Prediction of Vapor−Liquid Equilibrium at High Pressure Using a New Excess Free Energy Mixing Rule Coupled with the Original UNIFAC Method and the SRK Equation of State

Abstract

A new excess free energy mixing rule that employs a low-pressure reference state is proposed in this work. This new low-pressure mixing rule (LPMR), coupled with the original UNIFAC method and the Soave−Redlich−Kwong (SRK) equation of state (EoS), leads to an improved EoS/GE predictive model (LPMR−SRK model) that was applied to the high-pressure vapor−liquid phase equilibria of various systems including symmetric and asymmetric systems of n-alkanes with different gases (C2H6, C3H8, CO2, H2) and polar systems. The results are compared with those of other EoS/GE predictive models, such as the predictive Soave−Redlich−Kwong (PSRK), Chen-modified PSRK (MPSRK), volume-translated Peng−Robinson group contribution equation of state (VTPR), and linear combination of the Vidal and Michelsen rules (LCVM) models. It is demonstrated that LPMR−SRK method gives similar accuracy as the PSRK approach for symmetric or slightly asymmetric systems and gives better results than the MPSRK, VTPR, and LCVM models. For highly asy...