ABSTRACT
Having been introduced in 2003, Deep Eutectic Solvents (DESs) make up a most recent category of green solvents. Due to their unique characteristics, and also their tunable physical properties, DESs have shown high potentials for use in various applications. One of the investigated applications is CO2 absorption. The thermodynamic modeling of CO2 solubility in DESs has been pursued by a number of researchers to estimate the capacity and capability of DESs for such tasks. Among the advanced equations of state (EoSs), the Perturbed Chain-Statistical Associating Fluid Theory (PC-SAFT) is a well-known EoS. In this study, the performance of the PC-SAFT EoS for estimating CO2 solubility in various DESs, within wide ranges of temperatures and pressures, was investigated. A large data bank, including 2542 CO2 solubility data in 109 various-natured DESs was developed and used for this study. This is currently the most comprehensive study in the open literature on CO2 solubility in DESs using an EoS. For modeling, the DES was considered as a pseudo-component with a 2B association scheme. CO2 was considered as both an inert and a 2B-component and the results of each association scheme were compared. Considering the very challenging task of modeling a complex hydrogen bonding mixture with gases, the results of AARD% being lower than 10% for both of the investigated association schemes of CO2, showed that PC-SAFT is a suitable model for estimating CO2 solubilities in various DESs. Also, by proposing generalized correlations to predict the PC-SAFT parameters, covering different families of DESs, the developed model provides a global technique to estimate CO2 solubilities in new and upcoming DESs, avoiding the necessity of further experimental work. This can be most valuable for screening and feasibility studies to select potential DESs from the innumerable options available.
ABSTRACT
In this study, a new modification of the perturbed chain-statistical associating fluid theory (PC-SAFT) has been proposed by incorporating the lattice fluid theory of Guggenheim as an additional term to the original PC-SAFT terms. As the proposed model has one more term than the PC-SAFT, a new mixing rule has been developed especially for the new additional term, while for the conventional terms of the PC-SAFT, the one-fluid mixing rule is used. In order to evaluate the proposed model, the vapor-liquid equilibria were estimated for binary CO2 mixtures with 16 different ionic liquids (ILs) of the 1-alkyl-3-methylimidazolium family with various anions consisting of bis(trifluoromethylsulfonyl) imide, hexafluorophosphate, tetrafluoroborate, and trifluoromethanesulfonate. For a comprehensive comparison, three different modes (different adjustable parameters) of the proposed model were compared with the conventional PC-SAFT. Results indicate that the proposed modification of the PC-SAFT EoS is generally more reliable with respect to the conventional PC-SAFT in all the three proposed modes of vapor-liquid equilibria, giving good agreement with literature data.
