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神华上湾煤在含CO气氛下的直接液化行为研究

唐博文 张瑞 刘海云 靳立军 胡浩权

唐博文, 张瑞, 刘海云, 靳立军, 胡浩权. 神华上湾煤在含CO气氛下的直接液化行为研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60451-2
引用本文: 唐博文, 张瑞, 刘海云, 靳立军, 胡浩权. 神华上湾煤在含CO气氛下的直接液化行为研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60451-2
TANG Bowen, ZHANG Rui, LIU Haiyun, JIN Lijun, HU Haoquan. Direct liquefaction behavior of Shenhua coal under CO containing atmosphere[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60451-2
Citation: TANG Bowen, ZHANG Rui, LIU Haiyun, JIN Lijun, HU Haoquan. Direct liquefaction behavior of Shenhua coal under CO containing atmosphere[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60451-2

神华上湾煤在含CO气氛下的直接液化行为研究

doi: 10.1016/S1872-5813(24)60451-2
基金项目: 中国神华煤制油化工有限公司揭榜挂帅项目(MZYHG-22-02)和国家重点研发计划(2022YFB4101302)资助
详细信息
    通讯作者:

    Tel: 0411-84986157, E-mail: hhu@dlut.edu.cn.

  • 中图分类号: TK6

Direct liquefaction behavior of Shenhua coal under CO containing atmosphere

Funds: The project was supported by China Shenhua Coal to Liquid and Chemical Co, LTD (MZYHG-22-02), and National Key Research and Development Program of China (2022YFB4101302).
  • 摘要: 本研究通过对比CO、H2、N2三种气氛下的液化行为,探究了CO对神华上湾煤液化过程的影响,并进一步研究不同CO/H2比以及催化剂对合成气条件下液化过程的影响。结果显示,在CO气氛下煤直接液化的油产率达到43.1%,比H2气氛中低4.2%,但比N2气氛下高10.2%,添加神华863催化剂后液化效果得到进一步的提升,表明,CO在液化过程中可通过水煤气变换反应和CO与煤有机结构间的反应促进煤液化。对液化产物进行GC-MS、FI-TR等分析发现,CO使液化油中苯系物、脂肪烃与含氧化合物同时增多,对液化残渣中官能团与自由基浓度的影响不明显。在CO+H2合成气下的实验结果表明,在20%CO的合成气中煤液化具有最高的油产率,达到57.4%;适当提高煤的含水量能够提升液化效果;神华863催化剂对液化过程与水煤气变换反应均具有良好的催化作用。研究工作为煤在合成气下的直接液化提供理论基础。
  • 图  1  实验设备及产物分离流程示意图

    Figure  1  Schematic diagram of experimental equipment and product separation procedure

    图  2  不同气氛下催化与非催化液化的气液固产物产率和氢耗分布

    Figure  2  Product yields and hydrogen consumption distribution of catalytic and non-catalytic liquefaction under different atmospheres

    图  3  不同气氛下催化与非催化液化的水产率和CO消耗分布

    Figure  3  Water yield and CO consumption distribution of catalytic and non-catalytic liquefaction under different atmospheres

    图  4  不同气氛下液化油的GC-MS结果

    Figure  4  GC-MS results of liquefaction oil under different atmospheres

    图  5  不同气氛下煤液化产生的沥青烯和液化残渣的FT-IR谱图

    Figure  5  FT-IR spectra of asphaltene and liquefaction residue under different atmospheres

    (a): asphaltene; (b): liquefaction residue.

