Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin

Semi-open hydrous pyrolysis experiments on coal-measure source rocks in the Xihu Sag were conducted to investigate the carbon isotope evolution of kerogen, bitumen, generated expelled oil, and gases with increasing thermal maturity. Seven corresponding experiments were conducted at 335 °C, 360 °C, 4...

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Main Authors: Qiang Cao, Jiaren Ye, Yongchao Lu, Yang Tian, Jinshui Liu, Chenjie Xu, Hanwen Yu, Lina Sun
Format: Article
Language:English
Published: MDPI AG 2021-12-01
Series:Energies
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Online Access:https://www.mdpi.com/1996-1073/14/24/8317
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author Qiang Cao
Jiaren Ye
Yongchao Lu
Yang Tian
Jinshui Liu
Chenjie Xu
Hanwen Yu
Lina Sun
author_facet Qiang Cao
Jiaren Ye
Yongchao Lu
Yang Tian
Jinshui Liu
Chenjie Xu
Hanwen Yu
Lina Sun
author_sort Qiang Cao
collection DOAJ
description Semi-open hydrous pyrolysis experiments on coal-measure source rocks in the Xihu Sag were conducted to investigate the carbon isotope evolution of kerogen, bitumen, generated expelled oil, and gases with increasing thermal maturity. Seven corresponding experiments were conducted at 335 °C, 360 °C, 400 °C, 455 °C, 480 °C, 525 °C, and 575 °C, while other experimental factors, such as the heating time and rate, lithostatic and hydrodynamic pressures, and columnar original samples were kept the same. The results show that the simulated temperatures were positive for the measured vitrinite reflectance (Ro), with a correlation coefficient (<i>R</i><sup>2</sup>) of 0.9861. With increasing temperatures, lower maturity, maturity, higher maturity, and post-maturity stages occurred at simulated temperatures (<i>Ts</i>) of 335–360 °C, 360–400 °C, 400–480 °C, and 480–575 °C, respectively. The increasing gas hydrocarbons with increasing temperature reflected the higher gas potential. Moreover, the carbon isotopes of kerogen, bitumen, expelled oil, and gases were associated with increased temperatures; among gases, methane was the most sensitive to maturity. Ignoring the intermediate reaction process, the thermal evolution process can be summarized as <i>kerogen</i><sub>0</sub><i>(original) + bitumen</i><sub>0</sub><i>(original)</i><i>→kerogen<sub>r</sub> (residual kerogen) + expelled oil (generated) + bitumen<sub>n+r</sub> (generated + residual) + C</i><sub>2<i>+</i></sub><i>(generated + residual) + CH</i><sub>4</sub><i>(generated)</i>. Among these, bitumen, expelled oil, and C<sub>2-5</sub> acted as reactants and products, whereas kerogen and methane were the reactants and products, respectively. Furthermore, the order of the carbon isotopes during the thermal evolution process was identified as: δ<sup>13</sup>C<sub>1</sub> < <sup>13</sup>C<sub>2-5</sub> < δ<sup>13</sup>C<sub>expelled oil</sub> < δ<sup>13</sup>C<sub>bitumen</sub> < δ<sup>13</sup>C<sub>kerogen</sub>. Thus, the reaction and production mechanisms of carbon isotopes can be obtained based on their changing degree and yields in kerogen, bitumen, expelled oil, and gases. Furthermore, combining the analysis of the geochemical characteristics of the Pinghu Formation coal–oil-type gas in actual strata with these pyrolysis experiments, it was identified that this area also had substantial development potential. Therefore, this study provides theoretical support and guidance for the formation mechanism and exploration of oil and gas based on changing carbon isotopes.
