New insights into the role of system sealing capacity in shale evolution under conditions analogous to geology: Implications for organic matter evolution and petroleum generation

Closed and semi-closed pyrolysis of a lacustrine shale sample were conducted using the same instrument characterized by lithostatic pressure and limited reactive space in order to unravel the impacts of system sealing capacity on organic matter evolution and hydrocarbon generation in shales under conditions analogous to natural processes. The products and solid residues were subjected to chemical composition determination, gaseous carbon isotopic composition analysis, solvent extraction, and Rock-Eval pyrolysis. Higher organic matter transformation and oil retention contents were obtained at 300–500 °C in the closed pyrolysis system compared to those in the semi-closed system at the same temperature ranges. However, lower yields of hydrocarbons except for methane were obtained in the closed system at this temperature range, while the iso-/n-C4,5 as well as C1/C1-5 values were significantly higher in this system. Stronger recombined reactions between kerogen and hydrocarbons were proposed to occur at 300–500 °C during the closed pyrolysis process, leading to the consumption of oil and hydrocarbon gases. Ultimately, positive deviations of initially more negative δ13C2∼3 values were occurred in the closed system, resulting in similar δ13C2∼3 values from the two systems before secondary cracking of hydrocarbon gases commences, but the δ13C1 value from the closed system was overall more negative. Different water retention ratios and hydrocarbon expulsion efficiencies induced by system sealing capacity are the predominant factor controlling organic matter evolution and petroleum generation during the pyrolysis processes. This highlights that the different gas contents of the Cambrian and Silurian shales in South China may be associated with the differences in the system sealing capacities of shales, although the sedimentary environment of the studied sample is lacustrine, and the lower methane content of the Cambrian shale gas is probably ascribed to semi-closed system. Finally, a higher ratio of oil cracking gas may be an important signal for natural gas systems that have better exploration potential.