Molecular insights into the impact of mineral pore size on methane hydrate formation

Abstract

Natural gas hydrates are not only substantial energy sources but also have significant applications in the chemical industry and other fields. Although investigating hydrate formation in sediment minerals is crucial for their development and utilization, the underlying hydrate formation mechanism remains unclear. Here, molecular simulations were conducted in systems incorporating hydrophobic and hydrophilic pores of different sizes to investigate methane hydrate formation processes. The findings suggest that, as the hydrophobic slit size increases, there is a larger number of dissolved methane after the system reaches a metastable equilibrium state. The probability of cage formation indicates that hydrate cages readily form on hydrophobic surfaces or in the solution phase near the solution/gas interface. The larger slits are preferred for hydrate nucleation, regardless of whether the surface is hydrophobic, with most initial nuclei located near the liquid/methane interface. However, the interface perturbation can lead to the movement and growth of hydrate nuclei near the solution/methane interface into the bulk solution phase. Additionally, hydrate can nucleate and grow on the hydrophobic surface, facilitated by the adsorbed methane molecules and nonstandard cages. Pores hinder methane storage capacity in the hydrate phase due to the confinement effect and the amorphous nature of the hydrate formed. These molecular-level findings enhance our understanding of hydrate formation in sedimentary environments and porous materials, benefiting the development of natural gas hydrates and the use of porous materials for gas storage and transportation.