PROCESS FOR SEPARATING COMPONENTS OF AZEOTROPIC MIXTURES USING IONIC LIQUIDS

Abstract

Processes for separating an azeotropic mixture are provided. In one embodiment, the process comprises exposing an azeotropic mixture comprising a first (hydro)fluorocarbon and a second (hydro)fluorocarbon to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of the first and second (hydro)fluorocarbon than the other, determined on a mass basis, to form an ionic liquid containing the (hydro)fluorocarbon and a processed azeotropic mixture.

Description

PROCESS FOR SEPARATING COMPONENTS OF AZEOTROPIC MIXTURES USING IONIC LIQUIDS Cross-reference to related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 915,074 filed on October 15, 2019 and U.S. Provisional Patent Application No. 63 / 060,230 filed on August 3, 2020, the full content of which is incorporated herein by reference. Background of the invention Refrigerant blends are commonly composed of two (binary) or three (ternary) pure refrigerants. Many of these blends are azeotropic or nearly azeotropic and behave like a pure fluid; that is, under constant pressure they condense and evaporate at a constant temperature, and the composition of the blend in the vapor and liquid phases will be essentially the same. Therefore, any refrigerant leakage from an azeotropic blend does not change the composition of the remaining refrigerant. While this is essential for modern cooling systems, it greatly complicates refrigerant recycling and responsible disposal. Brief description of the invention This disclosure describes the separation of (hydro)fluorocarbons in azeotropic mixtures that cannot be separated using differences in boiling points by distillation. Ionic liquids have been identified that can absorb large quantities of (hydro)fluorocarbon refrigerants and differentiate between different types of (hydro)fluorocarbons. In one embodiment, a process for separating an azeotropic mixture comprises exposing an azeotropic mixture comprising a first (hydro)fluorocarbon and a second (hydro)fluorocarbon to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of the first and second (hydro)fluorocarbon than the other of the first and second (hydro)fluorocarbon determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a transformed azeotropic mixture. In another embodiment, a process for separating an azeotropic mixture consists of exposing an azeotropic mixture comprising difluoromethane and pentafluoroethane to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of the difluoromethane and pentafluoroethane than another of the difluoromethane and pentafluoroethane determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a processed azeotropic mixture. In another embodiment, a process for separating an azeotropic mixture comprises exposing an azeotropic mixture comprising pentafluoroethane and 1,1,1-trifluoroethane to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of pentafluoroethane and 1,1,1-trifluoroethane than the other of pentafluoroethane and 1,1,1-trifluoroethane as determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a processed azeotropic mixture. Other key features and advantages of the disclosure will become apparent to those skilled in the art upon review of the following drawings, detailed description, and accompanying claims. Brief description of the figures The illustrative methods of disclosure will be described from now on with reference to the accompanying drawings. Figures 1A to 1C show illustrative cations that can be used to form an ionic liquid for use in current processes. Figure 2 shows illustrative anions that can be used to form an ionic liquid for use in current processes. Figure 3 shows the chemical structures and acronyms of the HFC and IL refrigerants. Figure 4 shows the vapor-liquid equilibrium (VLE) data for HFC-32 in [C4Ciim][SCN] (▼), [C60iim][CI] (*), [C4C1 im][CiCO2] (♦), [C4Ci ¡m][BF4] (·), [C4Ci im][PFe] (), and [C6Ciim][FAP] (A) at 298.15 K. The symbols