Hydrate phase equilibria in porous media: effect of pore size and salinity

Considering the ever-increasing importance of marine gas hydrates, it is crucial to gain a better understanding of clathrate formation and decomposition in porous media. It is well established that, due to capillary effects, small-diameter pores - similar to those found in natural sediments - act to inhibit hydrate stability. However, accurate data constraining these effects are still lacking. Here, we present experimental methane clathrate dissociation data for 3.5 mass% methanol aqueous solutions in confined silica glass pores of narrow distribution (30.6, 15.8, and 9.2 nm mean diameters). These data have been used to validate a thermodynamic model for clathrate stability porous media. Experimental data show a marked improvement on literature data - which we attribute to the experimental and interpretative methods used - and are in good agreement with the model predictions. Results suggest that mass transfer of inhibitors (methanol) and dissolved gas during clathrate formation/dissociation within the porous network plays an important role in controlling gas hydrate equilibria.