Molecular Simulation of Methane Adsorption in Deep Shale Nanopores: Effect of Rock Constituents and Water

The molecular models of nanopores for major rock constituents in deep shale were constructed. The microscopic adsorption behavior of methane was simulated by coupling the grand canonical Monte Carlo and Molecular Dynamics methods and the effect of rock constituents was discussed. Based on the illite and kerogen nanopore models, the discrepancies in microscopic water distribution characteristics were elucidated, the effects of water on methane adsorption and its underlying mechanisms were revealed, and the competitive adsorption characteristics between water and methane were elaborated. The results show a similar trend in the microscopic distribution of methane between different shale rock constituents. Illite and kerogen slit pores have no significant difference in methane adsorption capacity. The adsorption capacity per unit mass of kerogen is greater than that of illite due to the smaller molar mass of the kerogen skeleton and its large intermolecular porosity. Illite has a greater affinity for water than methane. With increasing water content, water molecules preferentially occupy the high-energy adsorption sites and then overspread the entire pore walls to form water adsorption layers. Methane molecules are adsorbed on the water layers, and methane adsorption has little effect on water adsorption. Kerogen is characterized as mix-wetting. Water molecules are preferentially adsorbed on polar functional groups and gather around to form water clusters. In kerogen with high water content, methane adsorption can facilitate water cluster fusion and suppress water spreading along pore walls. In addition to adsorption, some water molecules dissolve in the kerogen matrix.