Molecular dynamics investigation on the interaction of nitrile-based ionic liquids in the separation of azeotropic refrigerant R-513A

Abstract

The reclamation of mixed refrigerants stands as a potent measure to substantially mitigate the emission of fluorinated gases (F-gases). In the separation of the azeotropic refrigerant R-513A (comprising 56 wt% R-1234yf, 2,3,3,3-Tetrafluoropropene, and 44 wt% R-134a, 1,1,1,2-Tetrafluoroethane), the extractive distillation process using ionic liquids (ILs) was employed. The molecular structure of nitrile-based ILs ([C4C1im][SCN], [C4C1im][N(CN)2], [C4C1im][C(CN)3], [C4C1im][B(CN)4]) exerts a regular impact on the solubility of refrigerants, thereby necessitating molecular dynamics simulation to ascertain the law of refrigerant solubility in ILs concurrent with the augmentation in the number of –CN in the anion. Additionally, an analysis was conducted to elucidate the mechanism underlying the high selectivity of nitrile-based ILs. The results revealed pronounced interactions between R-1234yf and R-134a, predominantly occurring between carbon atoms (-CF3 groups in R-134a and R-1234yf), and chiefly van der Waals interactions. An enhancement in the number of –CN in anion led to the fortification of the van der Waals interaction between R-134a/R-1234yf and the anion. The stronger nonbonding interaction energy between R-134a and the anion, as well as the higher radial distribution function (RDF) peak height between R-134a and the anion, signified a more robust interaction between R-134a and the anion compared to R-1234yf and the anion. Concurrently, the variance in the RDFs in the anion-C atom (-CH2F group in R-134a and -CF group in R-1234yf) revealed the selectivity of the four ILs to R-134a and R-1234yf. Among the four anions, [B(CN)4]− exhibited the most interaction sites with R-134a. This investigation contributes significantly to comprehending the interaction mechanism of azeotropic refrigerants and the interaction mechanism between refrigerants and nitrile-based ILs.