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反应条件对哈密煤温和液化沥青质结构和热反应性的影响

张宴龙 白宗庆 冯智皓 侯冉冉 贾宇星 张婷婷 侯郁洁 孔令学 郭振兴 白进 李文

张宴龙, 白宗庆, 冯智皓, 侯冉冉, 贾宇星, 张婷婷, 侯郁洁, 孔令学, 郭振兴, 白进, 李文. 反应条件对哈密煤温和液化沥青质结构和热反应性的影响[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022020
引用本文: 张宴龙, 白宗庆, 冯智皓, 侯冉冉, 贾宇星, 张婷婷, 侯郁洁, 孔令学, 郭振兴, 白进, 李文. 反应条件对哈密煤温和液化沥青质结构和热反应性的影响[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022020
ZHANG Yan-long, BAI Zong-qing, FENG Zhi-hao, HOU Ran-ran, JIA Yu-xing, ZHANG Ting-ting, Hou Yu-jie, KONG Ling-xue, GUO Zhen-xing, BAI Jin, LI Wen. Effect of reaction conditions on structure and thermal reactivity of asphaltenes from mild liquefaction of Hami coal[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022020
Citation: ZHANG Yan-long, BAI Zong-qing, FENG Zhi-hao, HOU Ran-ran, JIA Yu-xing, ZHANG Ting-ting, Hou Yu-jie, KONG Ling-xue, GUO Zhen-xing, BAI Jin, LI Wen. Effect of reaction conditions on structure and thermal reactivity of asphaltenes from mild liquefaction of Hami coal[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022020

反应条件对哈密煤温和液化沥青质结构和热反应性的影响

doi: 10.19906/j.cnki.JFCT.2022020
基金项目: 国家自然科学基金(22178371, 22078353),山西省自然科学基金重点项目(201901D111002(ZD))和中国科学院战略性先导科技专项(XDA21020100)资助
详细信息
    通讯作者:

    Tel: 0351-4040289, E-mail: baizq@ sxicc.ac.cn

  • 中图分类号: TQ530.2

Effect of reaction conditions on structure and thermal reactivity of asphaltenes from mild liquefaction of Hami coal

Funds: The project was supported by National Natural Science Foundation of China (22178371, 22078353), Natural Science Foundation Project of Shanxi Province (201901D111002(ZD)), Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21020100)
  • 摘要: 沥青质(包括沥青烯和前沥青烯,PAA)作为煤液化的重要产物,其结构和性质对煤的高效液化及其后续利用至关重要。沥青质的结构和性质与液化反应条件密切相关,因此,本研究以四氢萘为溶剂,考察了反应温度、停留时间、反应压力、溶煤比等条件对哈密煤温和液化沥青质(HMPAA)结构和性质的影响。利用元素分析、红外光谱、固体13C-NMR等分析了不同温和液化反应条件下所得HMPAA的结构特征;利用TG-MS考察了HMPAA的热解反应性和热解过程中的气体逸出规律。结果表明,HMPAA的收率随反应温度降低、压力升高、停留时间缩短及溶煤比增加而升高。在温度为340 °C、停留时间为1 h、压力为3 MPa、溶煤比为2∶1的条件下,HMPAA收率最高,达到35.0%。HMPAA碳结构由脂肪碳和芳香碳组成,其中,芳香碳占80%左右。升高温度有利于哈密煤液化反应向生成芳香化程度更高的HMPAA组分的方向进行;延长停留时间,HMPAA的芳环缩合程度增大;增大溶煤比,HMPAA芳香度和芳环缩合程度均减小;在本研究考察的范围内改变压力对HMPAA结构性质影响不大。HMPAA在250 °C左右开始发生热解反应,最大失重峰温为400−500 °C,最终失重率基本40%以上。HMPAA热反应性随反应温度降低、溶煤比增加而增大,改变压力对HMPAA热反应性影响较小。
  • 图  1  不同反应条件下HM煤温和液化转化率及产物分布

    Figure  1  Conversion and product distribution of mild liquefaction of Hami coal under different conditions

    (a): reaction temperature; (b): reaction pressure; (c): residence time; (d): ratio of solvent to coal

