Importance of clay-H2 interactions for large-scale underground hydrogen storage

Underground hydrogen storage is considered an option for large-scale green hydrogen storage. Among different geological storage types, depleted oil/gas fields and saline aquifers stand out. In these cases, hydrogen will be prevented from leaking back to the surface by a tight caprock seal. It is therefore essential to understand hydrogen interactions with shale-type caprocks. To this end, natural pure montmorillonite clay was exposed to hydrogen gas at different pressures (0-50 bar) and temperatures (77, 195, 303 K) to acquire data on its adsorption capacity related to UHS and caprock saturation. Montmorillonite was chosen because of its large specific surface area enabling quantification of the adsorption process. Hydrogen adsorption was successfully fitted with a Langmuir isotherm model and yielded small partition coefficients indicating that hydrogen does not preferentially adsorb to the clay surface. Adsorption on montmorillonite goes back to weak physisorption as inferred from minor negative changes in the enthalpy of reaction (-790 J/ mol), derived from an Excel Solver approach to the van't Hoff equation. Based on own as well as literature values, adsorption capacities, which were originally reported as mol/kg or wt%, are recast as hydrogen volume adsorbed per specific surface area (mL/m2). The ac-quired range is surprisingly narrow, with values ranging from 3 to 6 mL/m2, and indicates the normalised volume of hydrogen that can be expected to remain in the shale-type caprock after injected hydrogen migrated upwards through the porous reservoir. This 'residual' caprock saturation with hydrogen can be further restrained by considering the geothermal gradient and its effect on the molar volume of hydrogen. The experimental results presented here recommend injecting hydrogen deeper rather than shallower as pressure and temperature work in favour of increased storage volumes and decreased hydrogen loss through clay adsorption in the caprock.