title: 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 CH(4) (90%) + C(3)H(8) (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 CH(4) (90%) + C(3)H(8) (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 CH(4) (90%) + C(3)H(8) (10%) hydrate-water interfacial tension (sigma(HW)) of 42 +/- 3 mJ/m(2) 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 solutions within silica gel pores. At a specified temperature, three-phase H-L(W)-V equilibrium curves of pore hydrates were shifted to higher-pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent (13)C NMR chemical shifts of enclathrated guest molecules, the mixed CH(4) (90%) + C(3)H(8) (10%) gas hydrate was confirmed to be structure II.
authors.affiliation: Department of Chemical Engineering, Changwon National University, 9 Sarim-dong, Changwon, Gyeongnam 641-773, Republic of Korea.
authors.forename: Seungmin
authors.initials: S
authors.lastname: Lee
authors.forename: Yongwon
authors.initials: Y
authors.lastname: Seo