Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977-984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ¹³C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of natural gas generation in these experiments is attributed to the metals not occurring in the proper form or the poisoning of potential catalytic microcosms by polar-rich bitumen, which impregnates the rock matrix during the early stages of petroleum formation.