Lawrence Berkeley National Laboratory

We form methane hydrate by injecting methane gas into a brine-saturated, coarse-grained sample under hydrate-stable thermodynamic conditions. Hydrate forms to a saturation of 11%, which is much lower than that predicted assuming three-phase (gas-hydrate-brine) thermodynamic equilibrium (67%). During hydrate formation, there are temporary flow blockages. We interpret that a hydrate skin forms a physical barrier at the gas-brine interface. The skin fails periodically when the pressure differential exceeds the skin strength. Once the skin is present, further hydrate formation is limited by the rate that methane can diffuse through the solid skin. This process produces distinct thermodynamic states on either side of the skin that allows gas to flow through the sample. This study illuminates how gas can be transported through the hydrate stability zone and thus provides a mechanism for the formation of concentrated hydrate deposits in sand reservoirs. It also illustrates that models that assume local equilibrium at the core-scale and larger may not capture the fundamental behaviors of these gas flow and hydrate formation processes.