Abstract
To investigate the characteristics and generation potential of gas generated from over-mature shale, hydrous and anhydrous pyrolysis experiments were carried out on the Longmaxi Formation in the Anwen 1 well of the Sichuan Basin of China at temperatures of 400−598 °C and pressures of 50 Mpa, with (hydrous) and without (anhydrous) the addition of liquid water. The results show that in the presence of water, the total yield of carbon-containing gases (i.e., the sum of methane, ethane, and carbon dioxide) was increased by up to 1.8 times when compared to the total yield from the anhydrous pyrolysis experiments. The increased yield of carbon dioxide and methane accounted for 89% and 10.5% of the total increased yield of carbon-containing gases. This indicated that the participation of water could have promoted the release of carbon from over-mature shale, like we used in this study. The methane generated in the hydrous pyrolysis experiments was heavier, with a δ13C value of −21.27‱ (544 °C) compared to that generated in the anhydrous pyrolysis experiments, which showed a lighter δ13C of −33.70‱ (544 °C). It is noteworthy that the δ13C values of the methane from hydrous pyrolysis at >500 °C were even heavier than that of the kerogen from the over-mature shale, although the δ13C values of the methane show an overall increasing trend with increasing temperature both in hydrous and anhydrous pyrolysis. The carbon dioxide from hydrous pyrolysis was less enriched in 13C relative to that from anhydrous pyrolysis. Specifically, the δ 13C values of the carbon dioxide increased with the increasing temperature in anhydrous pyrolysis, whereas they remained nearly constant with increasing temperature in hydrous pyrolysis. The overall lighter δ13C values of the carbon dioxide generated in the hydrous pyrolysis experiments likely indicate that water tends to prompt the release of lighter carbon and/or suppress the release of heavier carbon from over-mature shale in the form of carbon dioxide, especially at higher temperatures, for example, of >510 °C.