An examination of the ternary methane + carbon dioxide + water phase diagram using the SAFT-VR approach.

In this work, the molecular based Variable Range Statistical Associating Fluid Theory (SAFT-VR) has been used to estimate the global phase equilibria diagram of the ternary mixture water + carbon dioxide + methane, over a wide pressure and temperature range. An accurate determination of the phase equilibria of this mixture is relevant in Petrophysics, as, for instance, in enhanced natural gas recovery from low permeability reservoirs (the so-called tight gas reservoirs), or in geology, as it is the basic composition of many geological fluids. A previous study on the phase behavior of the binary mixtures involved is presented, using in a transferable manner the characteristic molecular parameters for the three molecules involved. The ternary mixture presents a very rich and complex phase behavior, with a wide region of the thermodynamic space of phases (at higher pressures) presenting a large gap of ternary liquid-liquid equilibria, that upon descending pressures leads to the transition to a three-phase liquid-liquid-vapor equilibria region, and both regions are separated by a continuous critical end point line. The ability of the theory to describe this complex multicomponent mixture phase transition with a reduced and physically sound set of characteristic parameters must be underlined.