Abstract
Hydrate phase equilibria for the binary CH4 + water and CO2 + water mixtures in silica gel pores of nominal diameters 6.0, 15.0, and 30.0 nm were measured and compared with the calculated results based on van der Waals and Platteeuw model. At a specified temperature, three phase H−LW−V equilibrium curves of pore hydrates were shifted to the higher pressure region depending on pore sizes when compared with those of bulk hydrates. The activities of water in porous silica gels were expressed with a correction term to account for both capillary effect and activity decrease. By using the values of interfacial tension between hydrate and liquid water phases which were recently presented by Uchida et al.,5 the calculation values were in better agreement with the experimental ones. The structure and hydration number of CH4 hydrate in silica gel pores (6.0, 15.0, and 30.0 nm) were found to be identical with those of bulk CH4 hydrate through NMR spectroscopy.
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