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spelling doaj.art-b6971776770d4428afb128d44918f3512023-11-23T08:05:34ZengMDPI AGEnergies1996-10732021-12-011424831710.3390/en14248317Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea BasinQiang Cao0Jiaren Ye1Yongchao Lu2Yang Tian3Jinshui Liu4Chenjie Xu5Hanwen Yu6Lina Sun7Key Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, ChinaKey Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, ChinaKey Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, ChinaHubei Cooperative Innovation Center of Unconventional Oil and Gas, Yangtze University, Wuhan 430100, ChinaCNOOC Shanghai Branch, Shanghai 200030, ChinaKey Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, ChinaKey Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Ministry of Education, Wuhan 430074, ChinaHubei Cooperative Innovation Center of Unconventional Oil and Gas, Yangtze University, Wuhan 430100, ChinaSemi-open hydrous pyrolysis experiments on coal-measure source rocks in the Xihu Sag were conducted to investigate the carbon isotope evolution of kerogen, bitumen, generated expelled oil, and gases with increasing thermal maturity. Seven corresponding experiments were conducted at 335 °C, 360 °C, 400 °C, 455 °C, 480 °C, 525 °C, and 575 °C, while other experimental factors, such as the heating time and rate, lithostatic and hydrodynamic pressures, and columnar original samples were kept the same. The results show that the simulated temperatures were positive for the measured vitrinite reflectance (Ro), with a correlation coefficient (<i>R</i><sup>2</sup>) of 0.9861. With increasing temperatures, lower maturity, maturity, higher maturity, and post-maturity stages occurred at simulated temperatures (<i>Ts</i>) of 335–360 °C, 360–400 °C, 400–480 °C, and 480–575 °C, respectively. The increasing gas hydrocarbons with increasing temperature reflected the higher gas potential. Moreover, the carbon isotopes of kerogen, bitumen, expelled oil, and gases were associated with increased temperatures; among gases, methane was the most sensitive to maturity. Ignoring the intermediate reaction process, the thermal evolution process can be summarized as <i>kerogen</i><sub>0</sub><i>(original) + bitumen</i><sub>0</sub><i>(original)</i><i>→kerogen<sub>r</sub> (residual kerogen) + expelled oil (generated) + bitumen<sub>n+r</sub> (generated + residual) + C</i><sub>2<i>+</i></sub><i>(generated + residual) + CH</i><sub>4</sub><i>(generated)</i>. Among these, bitumen, expelled oil, and C<sub>2-5</sub> acted as reactants and products, whereas kerogen and methane were the reactants and products, respectively. Furthermore, the order of the carbon isotopes during the thermal evolution process was identified as: δ<sup>13</sup>C<sub>1</sub> < <sup>13</sup>C<sub>2-5</sub> < δ<sup>13</sup>C<sub>expelled oil</sub> < δ<sup>13</sup>C<sub>bitumen</sub> < δ<sup>13</sup>C<sub>kerogen</sub>. Thus, the reaction and production mechanisms of carbon isotopes can be obtained based on their changing degree and yields in kerogen, bitumen, expelled oil, and gases. Furthermore, combining the analysis of the geochemical characteristics of the Pinghu Formation coal–oil-type gas in actual strata with these pyrolysis experiments, it was identified that this area also had substantial development potential. Therefore, this study provides theoretical support and guidance for the formation mechanism and exploration of oil and gas based on changing carbon isotopes.https://www.mdpi.com/1996-1073/14/24/8317coal-measure source rockXihu Sagsemi-open hydrous pyrolysiscarbon isotopematurityreaction mechanism
spellingShingle Qiang Cao
Jiaren Ye
Yongchao Lu
Yang Tian
Jinshui Liu
Chenjie Xu
Hanwen Yu
Lina Sun
Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
Energies
coal-measure source rock
Xihu Sag
semi-open hydrous pyrolysis
carbon isotope
maturity
reaction mechanism
title Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
title_full Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
title_fullStr Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
title_full_unstemmed Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
title_short Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin
title_sort evidence from the changing carbon isotopic of kerogen oil and gas during hydrous pyrolysis from pinghu formation the xihu sag east china sea basin
topic coal-measure source rock
Xihu Sag
semi-open hydrous pyrolysis
carbon isotope
maturity
reaction mechanism
url https://www.mdpi.com/1996-1073/14/24/8317
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