    图  6  不同气氛下煤液化产生的沥青烯和液化残渣的总自由基浓度和g

    Figure  6  Total radical concentrations and g value of asphaltene and liquefaction residue under different atmospheres

    图  7  原煤以及不同反应条件下液化残渣的EPR谱图

    Figure  7  EPR spectra and fitted sub-curve of SW and its liquefaction residue under different reaction conditions

    图  8  不同CO/H2比例合成气气氛下的液化

    Figure  8  Liquefaction results under different CO/H2 ratios of syngas

    图  9  添加水量对上湾煤在20% CO合成气下液化的影响

    Figure  9  Effect of water addition on DCL

    图  10  催化剂对上湾煤在20%CO合成气下液化的影响

    Figure  10  Effect of catalyst on SW DCL

    表  1  上湾煤及神华铁基催化剂工业分析和元素分析

    Table  1  Proximate and ultimate analyses of SW and iron-based catalyst

    Sample Proximate analysis/% Ultimate analysis wdaf/%
    Mad Ad Vdaf C H N S O*
    SW 1.30 5.54 37.04 71.91 4.95 0.99 0.36 21.79
    Fe catalyst 3.96 13.12 37.40
    *: by difference.
    下载: 导出CSV

    表  2  不同实验条件下的CO2产率*

    Table  2  Yield of CO2 under different conditions

    Run Catalyst Atmosphere $Y_{{\mathrm{CO}}_2} $ (mmol·g−1)
    1 none N2 0.68
    2 none N2 0.69
    3 none H2 0.60
    4 none H2 0.63
    5 1%Fe N2 0.75
    6 1%Fe N2 0.66
    7 1%Fe H2 0.57
    8 1%Fe H2 0.59
    * Experiments at same conditions except for the catalyst and atmosphere, each condition repeated twice.
    下载: 导出CSV

    表  3  原煤及不同气氛下液化反应后残渣的EPR谱图拟合

    Table  3  Fitted results of EPR spectra of SW and liquefaction residue under different atmospheres

    Sample Fitted curve g value Line width(Gauss) Line shape Radical concentration(spins/g×1018)
    SW Sub-curve-1 2.00513 9.20 G/L 5.09
    Sub-curve-2 2.00540 5.45 G/L 6.75
    N2 Sub-curve-1 2.00474 3.25 Gauss 12.17
    Sub-curve-2 2.00369 12.50 G/L 8.41
    Sub-curve-3 2.00467 6.84 Lorenz 7 .38
    N2-Fe Sub-curve-1 2.00476 2.92 Gauss 8.44
    Sub-curve-2 2.00408 11.10 G/L 10.56
    Sub-curve-3 2.00474 6.24 Lorenz 6.80
    H2 Sub-curve-1 2.00495 3.06 Gauss 7.87
    Sub-curve-2 2.00433 11.24 G/L 7.55
    Sub-curve-3 2.00490 6.27 Lorenz 4.54
    H2-Fe Sub-curve-1 2.00490 11.64 Gauss 6.92
    Sub-curve-2 2.00367 36.70 G/L 5.16
    Sub-curve-3 2.00478 6.80 Lorenz 4.09
    CO Sub-curve-1 2.00483 3.03 Gauss 10.09
    Sub-curve-2 2.00412 11.36 G/L 11.07
    Sub-curve-3 2.00479 6.37 Lorenz 7.47
    CO-Fe Sub-curve-1 2.00496 11.63 Gauss 8.41
    Sub-curve-2 2.00427 6.58 G/L 8.88
    Sub-curve-3 2.00493 25.36 Lorenz 5.69
    下载: 导出CSV

    表  4  不同充压比合成气的色谱测量值

    Table  4  Chromatographic measurements of reaction gas

    Syngas* Initial CO pressure/
    MPa
    Measured volume
    fraction of gas/
    %
    CO H2
    20% CO 1.2 25.16 74.84
    40% CO 2.4 44.55 55.45
    60% CO 3.6 63.27 36.73
    80% CO 4.8 80.85 19.15
    * Fill the reactor with CO at the specified pressure, and then fill the reactor pressure with H2 to 6 MPa.
    下载: 导出CSV
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  • 收稿日期:  2024-03-08
  • 修回日期:  2024-04-09
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