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Char structure evolution and behaviors of sodium species during catalytic gasification of sodium-rich direct coal liquefaction residue under CO2 atmosphere

LI Pei ZHU Chao-chao HAN Lu LI Xiao FENG Xiao-bo YAO Qin YU Shi MENG Xian-liang WANG Peng WEI Shuai

李佩, 朱超超, 韩露, 李晓, 冯晓博, 姚钦, 俞时, 孟献梁, 王鹏, 卫帅. 富钠液化残渣CO2气化过程煤焦结构演化及钠赋存形态迁移规律[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60077-X
引用本文: 李佩, 朱超超, 韩露, 李晓, 冯晓博, 姚钦, 俞时, 孟献梁, 王鹏, 卫帅. 富钠液化残渣CO2气化过程煤焦结构演化及钠赋存形态迁移规律[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60077-X
LI Pei, ZHU Chao-chao, HAN Lu, LI Xiao, FENG Xiao-bo, YAO Qin, YU Shi, MENG Xian-liang, WANG Peng, WEI Shuai. Char structure evolution and behaviors of sodium species during catalytic gasification of sodium-rich direct coal liquefaction residue under CO2 atmosphere[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60077-X
Citation: LI Pei, ZHU Chao-chao, HAN Lu, LI Xiao, FENG Xiao-bo, YAO Qin, YU Shi, MENG Xian-liang, WANG Peng, WEI Shuai. Char structure evolution and behaviors of sodium species during catalytic gasification of sodium-rich direct coal liquefaction residue under CO2 atmosphere[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60077-X

富钠液化残渣CO2气化过程煤焦结构演化及钠赋存形态迁移规律

doi: 10.1016/S1872-5813(22)60077-X
详细信息
  • 中图分类号: TQ541

Char structure evolution and behaviors of sodium species during catalytic gasification of sodium-rich direct coal liquefaction residue under CO2 atmosphere

  • 摘要: 利用气化技术处理煤液化残渣制备合成气是煤液化残渣高效洁净利用的有效方式。为详细研究富钠液化残渣原位催化气化反应过程,本文采用N2吸附、FTIR、XRD、SEM和Raman分析,系统考察了富钠液化残渣CO2气化过程煤焦结构演化和钠赋存形态变迁规律。实验结果表明,富钠液化残渣钠离子高温下易诱导液化残渣孔结构发生变化,尤其拓展了介孔结构,介孔体积由0.05 cm3/g增加至最大0.16 cm3/g。随气化反应进行,煤焦中相继出现不同晶体化合物,XRD分析显示多数晶体矿物质为含钙矿物质,没有明显含钠矿物质的衍射峰,可能是钠离子高温下易挥发及含钠化合物晶体存在缺陷所致。与含钠矿物质相比,含钙矿物质更易与液化残渣中铝硅酸盐反应,从而使含钠矿物质气化过程保持了催化活性。煤焦(GR + VL + VR)/D的比率先升高后降低,分别与芳香族的解离及小芳香环结构重排成大芳香环结构有关。此外,钠离子释放率与气化反应时间密切相关,液化残渣中大部分钠离子在气化初期挥发至气相,与负载水溶性钠盐液化残渣相比,富钠液化残渣钠离子高温释放率较低。
  • Figure  1  The diagram of fixed-bed reactor (1-Control panel, 2-Balance, 3-Heating furnace, 4-Quartz tube, 5-Condenser, 6-Tar collecting plant)

    Figure  2  Pore size distribution of chars obtained at different gasification time

    Figure  3  SEM images of Char-25 and the colour mapping of sodium species

    Figure  4  XRD patterns of chars obtained at different time

    Figure  5  FTIR spectra of chars obtained at different time

    Figure  6  Raman spectra of chars obtained at different time

    Figure  7  Deconvolution of Raman spectra for zone 1800–800 cm–1

    Figure  8  Release ratio of sodium species during gasification process

    Figure  9  XRD patterns of DCLR and corresponding chars

    Figure  10  FTIR spectra of Char-1, Char-2, and Char-3

    Figure  11  Raman spectra of gasification chars (a) and typical deconvolution for zone 1800–800 cm–1(b, c, d)

    Table  1  Pore characteristics of chars obtained at different gasification time

    SampleVmic (cm3·g–1)Vmes (cm3·g–1)SBET (m2·g–1)
    Char-50.040.05287.73
    Char-150.050.05322.53
    Char-250.050.16336.85
    Char-350.050.11266.51
    Char-450.040.07224.20
    Char-550.030.05148.20
    下载: 导出CSV

    Table  2  Carbon conversion versus gasification time

    Gasification time (min)51525354555
    X (wt.%)44.8248.1259.3167.4979.3883.30
    下载: 导出CSV

    Table  3  Ultimate analysis of DCLR and chars

    SampleUltimate analysis (daf)
    CHNOaS
    Char-5 79.52 2.55 0.74 15.46 1.73
    Char-15 83.11 1.71 1.03 12.67 1.50
    Char-25 80.95 1.94 0.77 15.29 1.05
    Char-35 78.33 1.53 0.94 18.37 0.80
    Char-45 74.73 1.52 0.64 22.02 1.09
    Char-55 70.54 1.25 0.66 27.14 1.08
    Char-1 75.80 1.87 0.76 20.54 1.04
    Char-2 89.03 1.73 0.83 7.35 0.66
    Char-3 78.02 2.15 0.88 18.36 0.60
    a by difference
    下载: 导出CSV

    Table  4  Summary of band assignment [27]

    Band nameBand position, cm–1Description
    GL 1700 carbonyl group C=O
    G 1590 graphite $ {\mathrm{E}}_{2\mathrm{g}}^{2} $; aromatic ring quadrant breathing; alkene C=C
    GR 1540 aromatics with 3–5 rings; amorphous carbon structures
    VL 1465 methylene or methyl; semi-circle breathing of aromatic rings; amorphous carbon structures
    VR 1380 methyl group; semi-circle breathing of aromatic rings; amorphous carbon structures
    D 1300 D band on highly ordered carbonaceous materials; C–C between aromatic rings and aromatics with not less than 6 rings
    S 1230 aryl-alkyl ether; para-aromatics
    SL 1185 Caromatic–Calkyl; aromatic (aliphatic) ethers; C–C on hydro-aromatic rings; hexagonal diamond carbon sp3; C–H on aromatic rings
    SR 1060 C–H on aromatic rings; benzene (ortho-di-substituted) ring
    R 960–800 C–C on alkanes and cyclic alkanes; C–H on aromatic rings
    下载: 导出CSV

    Table  5  Parameters of Raman peak fitting curve

    AssignmentChar-5Char-15Char-25Char-35Char-45Char-55Char-1Char-2Char-3
    Total area ( × 105) 1.56 1.63 2.08 2.26 3.29 4.91 5.70 4.18 4.95
    (GR + VL + VR)/D 0.87 1.56 1.70 1.52 1.35 1.37 1.23 1.51 1.06
    GR/D 0.20 0.28 0.22 0.22 0.26 0.31 0.43 0.33 0.19
    下载: 导出CSV
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  • 收稿日期:  2022-09-29
  • 录用日期:  2022-10-25
  • 修回日期:  2022-10-25
  • 网络出版日期:  2022-12-26

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