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碱木质素强化煤焦粉化学链气化实验研究

高行龙 安风霞 胡耘 陈国庆 易群 武小燕 曹晋曾 姚炜珊 魏国强

高行龙, 安风霞, 胡耘, 陈国庆, 易群, 武小燕, 曹晋曾, 姚炜珊, 魏国强. 碱木质素强化煤焦粉化学链气化实验研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2023078
引用本文: 高行龙, 安风霞, 胡耘, 陈国庆, 易群, 武小燕, 曹晋曾, 姚炜珊, 魏国强. 碱木质素强化煤焦粉化学链气化实验研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2023078
GAO Xinglong, AN Fengxia, HU Yun, CHEN Guoqing, YI Qun, WU Xiaoyan, CAO Jinzeng, YAO Weishan, WEI Guoqiang. Experimental study on alkali lignin enhanced chemical looping gasification of pulverized coal char[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023078
Citation: GAO Xinglong, AN Fengxia, HU Yun, CHEN Guoqing, YI Qun, WU Xiaoyan, CAO Jinzeng, YAO Weishan, WEI Guoqiang. Experimental study on alkali lignin enhanced chemical looping gasification of pulverized coal char[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023078

碱木质素强化煤焦粉化学链气化实验研究

doi: 10.19906/j.cnki.JFCT.2023078
基金项目: 国家自然科学基金 (51976226,52276191 )资助
详细信息
    通讯作者:

    E-mail:12019471@ceic.com

    weigq@scau.edu.cn

  • 中图分类号: TK16

Experimental study on alkali lignin enhanced chemical looping gasification of pulverized coal char

Funds: The project was supported by National Natural Science Foundation of China (51976226,52276191).
  • 摘要: 中国煤炼焦工业副产物煤焦粉产量大、活性低,难以被直接回收利用,常规热化学利用方式反应条件苛刻、催化剂易失活且存在动力学限制。本研究通过造纸副产物碱木质素作为可弃型催化剂,构建碱木质素强化化学链气化的方式来处理煤焦粉,实现工业副产物协同资源化利用。热转化实验和动力学分析研究表明,碱木质素可强化煤焦粉化学链气化过程,促进煤焦粉热解峰向低温方向移动。当煤焦粉与碱木质素质量比为1∶3时,反应活化能比单独煤焦粉反应降低87.56%。固定床实验证实气化温度提高、碱木质素以及载氧体赋存量增加,可以有效提高燃料碳转化率及合成气产物择性,促进气化反应进行,但氧载体过量会导致合成气转化为终端产物,降低合成气选择性。在气化温度为950 ℃,煤焦粉与碱木质素质量比为1∶2, 氧载体与煤焦粉/碱木质素混合体系质量比为1∶1的最佳反应条件下,基于NiFe2O3的碱木质素/煤焦粉化学链气化合成气选择性高达82.85%。该研究为碱木质素与煤焦粉的资源化利用提供科学依据。
  • 图  1  碱木质素强化煤焦粉化学链气化示意图

    Figure  1  Schematic diagram of alkali lignin-enhanced coal char gasification chemical pathway

    Note: MexOy: oxidized oxygen carrier; MexOy−1: reduced oxygen carrier; [O]: lattice oxygen.

    图  2  碱木质素强化煤焦粉化学链气化实验装置示意图

    Figure  2  Schematic diagram of experimental setup for alkali lignin-enhanced pulverized coal char gasification chemical pathway

    图  3  不同升温速率下的TG/DTG曲线

    Figure  3  TG/DTG curves under different heating rates

    (a): Pulverized coal char and oxygen carrier; (b): Alkali lignin and oxygen carrier; (c): Pulverized coal char/Alkali lignin (1∶1) with oxygen carrier; (d): Pulverized coal char/alkai lignin (1∶3) with oxygen carrier.

    图  4  不同升温速率下煤焦碱木质素混合体系的理论失重量与实际失重量对比图

    Figure  4  presents a comparative analysis between the theoretical and experimental weight loss of a coal-coke-lignin composite system at various heating rate

    (a): Pulverized coal char/alkali lignin (1∶1) with oxygen carrier; (b): Pulverized coal char/alkai lignin (1∶3) with oxygen carrier.

    图  5  不同升温速率下的拟合直线

    Figure  5  Fitted lines at different heating rates

    (a): Pulverized coal char and oxygen carrier; (b): Pulverized coal char/Alkali lignin (1∶1) with oxygen carrier; (c): Pulverized coal char /Alkai lignin (1∶3) with oxygen carrier.

    图  6  反应温度对煤焦粉与碱木质素(1∶2)化学链气化过程的影响

    Figure  6  Effect of reaction temperature on the chemical pathway gasification process of C pulverized coal char and alkali lignin (1∶2)

    图  7  碱木质素加入量对碱木质素与煤焦粉化学链气化过程的影响

    Figure  7  Effect of alkali lignin addition on the chemical pathway gasification process of alkali lignin and pulverized coal char

    图  8  氧载体加入量对碱木质素与煤焦粉化学链气化过程的影响

    Figure  8  Effect of oxygen carrier loading on the chemical pathway gasification process of alkali lignin and pulverized coal char

    图  9  NiFe2O4氧载体的XRD谱图

    Figure  9  X-ray diffraction (XRD) pattern of NiFe2O4 oxygen carrie

    图  10  氧载体与煤焦粉和氧载体与煤焦粉和碱木质素两者混合物反应后的SEM照片

    Figure  10  The SEM images of the oxygen carrier, the mixture of oxygen carrier and coal char, and the mixture of oxygen carrier with coal char and alkaline lignin after reaction

    (a): Pulverized coal char (b): Pulverized coal char: alkali lignin =1∶2 (c): Pulverized coal char: alkali lignin =1∶3.

