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利用原位热解光电离飞行时间质谱研究Fe2O3对两种脱矿煤热解规律的影响

张学慧 朱家龙 班延鹏 刘方刚 靳立军 胡浩权

张学慧, 朱家龙, 班延鹏, 刘方刚, 靳立军, 胡浩权. 利用原位热解光电离飞行时间质谱研究Fe2O3对两种脱矿煤热解规律的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60065-8
引用本文: 张学慧, 朱家龙, 班延鹏, 刘方刚, 靳立军, 胡浩权. 利用原位热解光电离飞行时间质谱研究Fe2O3对两种脱矿煤热解规律的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60065-8
ZHANG Xue-hui, ZHU Jia-long, BAN Yan-peng, LIU Fang-gang, JIN Li-jun, HU Hao-quan. Effect of Fe2O3 on the pyrolysis of two kinds of demineralized coal by in-situ pyrolysis photoionization time-of-flight mass spectrometry[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60065-8
Citation: ZHANG Xue-hui, ZHU Jia-long, BAN Yan-peng, LIU Fang-gang, JIN Li-jun, HU Hao-quan. Effect of Fe2O3 on the pyrolysis of two kinds of demineralized coal by in-situ pyrolysis photoionization time-of-flight mass spectrometry[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60065-8

利用原位热解光电离飞行时间质谱研究Fe2O3对两种脱矿煤热解规律的影响

doi: 10.1016/S1872-5813(21)60065-8
基金项目: 国家重点研发计划(2016YFB0600301)和中央高校基本科研业务费(DUT2018TB02)资助
详细信息
    通讯作者:

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

  • 中图分类号: TQ530.2

Effect of Fe2O3 on the pyrolysis of two kinds of demineralized coal by in-situ pyrolysis photoionization time-of-flight mass spectrometry

Funds: The project was supported by National Key R&D Program of China (2016YFB0600301) and The Fundamental Research Funds for the Central Universities (DUT2018TB02)
  • 摘要: 利用原位热解真空紫外单光子电离飞行时间质谱系统研究了Fe2O3对脱矿红沙泉和大柳塔煤热解产物分布的影响。实验所用样品是经酸洗脱矿物质后的煤与Fe2O3以10∶1、5∶1和2∶1的质量比机械混合得到。在该热解检测系统中,由于原位捕捉、软电离和高真空环境的特点可以检测到热解初始挥发产物,主要包括烯烃、芳烃、单酚、双酚及少量含硫和含氮物质。结果表明:Fe2O3对两种脱矿煤的热解产物分布具有相似的影响规律,但对脱矿大柳塔煤的影响较为明显。随着Fe2O3添加量的增加,产物中烯烃、芳烃等轻质组分含量增加,双酚类的含量明显降低,重质产物的含量也有所降低,但产物的逸出峰值温度提高。Fe2O3在使重组分向轻质组分转变的同时,自身被还原成FeO并进一步还原成Fe。煤热解过程中形成产物的脂碳(或芳烃取代碳)愈多,其产生的峰值温度愈低。
  • 图  1  原位热解光电离飞行时间质谱装置示意图[12]

    Figure  1.  Schematic diagram of Py-PI-TOF MS

    图  2  混合煤样的TG和DTG曲线:(a) TG-HSQDM; (b) DTG-HSQDM; (c) TG-DLTDM; (d) DTG-DLTDM

    Figure  2.  TG and DTG curves of coal samples: (a) TG-HSQDM; (b) DTG-HSQDM; (c) TG-DLTDM; (d) DTG-DLTDM

    图  3  红沙泉混合煤样的PI-MS谱图:(a) HSQDM; (b) HSQDM∶Fe2O3 = 10∶1; (c) HSQDM∶Fe2O3 = 5∶1; (d) HSQDM∶Fe2O3 = 2∶1

    Figure  3.  Py-PI-TOF MS spectra of pyrolysis products of HSQDM coal samples: (a) HSQDM; (b) HSQDM∶Fe2O3 = 10∶1; (c) HSQDM∶Fe2O3 = 5∶1; (d) HSQDM∶Fe2O3 = 2∶1

