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溶剂溶胀对鄂尔多斯褐煤结构及热解产物分布的影响

彭志威 强路遥 白柏杨 张穗穗 孙鸣 马晓迅 王飞利

彭志威, 强路遥, 白柏杨, 张穗穗, 孙鸣, 马晓迅, 王飞利. 溶剂溶胀对鄂尔多斯褐煤结构及热解产物分布的影响[J]. 燃料化学学报, 2021, 49(4): 444-454. doi: 10.19906/j.cnki.JFCT.2021031
引用本文: 彭志威, 强路遥, 白柏杨, 张穗穗, 孙鸣, 马晓迅, 王飞利. 溶剂溶胀对鄂尔多斯褐煤结构及热解产物分布的影响[J]. 燃料化学学报, 2021, 49(4): 444-454. doi: 10.19906/j.cnki.JFCT.2021031
PENG Zhi-wei, QIANG Lu-yao, BAI Bo-yang, ZHANG Sui-sui, SUN Ming, MA Xiao-xun, WANG Fei-li. Effect of solvent swelling on structure and pyrolysis product distribution of Ordos lignite[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 444-454. doi: 10.19906/j.cnki.JFCT.2021031
Citation: PENG Zhi-wei, QIANG Lu-yao, BAI Bo-yang, ZHANG Sui-sui, SUN Ming, MA Xiao-xun, WANG Fei-li. Effect of solvent swelling on structure and pyrolysis product distribution of Ordos lignite[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 444-454. doi: 10.19906/j.cnki.JFCT.2021031

溶剂溶胀对鄂尔多斯褐煤结构及热解产物分布的影响

doi: 10.19906/j.cnki.JFCT.2021031
基金项目: 国家重点研发计划项目(2018YFB0604603),国家自然科学基金(21536009)和陕西省重点研发计划项目(2017ZDCXL-GY-10-03, 2018ZDXM-GY-167)资助
详细信息
    通讯作者:

    E-mail: maxym@nwu.edu.cn

    hgwfli@nwu.edu.cn

  • 中图分类号: TQ53

Effect of solvent swelling on structure and pyrolysis product distribution of Ordos lignite

Funds: The project was supported by the National Key Research and Development Program (2018YFB0604603), the National Natural Science Foundation of China (21536009) and the Shaanxi Provincial Key Research and Development Program (2017ZDCXL-GY-10-03, 2018ZDXMGY-167)
  • 摘要: 采用四种有机溶剂对鄂尔多斯褐煤进行溶胀预处理并在粉-粒流化床上进行快速热解,探究溶胀对褐煤结构及热解特性的影响。采用傅里叶变换红外光谱仪、热重分析仪、气相色谱-质谱联用仪、固体核磁、X射线衍射、全自动化学吸附仪等仪器对溶胀煤及热解产物进行表征。结果表明,非极性溶剂对煤结构影响较小。极性溶剂可以降低褐煤含氧官能团的氢键交联,增加小分子的流动性,增加煤的平均孔径。溶胀后的煤热解焦油和气相产率提高,热解水产率降低。与原煤相比,极性溶剂甲醇、丙酮、四氢呋喃处理煤样的热解焦油产率分别提高了18.88%、26.72%、33.58%,焦油的轻质组分中酚类、单环和双环类芳香烃组分含量明显增加。
  • FIG. 608.  FIG. 608.

    FIG. 608..  FIG. 608.

    图  1  粉-粒流化床热解装置示意图

    Figure  1.  Scheme of powder-particle fluidized bed equipment for pyrolysis.

    图  2  溶胀液总离子流色谱图

    Figure  2.  Total ion flow chromatogram of swelling solution

    图  3  煤样的孔径分布

    Figure  3.  Pore size distribution of coal samples

    图  4  煤样的热重分析,(a) TG;(b) DTG

    Figure  4.  Thermogravimetric analysis of coal samples (a) TG;(b) DTG

    图  5  煤样的XRD谱图(a)及ED-T分峰拟合图(b)

    Figure  5.  Coal samples XRD spectra (a) and ED peak fitting diagram (b)

    图  6  煤样的红外光谱谱图

    Figure  6.  Infrared spectra of coal samples

    图  7  煤样核磁谱图(a)及ED分峰拟合图(b)

    Figure  7.  NMR spectra of coal samples (a) and ED peak fitting diagram (b)

    图  8  热解焦油的红外光谱谱图

    Figure  8.  Infrared spectra of pyrolysis tar

    图  9  焦油组分图 (a) 焦油热重图(b) 焦油组分含量

    Figure  9.  Tar composition diagram (a) tar thermogravimetric diagram;(b) tar component content

    表  1  粉-粒流化床实验参数

    Table  1.   Experimental parameters of powder particle fluidized bed

    GasFeed rate/(gcoal·min−1Mass/gGas flow/(L·min−1Temperature/℃
    EDSiO2feed gasfluidized gasreactorcyclone separatorcondenser tube
    N20.25.056.9−57.01.20.6600350−40 ± 2
    下载: 导出CSV

