Phase behavior and structure transition of the mixed methane and nitrogen hydrates

Pure methane and nitrogen form structure I and II hydrate, respectively, and therefore the structure type of mixed gas hydrate was found to largely depend on their relative gas composition. In addition to the structural difference of size and shape, each hydrate structure shows different capacity to store the guest molecules. In this study, we investigated phase and structural behaviors according to the composition of methane+nitrogen gas mixture. Three-phase (H-Lw-V) equilibria of solid hydrate, water-rich liquid and vapor phase containing 25.24 mol%, 28.51 mol%, 31.23 mol% and 40.39 mol% of methane were determined at various temperatures (in the range from 273.30 K to 285.05 K) and pressures (from 8.325 MPa to 20.700 MPa). 13C solid-state NMR spectroscopy and powder XRD method were performed to identify the formed structure of hydrate samples. The experimental results showed that gas hydrate of the methane+nitrogen mixture changes its structure from sI to sII between 25.24 mol% and 28.51 mol% of methane concentration. These results of phase behavior and structure identification for the mixed gas hydrates are expected to be very helpful in evaluating the feasibility of exploitation of methane gas from natural gas hydrate and the separation process using gas hydrate as a storage-media