Adsorption of methane and carbon dioxide by water-saturated clay minerals and clay rocks

Understanding the effects of water on gas adsorption in geological media is of high importance in order to efficiently control numerous subsurface engineering process operating at gas/rock interfaces. Due to preferential interaction with clay surfaces, water fills their porous body, greatly reducing CH4 and CO2 adsorption capacity. In order to quantitatively describe CH4 and CO2 adsorption by hydrated clay minerals, this work proposes to rely on the mechanism of gas uptake by dissolution in pre-adsorbed pore water. This approach was employed to characterise water-saturated porous media of increasing complexity: mesoporous silica SBA-15 and silica gel with different pore sizes and geometry, isolated illite and montmorillonite and natural clay-rich rock (the Callovo-Oxfordian formation - COx, France) in powdered and crushed states. It was found that the solubility in water can reliably explain the CO2 uptakes by hydrated pore systems regardless of their nature as well as the CH4 uptakes, but only for solids with large mesopores and montmorillonite mineral. A so called "adsorption enhanced gas uptake in pore water" for CH4, exceeding its solubility in bulk water by a factor of 5-8, was observed for the systems with narrow pore sizes, highlighting the impact of surface energy on gas uptake and the occurrence of the interaction of weakly-soluble methane with the surface, promoting its uptake in comparison to pure dissolution.