Methane hydrate phase equilibrium considering dissolved methane concentrations and interfacial geometries from molecular simulations.

Natural gas hydrates, mainly existing in permafrost and on the seabed, are expected to be a new energy source with great potential. The exploitation technology of natural gas hydrates is one of the main focuses of hydrate-related studies. In this study, a large-size liquid aqueous solution wrapping a methane hydrate system was established and molecular dynamics simulations were used to investigate the phase equilibrium conditions of methane hydrate at different methane concentrations and interfacial geometries. It is found that the methane concentration of a solution significantly affects the phase equilibrium of methane hydrates. Different methane concentrations at the same temperature and pressure can lead to hydrate formation or decomposition. At the same temperature and pressure, in a system reaching equilibrium, the size of spherical hydrate clusters is coupled to the solution concentration, which is proportional to the Laplace pressure at the solid-liquid interface. Lower solution concentrations reduce the phase equilibrium temperature of methane hydrates at the same pressure; as the concentration increases, the phase equilibrium temperature gradually approaches the actual phase equilibrium temperature. In addition, the interfacial geometry of hydrates affects the thermodynamic stability of hydrates. The spherical hydrate particles have the highest stability for the same volume. Through this study, we provide a stronger foundation to understand the principles driving hydrate formation/dissociation relevant to the exploitation of methane hydrates.