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煤热解挥发分在活性炭上的积炭行为及其过程分析

靳鑫 王倩 李晓荣 李挺 王美君 孔娇 闫伦靖 常丽萍 王建成 鲍卫仁

靳鑫, 王倩, 李晓荣, 李挺, 王美君, 孔娇, 闫伦靖, 常丽萍, 王建成, 鲍卫仁. 煤热解挥发分在活性炭上的积炭行为及其过程分析[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60047-6
引用本文: 靳鑫, 王倩, 李晓荣, 李挺, 王美君, 孔娇, 闫伦靖, 常丽萍, 王建成, 鲍卫仁. 煤热解挥发分在活性炭上的积炭行为及其过程分析[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60047-6
JIN Xin, WANG Qian, LI Xiao-rong, LI Ting, WANG Mei-jun, KONG Jiao, YAN Lun-jing, CHANG Li-ping, WANG Jian-cheng, BAO Wei-ren. Coke formation on activated carbon during catalytic upgrading of coal pyrolysis volatiles[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60047-6
Citation: JIN Xin, WANG Qian, LI Xiao-rong, LI Ting, WANG Mei-jun, KONG Jiao, YAN Lun-jing, CHANG Li-ping, WANG Jian-cheng, BAO Wei-ren. Coke formation on activated carbon during catalytic upgrading of coal pyrolysis volatiles[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60047-6

煤热解挥发分在活性炭上的积炭行为及其过程分析

doi: 10.1016/S1872-5813(21)60047-6
基金项目: 国家重点研发计划(2016YFB0600302)和国家自然科学基金(22078224)资助
详细信息
    作者简介:

    靳鑫:jinxin0916@126.com

    通讯作者:

    E-mail:wangmeijun@tyut.edu.cn

    lpchang@tyut.edu.cn

  • 中图分类号: TQ530.2

Coke formation on activated carbon during catalytic upgrading of coal pyrolysis volatiles

Funds: The project was supported by the National Key Research and Development Program of China (2016YFB0600302) and the National Natural Science Foundation of China (22078224)
  • 摘要: 中低温热解煤焦油存在重质组分含量高、焦油品质差等问题,通过引入催化剂原位调控热解挥发分的反应,可有效改善焦油品质,但催化剂易积炭失活,影响其持续使用时间。利用下行床连续热解反应器,研究了挥发分在活性炭催化剂上的积炭行为,通过改变进煤时间(30、60和100 min),考察了挥发分的反应及其在活性炭上形成积炭的过程机制。结果表明,挥发分反应在活性炭上形成了大量积炭,随着进料时间的延长,活性炭上积炭的绝对量增加,但积炭形成的速率降低,因此,对于干基煤积炭的产率减小。随着活性炭上积炭量增加,活性炭的比表面积显著减小,催化裂解活性降低,焦油产率以及其中的沥青产率均有增大。焦油的组成分析表明,随着进料时间的延长,含氧化合物的相对含量增加,C−O弱键的断裂被抑制,这也使得积炭形成速率有所降低。
  • 图  1  下行床煤热解反应装置示意图

    Figure  1.  Schematic diagram of the experimental apparatus

    1-feeder; 2-quartz reactor; 3-furnace; 4-gas flowmeter; 5-preheating furnace; 6-condenser pipe; 7-condenser; 8-collection bottle; 9-U glass tube; 10-absorption bottle; 11-absorbent cotton filter; 12-wet gas flowmeter; 13-polymeter filter; 14-desiccant; 15-Raman laser gas analyzer

    图  2  NMH煤热解产物的分布

    Figure  2.  Product distribution of NMH coal during pyrolysis

    (Coke: the sum of Coke-S, Coke-C and Coke-D)

    图  3  NMH煤热解积炭的分布

    Figure  3.  Coke distribution of NMH coal pyrolysis

    图  4  NMH煤热解气体的产率

    Figure  4.  Yield of NMH coal pyrolysis gas

    图  5  两种活性炭的红外光谱谱图

    Figure  5.  FT-IR spectra of AC-1 and AC-2

    图  6  不同进料时间下NMH煤的热解产物分布

    Figure  6.  Pyrolysis product distribution of NMH coal at different feed time

    图  7  不同进料时间下NMH煤热解的积炭分布

    Figure  7.  Coke distribution of NMH coal pyrolysis at different feed time

    图  8  不同进料时间下NMH煤热解焦油的馏分产率

    Figure  8.  Fraction yield of tar at different feed time

    图  9  不同进料时间下NMH煤热解焦油轻重组分的产率

    Figure  9.  The light and heavy fraction yield of tar at different feed time

    图  10  不同进料时间下NMH煤热解焦油的组成分布

    Figure  10.  Composition of tar from NMH coal pyrolysis at different feed time

    图  11  不同进料时间下NMH煤热解焦油中含氧化合物的相对含量

    Figure  11.  Relative content of oxygen-containing compounds in tar from NMH coal pyrolysis at different feed time

    图  12  不同进料时间下NMH煤热解焦油中芳香化合物的相对含量

    Figure  12.  Relative content of aromatics in tar from NMH coal pyrolysis at different feed time

    图  13  不同进料时间下NMH煤热解气的产率

    Figure  13.  Yield of pyrolysis gas at different feed time

    表  1  NMH煤的工业分析、元素分析和格金干馏焦油产率

    Table  1.   Proximate analysis, ultimate analysis and tar yield by Gray-King assay of NMH coal

    Proximate analysis w/%Ultimate analysis wdaf/%Gray-King assay
    MadAdVdaf CHNStO* tar yield wd/%
    19.505.8050.1274.355.130.720.3119.4915.4
    note: ad: air dried basis; d: dried basis; daf: dried and ash-free basis; St: total sulfur; *: by difference
    下载: 导出CSV

    表  2  反应前后活性炭的氮气吸附孔结构特征参数

    Table  2.   Characteristic parameters of pore structure for fresh and used activated carbon by nitrogen adsorption characterization

    SampleSBET/(m2·g−1)Smic/(m2·g−1)Sext/(m2·g−1)vtot/(cm3·g−1)vmic/(cm3·g−1)vmes/(cm3·g−1)dave/nm
    AC-1-Fresh1221.24469.38751.860.580.190.382.13
    AC-1-Spent699.05367.46331.590.340.150.182.32
    AC-2-Fresh953.34836.00117.350.390.330.071.99
    AC-2-Spent725.42639.6285.810.300.250.051.88
    note: SBET: BET surface area, Smic: micropore area, Sext: external surface, vtot: total pore volume, vmic: micropore volume, vmes: mesopore volume, dave: average pore diameter
    下载: 导出CSV

    表  3  不同进料时间反应后活性炭的氮气吸附孔结构特征参数

    Table  3.   Characteristic parameters of pore structure for spent activated carbons at different times by nitrogen adsorption characterization

    SampleSBET/(m2·g−1)Smic/(m2·g−1)Sext/(m2·g−1)vtot/(cm3·g−1)vmic/(cm3·g−1)vmes/(cm3·g−1)dave/nm
    AC-1-30 min1125.44368.80756.640.470.150.321.93
    AC-1-60 min777.51315.57461.940.330.130.201.97
    AC-1-100 min699.05367.46331.590.340.150.182.32
    下载: 导出CSV
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  • 收稿日期:  2020-12-31
  • 修回日期:  2021-01-29
  • 网络出版日期:  2021-03-30

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