Determination of liquid–vapor equilibrium and critical properties of fatty acids for biodiesel production through molecular dynamics

Abstract

Abstract In recent years, biodiesel production has emerged as an option for renewable and green fuel generation due to the constant reduction of fossil fuel reservoirs. Biofuels as biodiesel also show valuable attributes, environmentally speaking, due to their low environmental impact, contributing to the achievement of sustainability. However, costs are not allowable for large-scale production. Thereby, several novel processes have been proposed (e.g., reactive distillation) to solve this issue. An inconvenience for the development of these processes is the little information in the literature about the critical properties of fatty acids, which are precursors of biodiesel. Determination of critical properties for fatty acids through experimentation is difficult. The reason is that fatty acids tend to self-associate (to dimerize) due to carboxylic groups presence through hydrogen bonds, and consequently, have higher boiling points than other compounds of similar molecular mass (e.g., hydrocarbons, esters). Therefore, alternative methods for this determination are required. One choice is the group-contribution method, which is based on the structure of the molecule; however, results can significantly vary among different group-contribution approaches. Another alternative (and the focus of this research) for the determination of these properties is molecular simulation techniques. In this work, the liquid–vapor equilibrium as a function of temperature and the surface tension of three pure fatty acids of long chain (linoleic, oleic, and palmitic acid) have been calculated. Simulations have been performed by molecular dynamics using the method of direct determination of phase coexistence with the software GROMACS; in which the transferable potentials for phase equilibria united atom forcefield (TraPPE-UA) have been implemented for these specific molecules. Orthobaric densities and surface tension values have been reported at temperatures near the critical point (from 650 K to 800 K). Critical properties (temperature, pressure, density) have been extrapolated from trajectories obtained in these simulations using scaling law relations. Critical properties for these compounds are not available experimentally, therefore, group contribution calculations from the literature were used as a reference. In this comparison, the palmitic acid properties calculated in this work, show the best agreement among the three substances investigated.