are measured experimental data (PTx) and the lines are predictions from the Van der Waals EoS model. Figure 5 shows VLE for HFC-125 in [C4Ciim][SCN] (▼), [C4Ciim][PF6] (), [C4Ciim][BF4] (·), [C6Ciim][FAP] (A), [C6Ciim][CI] (★), and [C4Ciim][CiCO2] (♦) at 298.15 K. The symbols are measured experimental data (PTx) and the solid lines are predictions from the Van der Waals EoS model. Figure 6 shows normalized fugacity for HFC-32 in [C4Ciim][SCN] (▼), [CsCiim][CI] (★), [C4Ciim][CiCO2] (♦), [C4Ciim][BF4] (·), [C4Ciim][PF6] (), and [C6Ciim][FAP] (A) as a function of the molar composition of the refrigerant at 298.15 K. The solid line represents Raoult's law. Dashed lines have been added as a guide for the reader. Figure 7 shows normalized fugacity for HFC-125 in [C4Ciim][SCN] (▼), [C4Ciim][PF6] (), [C4C1 im][BF4] (·), [CeCiimjIFAP] (A), [C6Ciim][CI] (★), and [C4Ciim][CiCO2] (♦) as a function of the molar composition of the refrigerant at 298.15 K. The solid line represents Raoult's law. Dashed lines have been added as a guide for the reader. Figure 8 shows an uncertainty analysis of the Van der Waals equation of state (EoS) model parameters for the solubility of HFC-32 in [C4C1 im][PF6]. Histograms for each parameter are shown on the diagonal, representing the variability of each parameter. Scatter plots below the diagonal show the pairwise variability of the fitted parameters, where dark gray squares indicate parameters calculated using the original dataset shown in Table 14. Figure 9 shows an ideal selectivity for the absorption of HFC-32 and HFC-125 in IL. The ideal selectivity was calculated based on the ratio of Henry's law constants (s^,) in IL at 298.15 K and the ratio of weight fractions (swíj) in IL at 1.0 MPa and 298.15 K. nzcccn / zznz / q / uιλι Figures 10A to 10F show the comparison of HFC-32 and HFC-125 VLE (mole fraction, χή in ionic liquids: (Figure 10A) [C4Ciim][BF4], (Figure 10B) [C4Ciim][PF6], (Figure 10C) [C6Ciim][FAP], (Figure 10D) [C4Ciim][CiCO2], (Figure 10E) [C4Ciim][SCN], and (Figure 10F) [C6Ciim][CI] at 298.15 K. Figures 11A to 11F show the comparison of HFC-32 and HFC-125 VLE (mass fraction, wj) in ionic liquids: (Figure 11A) [C4Ciim][BF4], (Figure 11B) [C4Ciim][PF6], (Figure 11C) [C6Ciim][FAP], (Figure 11D) [C4Ciim][CiCO2], (Figure 11E) [C4Ciim][SCN], and (Figure 11F) [CeCiimHCI] at 298.15 K. Detailed description of the invention Common refrigerants, their composition, environmental impact, and regulatory status are briefly presented in Table 1. Chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) refrigerants, such as R-502 and R-22 (CHF2CI), respectively, were phased out under the Montreal Protocol in 1987 due to their high ozone depletion potential (ODP). This spurred the development of more environmentally friendly refrigerants and refrigerant blends. For example, R-404a, a near-azeotropic blend composed of HFCs R-125 (CHF2CF3), R-143a (CH3CF3), and R-134a (CH2FCF3), and R-507, an azeotropic blend composed of R-125 and R-143a, are common replacements for R-502.R-22, which is widely used in residential and commercial air conditioning equipment, was replaced by the binary azeotropic mixture R-410a (R-32 and R-125) and the near-azeotropic mixture R-407c (R-32, R-125, and R-134a). Unfortunately, many HFCs, including R-404a, R-507, R-410a, and R-407c, exhibit high global warming potentials (GWPs). For example, R-125, a component in these four azeotropic mixtures, has a GWP 3,500 times greater than that of CO2. Recent international efforts, including the Kigali Amendment in 2016 and the European Union's fluorinated gas regulations in 2015, are attempting to reduce the use of high GWP refrigerants through restrictions on their use in new equipment and ongoing phase-outs planned through the 2020s.Therefore, it would be extremely useful to recover R-32 (CH2F2), which has a much lower GWP than other HFCs, from the millions of kilograms of R-410a and R-407c currently on the market so that it can be reused. However, it