Thermodynamic models for mixtures containing oxygenated compounds of non-fossil origin

The optimal and effective design of chemical engineering processes, particularly for biofuels and oxygenated compounds, greatly rely on accurate thermodynamic and kinetic modeling. The thesis focuses on the choice, evaluation, and comparison of equations of state (EOS) for modeling oxygenated compound-bearing mixtures from non-fossil sources, i.e., fatty acids, triglycerides, and their derivatives. The thesis primarily discusses the predictive capability of several EOS such as SAFT, PC-SAFT, Polar PC-SAFT (P-PCSAFT), PHSC, Sanchez & Lacombe (SL), and Peng-Robinson (PR) with particular focus on their performance in predicting phase behavior, thermodynamic and transport properties, and reaction kinetics for esterification reactions. With the aim to fulfill the aforementioned needs, the current study provides a new comparison to determine the most accurate equation of state for the estimation of oxygenated compounds' thermodynamic properties (e.g., VLE, LLE, SLE, Density, Enthalpy of vaporization) in biofuel and biodiesel applications. Besides, viscosity, which is another critical property in the production of biofuels, was the focus of this research too. Other than experimentally measuring the viscosity of oxygenated compounds, predictive viscosity using entropy scaling (ES) method and free volume theory (FVT) were also analyzed. Entropy scaling model has been discovered to make more reliable predictions for viscosity compared to the free volume theory model. These models were built and calibrated with experimental data such as liquid density and vapor pressure to extract and refine EOS parameters for pure components, particularly where experimental data were limited. The findings indicate that PC-SAFT model and its derivatives (e.g., Polar PC-SAFT and PC-SAFT with induced association interaction), provide improved accuracy for prediction of thermodynamic properties of oxygenated compounds based on the type of system and the components and the structure of each of the components.