    表  1  碱木质素和云南褐煤的工业分析和元素分析

    Table  1  Proximate and ultimate analysis of lignin alkaline and coal char

    SampleUltimate analysis wdry/% Proximate analysis wdry/% AAEMs/(mg·kg−1)
    CNHSO*VMAFCNaKMgCa
    Lignin alkaline59.40.095.303.1732.0 41.4934.3919.105.02 931101419376292
    Pulverized coal char69.770.613.911.0612.9740.3010.2211.6837.8
    O*: by difference.
    下载: 导出CSV

    表  2  常用固相动力学模型

    Table  2  Common solid-state kinetic models

    Symbolf (α)G (α)
    D1$ {1/2\alpha} $$ {{\alpha }}^{2} $
    D2${\text{[}-\text{ln}\left(1-\alpha\right)\text{]} }^{-\text{1} }$$ {\alpha + }\left(1-\alpha\right){\ln(1-\alpha)} $
    D3$ \left({3}/{2}\right){\text{[}{\left(1-\alpha\right)}^{-{1}/{3}}-{1]}}^{-{1}} $$ 1-(2/3)\alpha -{(1-\alpha )}^{2/3} $
    D4$ \text{(}{3}/{2)}{\left(1-\alpha\right)}^{{2}/{3}}{\text{[1}-{\left(1-\alpha\right)}^{{2}/{3}}\text{]}}^{-{1}} $$ {\text{[1}-{\left(1-\alpha\right)}^{{1}/{3}}\text{]}}^{{2}} $
    A1$ 1-{\alpha } $$ -\mathrm{l}\mathrm{n}(1-{\alpha }) $
    A2$ \text{2}\left(1-\alpha\right){\text{[}-\text{ln}\left(1-\alpha\right)\text{]}}^{\text{1}/\text{2}} $$ {\text{[}-\text{ln}\left(1-\alpha\right)\text{]}}^{{1}/{2}} $
    A33/(1−α)[−ln(1−α)]2/3$ {\text{[}-\text{ln}\left(1-\alpha\right)\text{]}}^{\text{1}/\text{3}} $
    R1$ 2{(1-{\alpha })}^{1/2} $$ 1-{(1-{\alpha })}^{1/2} $
    R2$ 3{(1-{\alpha })}^{2/3} $$ 1-{(1-{\alpha })}^{1/3} $
    C$ {(1-{\alpha })}^{2} $$ {(1-{\alpha })}^{-1}-1 $
    下载: 导出CSV

    表  3  不同固相动力学模型下的Pearson相关系数和残差平方和

    Table  3  Pearson correlation coefficients and sum of squares of residuals for different solid-state kinetic models

    SymbolPulverized coal char Pulverized coal char: alkali lignin=1∶1 Pulverized coal char: alkali lignin=1∶3
    PearsonRSSPearsonRSSPearsonRSS
    D1−0.957830.07751 −0.882230.07730 −0.907710.07487
    D2−0.982870.06168−0.965010.06173−0.974430.05194
    D3−0.992190.03960−0.985550.04032−0.993250.02115
    D4−0.992390.07720−0.987120.08862−0.996410.02670
    A1−0.95220.34100−0.916970.40541−0.936410.34202
    A2−0.941550.08440−0.816790.09102−0.877670.07790
    A3−0.926890.03717−0.394720.03616−0.673110.03140
    R1−0.993270.00832−0.969600.00874−0.994720.00211
    R2−0.990970.01910−0.976290.01853−0.995190.00465
    C−0.8566716.7274−0.8285722.3155−0.8436821.2446
    下载: 导出CSV

    表  4  不同条件下热解过程的活化能

    Table  4  Activation Energies of Pyrolysis Processes under Different Conditions

    SampleHeating
    rate/(K·min−1)
    Activation energy
    E/(kJ·mol−1)
    Pulverized coal char576.17875
    1084.09264
    1597.56443
    20125.00554
    Pulverized coal char:Alkali lignin =1∶1516.74055
    1024.11223
    1523.7565
    2024.28225
    Pulverized coal char:Alkali lignin =1∶3514.01977
    1015.12626
    1515.46651
    2015.55402
    下载: 导出CSV

    表  5  氧载体与煤焦粉、煤焦粉/碱木质素混合体系反应后比表面积与粒径分布

    Table  5  BET specific area and particle size distribution after the reaction of the oxygen carrier with pulverized coal char, pulverized coal char/alkali lignin mixture system

    Oxygen carrierBET specific surface area/(m2·g−1)Particle size distribution/μm
    d10%d50%d90%
    NiFe2O4/C2.385.8108.9904.8
    NiFe2O4/CA3.2860.3267.8868.2
    下载: 导出CSV
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  • 收稿日期:  2023-09-12
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