Phase equilibrium data and thermodynamic modeling of the system (CO2 + biodiesel + methanol) at high pressures

The main objective of this work was to investigate the high pressure phase behavior of the binary systems {CO2(1) + methanol(2)} and {CO2(1) + soybean methyl esters (biodiesel)(2)} and the ternary system {CO2(1) + biodiesel(2) + methanol(3)} were determined. Biodiesel was produced from soybean oil, purified, characterized and used in this work. The static synthetic method, using a variable-volume view cell, was employed to obtain the experimental data in the temperature range of (303.15 to 343.15) K and pressures up to 21 MPa. The mole fractions of carbon dioxide were varied according to the systems as follows: (0.2383 to 0.8666) for the binary system {CO2(1) + methanol(2)}; (0.4201 to 0.9931) for the binary system {CO2(1) + biodiesel(2)}; (0.4864 to 0.9767) for the ternary system {CO2(1) + biodiesel(2) + methanol(3)} with a biodiesel to methanol molar ratio of (1:3); and (0.3732 to 0.9630) for the system {CO2 + biodiesel + methanol} with a biodiesel to methanol molar ratio of (8:1). For these systems, (vapor + liquid), (liquid + liquid), (vapor + liquid + liquid) transitions were observed. The phase equilibrium data obtained for the systems were modeled using the Peng–Robinson equation of state with the classical van der Waals (PR-vdW2) and Wong-Sandler (PR–WS) mixing rules. Both thermodynamic models were able to satisfactorily correlate the phase behavior of the systems investigated and the PR–WS presented the best performance.

► We measured phase behavior for the system involving {CO2 + biodiesel + methanol}.
► The saturation pressures were obtained using a variable-volume view cell.
► The experimental data were modeled using PR-vdW2 and PR–WS equations of state.