Phase equilibrium for clathrate hydrates formed with methane, ethane, propane, or carbon dioxide at temperatures below the freezing point of water

This paper reports the three-phase (ice + hydrate + guest-rich vapor) equilibrium pressure-temperature conditions at temperatures (243 to 273) K in the systems of water and each of the following guest gases: methane, ethane, propane, and carbon dioxide. The measurements were also performed for the water-rich liquid + hydrate + guest-rich vapor three-phase equilibrium conditions at temperatures above 273 K. The pressure ranges of the present measurements in the four systems are (0.971 to 2.471) MPa in the methane system, (0.122 to 0.637) MPa in the ethane system, (41.0 to 280.0) kPa in the propane system, and (0.364 to 0.963) MPa in the carbon dioxide system. On the basis of the obtained three-phase equilibrium data, the quadruple points for the ice + water-rich liquid + hydrate + guest-rich vapor were also determined in the respective systems. The measurements were carried out using the batch, isochoric procedure. Fine-grained ice powders with diameters of (1 to 2) mm were used to form the hydrate. The measured data were compared with the corresponding data reported in the literature.