    图  4  红沙泉混合煤样的DTG (a)和TIC (b)图

    Figure  4.  DTG (a) and TIC (b) curves of HSQDM coal samples

    图  5  主要热解产物逸出特征曲线图:(a) 烯烃(m/z = 28, 42, 56, 70和84); (b) 芳烃(m/z = 78, 92, 106, 120和134); (c) 单酚(m/z = 94, 108, 122和134); (d) 双酚(m/z = 110, 124和138)

    Figure  5.  Evolved profiles of main products during pyrolysis of HSQDM coal samples: (a) alkenes; (b) aromatic hydrocarbons; (c) phenols; (d) diphenols

    图  6  Fe2O3对热解产物峰值温度与取代基碳数间关系的影响

    Figure  6.  Effect of Fe2O3 on the relationship between peak temperature and substituent carbon number of pyrolysis products

    图  7  不同Fe2O3添加的红沙泉混合煤样主要热解产物的相对含量图

    Figure  7.  Relative content of main pyrolysis products of during HSQDM pyrolysis with different Fe2O3 mixing ratio

    图  8  添加Fe2O3前后大柳塔脱矿煤的主要热解产物:(a) DLTDM及DLTDM:Fe2O3 = 5∶1的主要热解产物的相对含量;(b) 热解产物分类汇总和重质产物相对含量

    Figure  8.  Relative content of main pyrolysis products of DLTDM coal samples with and without addition of Fe2O3: (a) relative content of main pyrolysis products; (b) different types of pyrolysis products

    图  9  混合煤样反应前后的XRD谱图

    Figure  9.  XRD patterns of mixed coal samples before and after reaction

    表  1  大柳塔、红沙泉原煤及其脱矿煤的工业分析和元素分析

    Table  1.   Proximate and ultimate analyses of coal samples

    Coal sampleProximate analysis (wt.%)Ultimate analysis (wt.%, daf)
    MadAdVdafCHNSO*H/C
    DLT1.4313.9334.0678.324.751.090.6215.220.73
    DLTDM1.130.3032.0978.624.670.990.4515.270.71
    HSQ3.157.6035.4376.304.851.080.1217.650.76
    HSQDM1.960.1137.5976.564.721.060.0817.580.74
    * By difference
    下载: 导出CSV

    表  2  大柳塔和红沙泉原煤的灰成分分析

    Table  2.   XRF analyses of DLT and HSQ coal ash

    SampleFe2O3SiO2Al2O3Na2OCaOK2OSO3MgOOther*
    DLT7.8252.5617.221.0211.581.476.290.691.35
    HSQ14.8343.4419.703.348.470.473.924.001.83
    * By difference
    下载: 导出CSV

    表  3  煤原位热解光电离飞行时间质谱检测主要热解产物归属

    Table  3.   Mass attribution of major pyrolysis products of coal via in-situ Py-PI-TOF MS

    m/z Name Formula Formula IE (eV)a
    28 ethylene C2H4 10.51
    42 propylene C3H6 9.73
    56 butene/methylcyclopropane C4H8 9.10/9.30
    70 pentene/ethylcyclopropane C5H10 9.04/8.96
    78 benzene C6H6 9.244
    84 cyclohexane/hexene C6H12 9.88/8.97
    92 toluene C7H8 8.828
    94 phenol C6H6O 8.49
    106 dimethylbenzene/ethylbenzene C8H10 8.44/8.77
    108 methylphenol/anisole C7H8O 8.29/8.20
    110 benzenediol C6H6O2 7.94
    120 trimethylbenzene C9H12 8.4
    124 guaiacol/methylbenzenediol C7H8O2
    134 tetramethylbenzene C10H14 8.06/8.29
    136 2,4,6-trimethyl phenol C9H12O 8.00
    138 ethoxyphenol/dimethoxybenzene C8H10O2 8.49/7.80
    142 Methylnaphthalene C11H10 7.96
    144 Naphthalenol C10H8O 7.89
    146 Coumarin C9H6O2 8.72
    156 Dimethylnaphthalene C12H12 8.11
    158 methoxynaphthalene/methylnaphthalenol C11H10O 7.82/7.72
    160 1,8-naphthalenediol C10H8O2 7.62
    170 Trimethylnaphthalene C13H14
    174 Methylnaphthalenediol C11H10O2
    178 phenanthrene/anthracene C14H10 7.44/7.89
    a: IE values with reference to NIST Chemistry WebBook[15]
    下载: 导出CSV
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