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    一种解释高-过成熟烷烃气碳同位素系列倒转的新观点:芳香烃脱甲基作用

    彭威龙 刘全有 胡国艺 吕玥 孟庆强 郭丰涛 关海洋

    彭威龙, 刘全有, 胡国艺, 吕玥, 孟庆强, 郭丰涛, 关海洋, 2020. 一种解释高-过成熟烷烃气碳同位素系列倒转的新观点:芳香烃脱甲基作用. 地球科学, 45(4): 1308-1314. doi: 10.3799/dqkx.2019.133
    引用本文: 彭威龙, 刘全有, 胡国艺, 吕玥, 孟庆强, 郭丰涛, 关海洋, 2020. 一种解释高-过成熟烷烃气碳同位素系列倒转的新观点:芳香烃脱甲基作用. 地球科学, 45(4): 1308-1314. doi: 10.3799/dqkx.2019.133
    Peng Weilong, Liu Quanyou, Hu Guoyi, Lü Yue, Meng Qingqiang, Guo Fengtao, Guan Haiyang, 2020. A New Interpretation of Carbon Isotope Series Reverse of Highly-Over Mature Alkane Gases: Demethylation of Aromatic Hydrocarbons. Earth Science, 45(4): 1308-1314. doi: 10.3799/dqkx.2019.133
    Citation: Peng Weilong, Liu Quanyou, Hu Guoyi, Lü Yue, Meng Qingqiang, Guo Fengtao, Guan Haiyang, 2020. A New Interpretation of Carbon Isotope Series Reverse of Highly-Over Mature Alkane Gases: Demethylation of Aromatic Hydrocarbons. Earth Science, 45(4): 1308-1314. doi: 10.3799/dqkx.2019.133

    一种解释高-过成熟烷烃气碳同位素系列倒转的新观点:芳香烃脱甲基作用

    doi: 10.3799/dqkx.2019.133
    基金项目: 

    中国博士后科学基金项目 2019M650967

    国家自然科学基金项目 41902160

    国家自然科学基金项目 41625009

    国家重大科技专项 2016ZX05007-001

    国家重点研发计划 2017YFC0603102

    中国科学院A类战略先导科技专项 XDA14010404

    详细信息
      作者简介:

      彭威龙(1988-), 男, 博士后, 主要从事热模拟实验, 天然气地质和天然气地球化学方面的研究

    • 中图分类号: P618.13

    A New Interpretation of Carbon Isotope Series Reverse of Highly-Over Mature Alkane Gases: Demethylation of Aromatic Hydrocarbons

    • 摘要: 天然气成因机理复杂,鉴于在高-过成熟阶段烷烃气碳同位素系列倒转普遍存在,而高-过成熟阶段有机质中常富含芳环结构,利用芳香烃(甲苯)热裂解实验探讨高-过成熟阶段烷烃气碳同位素系列倒转成因.甲苯热裂解实验表明随着模拟温度的增加,烷烃气产率逐渐增大;模拟产物中H2产率也随着模拟温度的增加而增加.甲苯裂解产物中δ13C1、δ13C2和δ13C3分布区间分别为-31.8‰~-27.7‰,-31.0‰~-20.4‰和-31.0‰~-20.4‰.在甲苯热模拟实验450℃时,出现了烷烃气碳同位素系列的部分倒转(δ13C113C2 < δ13C3).发现无论是煤成气还是油型气,在高-过成熟阶段都会出现烷烃气碳同位素系列的倒转,结合本次模拟实验结果,认为芳香烃脱甲基作用可能是烷烃气高-过成熟阶段出现碳同位素系列倒转的一个重要原因.

       

    • 图  1  甲苯裂解产物产率特征(a)、相对含量特征(b)和烷烃气碳同位素连线(c)

      Fig.  1.  Yield characteristics (a), relative content characteristics (b) and carbon isotope series of alkane gas (c) of toluene pyrolysis products

      图  2  煤成气δ13C213C1和δ13C1相关图(a)和页岩气δ13C213C1和δ13C1相关图(b)

      Fig.  2.  δ13C213C1 vs. δ13C1 of coal type gas (a); δ13C213C1 vs. δ13C1 of shale gas (b)

      图  3  芳香族化合物脱甲基形成CH4示意图

      Fig.  3.  Demethylation of aromatic compounds to form CH4

      表  1  甲苯裂解主要产物产率特征

      Table  1.   Yield characteristics of main products from toluene pyrolysis

      温度(℃) 样品量(mg) 主要组分产率(mL/g) 烃类气产率(mL/g)
      CH4 C2H6 C3H8 iC4 nC4 H2
      450 72.9 13.23 0.25 0.07 0.01 0.01 1.16 13.56
      475 69.7 55.12 0.70 0.18 0.01 n.d. 1.36 56.02
      500 61.1 193.99 6.19 0.99 0.04 n.d. 3.61 201.22
      525 60.2 260.85 11.23 0.60 0.02 n.d. 5.08 272.70
      550 52.9 294.55 8.48 0.18 n.d. n.d. 6.26 303.21
        注:"n.d."表示没有检测到数据, 下同.
      下载: 导出CSV

      表  2  甲苯裂解主要产物相对含量及碳同位素组成

      Table  2.   Relative content and carbon isotope composition of main products from toluene pyrolysis

      温度(℃) 主要化学组成(%) C1/C1-4 δ13C(‰, VPDB)
      CH4 C2H6 C3H8 iC4 nC4 H2 C1 C2 C3
      450 12.42 0.24 0.06 0.01 0.01 1.09 0.975 -27.7 -28.1 -23.5
      475 64.61 0.82 0.21 0.02 n.d. 1.59 0.984 -31.8 -31.0 -23.1
      500 89.34 2.85 0.46 0.02 n.d. 1.66 0.964 -30.5 -28.8 -19.3
      525 91.17 3.93 0.21 0.01 n.d. 1.78 0.957 -29.9 -24.4 -15.1
      550 91.37 2.63 0.06 n.d. n.d. 1.94 0.971 -29.5 -20.4 -16.9
      下载: 导出CSV
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