Quantum physisorption behavior of methane in nanoporous shales: Model and new mechanism

Abstract

Methane adsorption in nanoporous shales plays a significant role in the storage and flow of shale gas. Although previously numerous theoretical models have been proposed to describe the gas adsorption behavior, how the potential energy distribution in nanopores impacts gas adsorption remains unclear. The mechanism of methane adsorption in extremely complicated nanopores is still no satisfactory explanation. In this study, a total of 28 shale samples located in the Paleozoic-Mesozoic strata from different sedimentary environments were utilized to investigate the nature and process of quantum physisorption of methane in nanoporous shales. It was suggested that methane confined within nanoscale space shows a quantum effect, and the physisorption behavior of methane may be the result of molecular energy level transition. Further, the quantum physisorption model was developed by considering the quantum potential energy distribution, maximum adsorption amount, gas temperature and gas pressure, which matches the isothermal adsorption data well for a various of shales under widely varied temperature and gas pressure condition. The adsorption amounts of methane with different energy levels can also be obtained by the model. Finally, a new mechanism of the methane quantum physisorption in nanoporous shales was proposed. Uneven spatial distribution of gas molecules and elementary space of gas adsorption are the intrinsic factors of controlling the quantum physisorption behavior. The former is mainly influenced by minimum potential unit (E₀) and gas temperature, while the latter is represented by the parameter of maximum adsorption amount (n_L) which impacted by specific surface area and gas temperature. Gas pressure only affects the molecule concentration with different energy levels, but does not affect the spatial distribution of molecule. E₀ and n_L vary in shales from different sedimentary environments, due to the difference in organic matter properties (TOC content and kerogen type), which indirectly impacts the methane physisorption behavior. These results are helpful to deeply understand the storage of methane in shales and improve the efficient development of shale gas. In addition, this study is expected to open a new research direction about the quantum physisorption of gas in nanoporous media.