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

Abstract

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 (R2) of 0.9861. With increasing temperatures, lower maturity, maturity, higher maturity, and post-maturity stages occurred at simulated temperatures (Ts) 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 kerogen0(original) + bitumen0(original)→kerogenr (residual kerogen) + expelled oil (generated) + bitumenn+r (generated + residual) + C2+(generated + residual) + CH4(generated). Among these, bitumen, expelled oil, and C2-5 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: δ13C1 < 13C2-5 < δ13Cexpelled oil < δ13Cbitumen < δ13Ckerogen. 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.