Adsorption and absorption of supercritical methane within shale kerogen slit

Gas storage in shale primarily includes three forms: free gas in the fractures or macropores, adsorbed gas upon the kerogen surface, and absorbed gas in the kerogen matrix. However, current techniques cannot distinguish the adsorbed and absorbed gas, which restrict the understanding of gas storage and transport mechanisms through shale kerogen. On the basis of the grand canonical Monte Carlo (GCMC) simulations, we propose a technique to determine the independent adsorption and absorption isotherms of methane within slit-shaped shale kerogen under supercritical conditions. We observe that if the pore pressure is higher than ~3.5 MPa, the absorption amount is much smaller than that of adsorbed gas; however, at lower pressures, the absorption capacity is superior to that of the adsorption. Meanwhile, the ratio between adsorption and absorption quantities continuously increases with pressure. We probe the underlying mechanisms and study the effect of slit aperture, temperature, as well as moisture on gas adsorption and absorption capacity. Enlarging the slit aperture increases the adsorbed gas contents but shows only a negligible effect on the absorption capacity. Heating facilitates the escapement of gas molecules, thus leading to the inhibition of both adsorption and absorption capacities. Water molecules occupying the adsorption site on the slit surface impedes methane adsorption, but the absorption capacity within the kerogen matrix remains unchanged. This work elucidates the gas adsorption and absorption behavior in shale kerogen and sheds light on the storage and transport of hydrocarbons in nanoporous materials.