Inclusion of variable characteristic length in microemulsion flash calculations

Recent developments in predicting microemulsion phase behavior for use in chemical flooding are based on the hydrophilic-lipophilic deviation (HLD) and net-average curvature (NAC) equation-of-state (EoS). The most advanced version of the HLD-NAC EoS assumes that the three-phase micelle characteristic length is constant as parameters like salinity and temperature vary. In this paper, we relax this assumption to improve the accuracy and thermodynamic consistency of these flash calculations. We introduce a variable characteristic length in the three-phase region based on experimental data that is monotonic with salinity or other formulation variables, such as temperature and pressure. The characteristic length at the boundary of the three-phase region is then used for flash calculations in the two-phase lobes for Winsor type I/II. The functional form of the characteristic length is made consistent with the Gibbs phase rule. The improved EoS can capture asymmetric phase behavior data around the optimum, whereas current HLD-NAC based models cannot. The variable characteristic length formulation also resolves the thermodynamic inconsistency of existing phase behavior models that give multiple solutions for the optimum. We show from experimental data and theory that the inverse of the characteristic length varies linearly with formulation variables. This important result means that it is easy to predict the characteristic length in the three-phase region, which also improves the estimation of surrounding two-phase lobes. The results show that the optimum solubilization ratio can change significantly by a factor of two when variable characteristic length is included as temperature and pressure change. This can in turn greatly impact the interfacial tension (IFT) at optimum. This improved physical understanding of microemulsion phase behavior should aid in the design of surfactant blends and improve recovery predictions in a chemical flooding simulator.