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

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 R1234yf), 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.