 38.59 47.77 50.27 51.97
    WO3 EB 4f7/2/eV 35.90 35.90 35.90 35.90 35.90
    relative content w/% 35.01 22.81 18.27 16.52 10.54
    NiS EB 2p3/2(eV) 854.2 854.2 854.2 854.2 854.2
    relative content w/% 20.27 26.48 28.51 39.61 43.36
    NiO EB 2p3/2/eV 856.2 856.2 856.2 856.2 856.2
    relative content w/% 79.73 73.52 71.49 60.39 56.64
    下载: 导出CSV

    表  7  GC-MS对煤焦油原料及加氢产物的分析

    Table  7  Analysis of coal tar and hydrogenation products with GC-MS

    Composition Coal tar cat-W16 cat-W20 cat-W24 cat-W28 cat-W32
    Alkane 22.93 25.08 23.78 26.92 27.25 24.79
    Cycloparaffin 0.64 18.27 19.62 14.44 19.14 19.57
    Benzene 3.04 17.70 15.33 14.82 13.66 19.08
    Phenol 31.45 0.59 0.57 0.53 0.71 1.62
    Naphthalenes 18.71 23.34 23.09 22.55 23.04 19.36
    Indene 2.62 7.25 8.45 11.51 9.34 8.06
    Fluorene 2.67 1.99 2.02 1.94 2.34 2.00
    Dibenzofuran 7.60 2.00 1.96 1.97 2.28 2.03
    Anthracene phenanthrene pyrene 8.47 2.60 2.93 3.10 2.23 2.95
    Else 1.83 1.18 2.25 2.22 0.01 0.54
    Grand total 100.00 100.00 100.00 100.00 100.00 100.00
    下载: 导出CSV
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  • 收稿日期:  2015-10-23
  • 修回日期:  2016-02-02
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-05-10

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