Abstract
To determine the ability of dimethyl sulfoxide (DMSO) to inhibit methane hydrate formation by the thermodynamic mechanism, we measured the pressures and temperatures of monovariant equilibrium of three phases: gaseous methane, aqueous DMSO solution, and methane hydrate. A total of 54 equilibrium points were obtained. Hydrate equilibrium conditions have been measured for eight different concentrations of dimethyl sulfoxide ranging from 0 to 55 mass%, at temperatures of 242-289 K and pressures of 3-13 MPa. Measurements were performed in an isochoric autoclave (volume of 600 cm(3), inside diameter of 8.5 cm) at a heating rate of 0.1 K/h and intense fluid agitation (600 rpm) with four-blade impeller (diameter of 6.1 cm, blade height of 2 cm). The specified stirring speed for aqueous DMSO solutions at 273-293 K is equivalent to a range of Reynolds numbers of 5.3‧10(3)-3.7‧10(4). The endpoint of methane hydrate dissociation at defined temperature and pressure values was taken as the equilibrium point. The anti-hydrate activity of DMSO was analyzed on a mass% and mol% scale. Precise correlations between the thermodynamic inhibition effect of dimethyl sulfoxide ΔT(h) and the influencing factors (DMSO concentration and pressure) were derived. Powder X-ray diffractometry was employed to examine the phase composition of the samples at 153 K. Measurement of ice freezing points in aqueous solutions of dimethyl sulfoxide (up to 50 mass%) at ambient pressure allowed us to clarify the location of the liquidus line in the DMSO-H(2)O system and to check the hydrate equilibrium data for thermodynamic consistency.