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<p>In this study, the qualitative composition and pyrolysis kinetics of kerogen in Longkou oil shale were investigated by pyrolysis–gas chromatography/mass spectrometry (PY-GC/MS). It was found that the pyrolysis products generated between 400 and 550&#xa0;°C can be classified into seven categories, i.e., n-alkanes (C<sub>8</sub>–C<sub>31</sub>), n-alkenes (C<sub>8</sub>–C<sub>23</sub>), aromatic hydrocarbons, and their derivatives, phenolic series, and aliphatic acid series, as well as a limited number of oxygen-containing compounds and isoprenoid alkanes. Subsequently, a global first-order reaction kinetics model was adopted to calculate the generation kinetic parameters of n-alkanes, n-alkenes, and alkylbenzenes. The activation energies were found to be mainly concentrated in the range of 26–86&#xa0;kJ&#xa0;mol⁻<sup>1</sup> for n-alkanes, 50–98&#xa0;kJ&#xa0;mol⁻<sup>1</sup> for n-alkenes, and 88–99&#xa0;kJ&#xa0;mol⁻<sup>1</sup> for alkylbenzenes. In addition, the influences of temperature and heating rate on the distribution of n-alkanes, n-alkenes, and alkylbenzenes were also explored. C<sub>24</sub>–C<sub>27</sub> hydrocarbons were the initial products generated at low pyrolysis temperatures. As the temperature rose, large-molecule compounds were more likely to break into small-molecule fragments. It was attributed to that the greater the activation energy of hydrocarbon compounds was, the higher the reaction rate constant increased. As the heating rate fell, the contents of small-molecule n-alkanes, n-alkenes, and alkylbenzenes increased due to intensified secondary decomposition of large-molecule hydrocarbons. Overall, the total contents of these three groups increased by approximately 40%, and the final pyrolysis products were predominantly composed of C<sub>13</sub>–C<sub>19</sub> hydrocarbons.</p>

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Distribution and generation kinetics of pyrolysis products of kerogen from Longkou oil shale by PY-GC/MS

  • 期刊论文

  • 发表日期：

    2025年7月29日

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  • Wei Wang,
  • Qiang Ma,
  • Naixin Kang,
  • Yujie Chen

摘要

In this study, the qualitative composition and pyrolysis kinetics of kerogen in Longkou oil shale were investigated by pyrolysis–gas chromatography/mass spectrometry (PY-GC/MS). It was found that the pyrolysis products generated between 400 and 550 °C can be classified into seven categories, i.e., n-alkanes (C8–C31), n-alkenes (C8–C23), aromatic hydrocarbons, and their derivatives, phenolic series, and aliphatic acid series, as well as a limited number of oxygen-containing compounds and isoprenoid alkanes. Subsequently, a global first-order reaction kinetics model was adopted to calculate the generation kinetic parameters of n-alkanes, n-alkenes, and alkylbenzenes. The activation energies were found to be mainly concentrated in the range of 26–86 kJ mol⁻1 for n-alkanes, 50–98 kJ mol⁻1 for n-alkenes, and 88–99 kJ mol⁻1 for alkylbenzenes. In addition, the influences of temperature and heating rate on the distribution of n-alkanes, n-alkenes, and alkylbenzenes were also explored. C24–C27 hydrocarbons were the initial products generated at low pyrolysis temperatures. As the temperature rose, large-molecule compounds were more likely to break into small-molecule fragments. It was attributed to that the greater the activation energy of hydrocarbon compounds was, the higher the reaction rate constant increased. As the heating rate fell, the contents of small-molecule n-alkanes, n-alkenes, and alkylbenzenes increased due to intensified secondary decomposition of large-molecule hydrocarbons. Overall, the total contents of these three groups increased by approximately 40%, and the final pyrolysis products were predominantly composed of C13–C19 hydrocarbons.