Molecular simulation study of methane hydrate decomposition in the presence of hydrophilic and hydrophobic solid surfaces

Natural gas hydrates (NGHs) exist mainly in marine muddy porous media, and it is of great significance to understand the hydrate decomposition in microporous sediments for hydrate exploration. In the paper, molecular dynamics (MD) simulations have been performed for CH4 hydrate decomposition in the slit nanopores of graphite and hydroxylated-silica surfaces. As expected, the higher the temperature, the faster the decomposition rate. Compared with the hydrate decomposition in the free system, the solid surface can enhance hydrate decomposition; the hydroxylated silica surface has better enhancement effect, and this effect is more obvious at lower temperatures. At 330 K, 340 K, 350 K and 360 K, the decomposition rates of hydrate in HS-H systems are 50.8%, 36.4%, 14.7% and 11.7%, respectively, which are higher than those in G-H systems. In the slit-nanopores, hydrate decomposition starts from the surface and then grows towards the bulk region, the hydrate near the pore surface decomposes faster. However, due to the strong ability of the hydrophilic surface to adsorb water molecules, the hydrophilic-silica pore has a more vital role in enhancing hydrate decomposition near the surface in the early stage. The higher the temperature, the stronger the diffusion ability of methane molecules and water molecules, and methane molecules diffuse more easily in pores in directions parallel to the surface than perpendicular to it. Due to the difference in wettability, the contact angles of nanobubbles on the surface are different, resulting in different forms of nanobubbles. For the G-H system, both surface cap bubbles and bulk spherical bubbles were formed at higher temperatures, while only surface cap bubbles were formed at lower temperatures. For the HS-H system, bulk spherical bubbles were formed over the temperature range studied. The formation conditions of the bulk spherical bubbles are more lenient than surface cap bubbles. The hydrates in the graphene pores proceed in an isotropic and uniform decomposition. At 330 K, the liquid methane concentration of HS-H system (0.03181-0.03397) is higher than that of G-H system (0.02452-0.02559) at t = 4-6 ns, while the decomposition rate is higher than that of G-H system, which is due to the formation of bulk spherical bubbles. Bulk spherical bubbles in the hydroxylated-silica pores leads to the uneven decomposition of the hydrates, this inhomogeneity leads to local differences in hydrate dissociation rate, and the difference in hydrate dissociation rates in different regions can be up to 4.3 times. The above findings provide the theoretical basis for the safe and efficient exploitation and transportation of hydrate in marine sediments.