Calculation of critical endpoints and phase diagrams of highly asymmetric binary systems

Abstract

The computation of Global Phase Equilibrium Diagrams (GPED) for binary systems, including critical and three-phase equilibrium curves, is crucial for analyzing process conditions and assessing thermodynamic models. In the past two decades, algorithmic strategies and GPEC software have become essential tools. However, numerical problems can arise with the original algorithm for highly asymmetric systems, such as gases or water with heavy compounds or polymers, hindering the completion of GPED and related diagrams.

This study presents an innovative calculation methodology to address these challenges. Our approach extends existing algorithms to achieve automatic GPED generation without user intervention, focusing on nearly pure phases. We apply our methodology to systems such as methane or water with heavy alkanes, and CO2 + silicones. The proposed algorithmic strategies effectively handle asymmetric systems, different types of phase behavior, and the estimation of extremely low concentrations in nearly pure phases along the vapor-liquid-liquid equilibrium curve.