    图  2  不同反应条件下HMPAA的红外光谱谱图

    Figure  2  Infrared spectrum of HMPAA obtained under different reaction conditions

    (a): reaction temperature; (b): residence time; (c): ratio of solvent to coal; (d): reaction pressure

    图  3  HMPAA固体核磁碳谱分峰拟合

    Figure  3  Curve–fitting process of solid–state 13C-NMR spectra of HMPAA

    图  4  Ar气氛下HMPAA的热重分析曲线

    Figure  4  TG and DTG curves of HMPAA under Ar atmosphere

    (a): reaction temperature; (b): residence time; (c): ratio of solvent to coal; (d): reaction pressure

    图  5  不同温度条件下所得HMPAA热解过程中H2和CH4的逸出规律

    Figure  5  Evolution curves of H2 and CH4 during pyrolysis of HMPAA obtained at different temperatures

    表  1  新疆HM煤煤质分析

    Table  1  Basic property analysis of HM coal

    Proximate analysis w/%Ultimate analysis wdaf/%St,d/%H/CO/C
    MadAdVdafCHNO*
    7.469.9353.0174.365.460.9217.581.510.880.18
    ad: air dry basis; d: dry basis; daf: dry and ash-free basis; *: by difference
    下载: 导出CSV

    表  2  不同条件下HMPAA的元素分析

    Table  2  Ultimate analysis of HMPAA obtained under different conditions

    ConditionUitimate analysis w/%H/CO/C
    CHO*NS
    340 ℃ 79.56 6.31 12.60 1.22 0.31 0.95 0.12
    360 ℃ 81.38 6.16 11.03 1.25 0.18 0.91 0.10
    380 ℃ 82.43 5.83 10.10 1.49 0.15 0.85 0.09
    400 ℃ 84.64 5.48 8.05 1.70 0.13 0.78 0.07
    420 ℃ 81.40 5.48 11.52 1.49 0.11 0.81 0.11
    2 Mpa 78.92 5.35 14.13 1.47 0.13 0.81 0.13
    3 Mpa 81.40 5.48 11.52 1.49 0.11 0.81 0.11
    4 Mpa 86.20 5.28 6.81 1.63 0.08 0.74 0.06
    0.5 h 80.81 5.20 12.20 1.54 0.25 0.77 0.11
    1 h 81.40 5.48 11.52 1.49 0.11 0.81 0.11
    1.5 h 82.55 5.37 10.41 1.56 0.11 0.78 0.09
    1.5∶1 (S/C) 88.37 5.04 4.94 1.57 0.08 0.68 0.04
    2∶1 (S/C) 81.40 5.48 11.52 1.49 0.11 0.81 0.11
    3∶1 (S/C) 81.57 5.76 10.75 1.83 0.09 0.85 0.10
    *: by difference
    下载: 导出CSV

    表  3  不同反应条件下HMPAA的碳结构参数

    Table  3  Carbon structure parameters of HMPAA obtained under different reaction conditions

    ParameterConditions
    T/°Ct/hS/Cp/MPa
    3403603804004200.511.51.5∶12∶13∶1234
    fal /% 42.60 38.71 28.08 22.01 18.15 16.14 18.15 24.23 13.12 18.15 28.79 22.37 18.15 22.67
    fa /% 57.28 61.09 71.56 77.92 81.84 83.63 81.84 74.91 86.85 81.84 71.18 77.58 81.84 77.24
    faB /% 11.61 13.04 16.21 19.22 21.86 25.85 21.86 18.03 27.11 21.86 16.85 20.62 21.86 21.45
    χb 0.20 0.21 0.23 0.25 0.27 0.31 0.27 0.24 0.31 0.27 0.24 0.27 0.27 0.28
    T, temperature; t, time; S/C, ratio of solvent to coal; p, pressure; fal, fraction of alkyl carbon; fa, aromaticity; faB, fraction of bridgehead carbon; χb, size of aromatic cluster
    下载: 导出CSV
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  • 收稿日期:  2022-02-23
  • 录用日期:  2022-03-15
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  • 网络出版日期:  2022-03-25

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