Yongwon Seo

Phase Equilibria and Thermodynamic Modeling of Ethane and Propane Hydrates in Porous Silica Gels

In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

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

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.

Phase Behavior and 13C NMR Spectroscopic Analysis of the Mixed Methane + Ethane + Propane Hydrates in Mesoporous Silica Gels

In this study, the phase behavior and quantitative determination of hydrate composition and cage occupancy for the mixed CH(4) + C(2)H(6) + C(3)H(8) hydrates were closely investigated through the experimental measurement of three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria and (13)C NMR spectra. To examine the effect of pore size and salinity, we measured hydrate phase equilibria for the quaternary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + water mixtures in silica gel pores of nominal diameters of 6.0, 15.0, and 30.0 nm and for the quinary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt %) in silica gel pores of a nominal 30.0 nm diameter. The value of hydrate-water interfacial tension for the CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) hydrate was found to be 47 ± 4 mJ/m(2) from the relation of the dissociation temperature depression with the pore size of silica gels at a given pressure. 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(2)H(6) (7%) + C(3)H(8) (3%) gas hydrate was confirmed to be structure II. The cage occupancies of each guest molecule and the hydration number of the mixed gas hydrates were also estimated from the (13)C NMR spectra.

Accurate measurement of phase equilibria and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl for potential application in desalination

Phase equilibria, structure identification, and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl are investigated for potential application in desalination. To verify the influence of NaCl on the thermodynamic hydrate stability of the HFC-134a hydrate, the three-phase (hydrate (H) - liquid water (LW) - vapor (V)) equilibria of the HFC-134a+NaCl (0, 3.5, and 8.0 wt%)+water systems are measured by both a conventional isochoric (pVT) method and a stepwise differential scanning calorimeter (DSC) method. Both pVT and DSC methods demonstrate reliable and consistent hydrate phase equilibrium points of the HFC-134a hydrates in the presence of NaCl. The HFC-134a hydrate is identified as sII via powder X-ray diffraction. The dissociation enthalpies (ΔHd) of the HFC-134a hydrates in the presence of NaCl are also measured with a high pressure micro-differential scanning calorimeter. The salinity results in significant thermodynamic inhibition of the HFC-134a hydrates, whereas it has little effect on the dissociation enthalpy of the HFC-134a hydrates. The experimental results obtained in this study can be utilized as foundational data for the hydrate-based desalination process.