A comparative study of thermodynamic models to describe the VLE of the ternary electrolytic mixture H2O–NH3–CO2

Abstract

Abstract This study aims to ascertain the influence of the activity coefficient model and equation of state for predicting the vapor–liquid equilibrium (VLE) of the multi-electrolytic system H2O–NH3–CO2. The non-idealities of the liquid phase are described by the eUNIQUAC and eNRTL models. The vapor phase is modeled with the Nakamura equation, which is compared with the ideal gas assumption. The models are validated with experimental data from literature on total pressure and ammonia partial pressure. Results show that the models UNIQUAC and NRTL without dissociation can only reproduce the experimental conditions in the absence of CO2. When the electrolytic term is considered, the eUNIQUAC model is able to reproduce the experimental data with greater accuracy than the eNRTL. The equation of state which describes the vapor phase plays no major role in the accuracy of the VLE prediction in the operational conditions evaluated here. Indeed, the accuracy relies on the activity coefficient, therefore the ideal gas equation can be considered if the non-idealities of the liquid phase are described by a well-tuned model. These findings could be useful for equipment design, flowsheet simulations and large-scale simultaneous optimization problems.