Experimental Measurement and Thermodynamic Modeling of the Mixed CH4 + C3H8 Clathrate Hydrate Equilibria in Silica Gel Pores: Effects of Pore Size and Salinity

Abstract

We measured hydrate phase equilibria for the ternary CH4 (90%)+ C3H8 (10%)+ water mixtures in silica gel pores with nominal diameters of 6.0, 15.0, 30.0, and 100.0 nm and for the quaternary CH4 (90%)+ C3H8 (10%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt%) in silica gel pores with nominal diameters of 6.0, 15.0, and 30.0 nm. The CH4 (90%)+ C 3H8 (10%) hydrate-water interfacial tension (σHW) of 42 ± 3mJ/m2 was obtained through the Gibbs-Thomson equation for dissociation within cylindrical pores. With this value, the experimental results were in good agreement with the calculated ones based on the van der Waals and Platteeuw model. A correction term for the capillary effect and a Pitzer model for electrolyte solutions were adopted to calculate the activity of water in the aqueous electrolyte solutionswithin silica gel pores. At a specified temperature, three-phaseH-LW- Vequilibriumcurves of pore hydrateswere shifted to higher-pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent 13CNMR chemical shifts of enclathrated guest molecules, the mixed CH4 (90%)+ C3H8 (10%) gas hydrate was confirmed to be structure II.