    表  2  实验煤样的溶胀度、工业分析和元素分析

    Table  2.   Swelling degree and proximate and ultimate analyses of coal samples used in the experiment

    SampleQProximate analysis w/%Ultimate analysis wdaf/%Atomic ratio
    MdAdVdafFCdaf*NCHSO*O/CH/C
    ED2.596.2137.2762.731.2479.454.520.4014.400.2250.683
    ED-N1.073.016.2536.5463.461.2280.544.280.3313.630.2150.637
    ED-M1.273.296.1237.3662.641.1881.174.270.3014.170.2210.639
    ED-A1.363.896.1636.9163.091.2179.704.140.2614.690.2270.624
    ED-T1.503.456.2937.8462.161.1679.854.230.2514.520.2250.635
    note: * means the data obtained by subtraction method; the data of proximate and ultimate analyses are obtained after the coal samples were dried at 105 ℃ for 12 h
    下载: 导出CSV

    表  3  煤样孔结构参数

    Table  3.   Pore structure parameters of coal sample

    SamplesSurface
    area /(m2·g−1)
    Pore volume/
    (mL·g−1
    Pore size/
    nm
    ED7.860.01537.78
    ED-N6.510.01569.61
    ED-M2.230.010218.30
    ED-A2.700.012418.42
    ED-T0.770.006232.40
    下载: 导出CSV

    表  4  TG参数

    Table  4.   TG parameters

    Samplew/%ti/℃tmax/℃tf/℃tp/℃Rmax/(%·min−1)
    ED33.483554525497001.34
    ED-N31.513444505601.16
    ED-M34.413224455686761.18
    ED-A35.283444475501.26
    ED-T33.373394495591.21
    note: − means that there is no obvious peak
    下载: 导出CSV

    表  5  XRD分峰拟合参数

    Table  5.   Fitting parameters of XRD peaks

    Sample2θ002/(°)d002/nmLc/nmn2θ100/(°)La/nm
    ED25.320.18021.21576.7543.741.9479
    ED-N25.280.18041.19826.6443.771.7195
    ED-M25.210.18091.12066.2043.251.8019
    ED-A25.010.18221.05945.8144.112.0501
    ED-T24.920.18290.94455.1643.121.9966
    下载: 导出CSV

    表  6  煤样的核磁分峰数据

    Table  6.   NMR peak data of coal samples

    SampleAl-CAr-CCarboxy-CCH2/CH3
    ED31.9957.6610.351.23
    ED-N32.0357.5810.391.37
    ED-M32.3057.3710.331.20
    ED-A32.7657.349.901.19
    ED-T32.9957.359.661.17
    note: aliphatic carbon content Al-C=$ f_{\mathrm{a}\mathrm{l}}^{3} $+$ f_{\mathrm{a}\mathrm{l}}^{\mathrm{a}} $+$ f_{\mathrm{a}\mathrm{l}}^{2} $+$ f_{\mathrm{a}\mathrm{l}}^{1} $+$ f_{\mathrm{a}\mathrm{l}}^{\mathrm{*}} $+$ f_{\mathrm{a}\mathrm{l}}^{\mathrm{O}} $;aromatic carbon content Ar-C=$ f_{\mathrm{a}}^{\mathrm{H}} $+$ f_{\mathrm{a}}^{\mathrm{B}} $+$ f_{\mathrm{a}}^{\mathrm{S}} $+$ f_{\mathrm{a}}^{\mathrm{O}} $;carbonyl carbon content Carboxy-C=$ f_{\mathrm{a}}^{\mathrm{C}\mathrm{C}} $;CH2/CH3=($ f_{\mathrm{a}\mathrm{l}}^{3} $+$ f_{\mathrm{a}\mathrm{l}}^{\mathrm{a}} $)/$ f_{\mathrm{a}\mathrm{l}}^{2} $
    下载: 导出CSV

    表  7  煤样热解产物的收率

    Table  7.   Yield of pyrolysis products of coal samples

    Yield w/%
    EDED-NED-MED-AED-T
    Tar9.329.5611.0811.8112.45
    Char71.0170.8269.3968.7268.14
    Gas16.4416.4717.0317.1217.25
    Water3.233.152.502.352.16
    note: the data above were obtained after eliminating the residual solvent in tar, and the gas yield was obtained by subtraction method
    下载: 导出CSV

    表  8  热解气相产物分布

    Table  8.   Distribution of pyrolysis gas products

    SampleComponent content/($ {\rm{mmol}} \cdot {\rm{g}}_{{\rm{coal{\text{,}}daf}}}^{-1} $)
    COCH4CO2C2C3H2
    ED1.051.040.480.150.070.21
    ED-N0.970.750.490.130.080.12
    ED-M1.120.880.620.170.090.21
    ED-A1.170.680.660.150.070.14
    ED-T1.230.940.650.170.090.16
    下载: 导出CSV
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  • 收稿日期:  2020-12-18
  • 修回日期:  2021-01-11
  • 网络出版日期:  2021-03-30
  • 刊出日期:  2021-04-10

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