Dissociation Conditions of Methane Hydrate in Mesoporous Silica Gels in Wide Ranges of Pressure and Water Content

Abstract

The temperature of methane hydrate dissociation in silica mesopores has been monitored within a wide range of pressures from 10 MPa to 1 GPa. Because the determination of pore size appears to be crucial for the studied phenomenon, several methods of calculation have been applied. According to our findings, the size that corresponds to the mean size of the most representative pores is to be considered as the most reliable. It was concluded that the shape of hydrate particles replicates a host space of pores and may have a complex (e.g., fractal) shape. An attempt to simulate the curvature of hydrate particles by globular (quasi-spherical), elongated (quasi-cylindrical), or any intermediate models has been done. The quasi-spherical model seems to be more adequate for hydrate particles in small pores (<8 nm), while the quasi-cylindrical model fits better the experimental data for hydrate particles in larger pores. According to our experimental results, the hydrate can be formed in pores only by capillary condensate, without involving the water layers tightly bound by the surface, and pressure has an insignificant effect on the decrease of the dissociation temperature of the confined hydrate. A new effect of the formation of hydrates at a temperature higher than the bulk hydrate dissociation temperature has been observed for silica gels with the narrowest pores studied.