is not currently possible to easily separate R-32 from R-125, which form an azeotropic mixture. Furthermore, separating R-125 from R-143a is also not currently possible, and separating R-125 from R-134a is very energy-intensive. Table 1. Brief description of refrigerants, their composition, environmental impact, and regulatory status. ODP: Ozone depletion potential with reference R-11 = 1. GWP: 100-year greenhouse warming potential with reference CO2 = 1. Montreal Protocol (M): χ phase-down, χχ global ban. Kigali Agreement (K): V low GWP, χ high GWP. EU fluorinated gas (F): J no controls, χ some restrictions, χχ substantial restrictions. Tipo Nombre Composición (% en peso para mezclas) ODP GWP: M K F CFC R-115 cloropentafluoroetano 0.6 7370 X X X X X R-502 48.8% R-22, 51.2% R-115 0.33 4657 X X X XX HCFC R-22 clorodifluorometano 0.055 1810 X X X HFC R-143a 1,1,1 -trifluoroetano 0 4470 X X X R-404a 44 % R-125, 52 % R-143a, 4 % R-134a 0 3922 X XX R-507 50% R-125, 50% R-143a 0 3900 X X X R-125 pentafluoroetano 0 3500 X X X R-410a 50% R-32, 50% R-125 0 2088 X X R-407C 23 % R-32, 25 % R-125, 52 % R134a 0 1774 X X R-134a 1,1,1,2-tetrafluoroetano 0 1430 X X R-32 difluorometano 0 675 X R-152a 1,1-difluoroetano 0 124 HFO R-1234yf 2,3,3,3-tetrafluoropropeno 0 4 ó R-1234ze 1,3,3,3-tetrafluoropropeno 0 7 ó HCFO R-1233zd(E) trans-1 -cloro-3,3,3-trifluoro-1 propeno <0.01 4 R-1233zd(Z) cis-1 -cloro-3,3,3-trif I uoro-1 propeno <0.01 4 HFO / HFC R-513a 56 % R-1234yf, 44 % R-134a 0 631 7 / ó nzcccn / zznz / q / υιλι Without the ability to separate R-32 from these other refrigerants, phasing out R-410a and R-407c will require the refrigerants to be recovered and incinerated or simply vented into the atmosphere. Incineration is wasteful and likely to lead to the release of hazardous emissions, while venting will release large quantities of potent, long-lived greenhouse gases into the atmosphere. Furthermore, preventing the release of R-125 into the atmosphere would be equivalent to eliminating 175 million metric tons of CO2 (or the emissions of 35 million cars in a year). This disclosure provides a process for separating (extracting) components from azeotropic mixtures. The phrase "azeotropic mixture and the like" encompasses nearly azeotropic mixtures and refers to a mixture of two or more components (e.g., 2, 3, etc.) where the vapor-phase and liquid-phase compositions are equal or nearly equal at a selected pressure and temperature. The phrase also refers to mixtures of components in which the components have normal boiling points that are equal to or within 10°C of each other (including within 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, 2°C, or 1°C). The components of azeotropic mixtures can be fluorocarbons, hydrofluorocarbons, or combinations thereof. The term (hydro)fluorocarbon refers to both fluorocarbons and hydrofluorocarbons. A fluorocarbon is a compound comprising fluorine and carbon, but not hydrogen. A fluorocarbon compound includes a fluorocarbon compound (FC), which consists solely of fluorine and carbon, as well as a chlorofluorocarbon compound (CFC), where FC and CFC are well-known terms used to define refrigerants. Fluorocarbon compounds also include, however, compounds selected from the group consisting of fluoroether compounds, fluoroketone compounds, fluoroaromatic compounds, and fluoroolefin compounds. Fluorocarbon compounds also include compounds in which one or more optional substituents can be selected from one or more of bromine, chlorine, and iodine.A hydrofluorocarbon is a compound comprising fluorine, carbon, and at least one hydrogen atom. Hydrofluorocarbon compounds include hydrofluorocarbon compounds (HFCs), which consist solely of fluorine, carbon, and hydrogen, as well as hydrochlorofluorocarbon compounds (HCFCs), where HFC and HCFC are well-known terms used to define refrigerants. Hydrofluorocarbon compounds also include compounds selected from the group consisting of hydrofluoroether compounds, hydrofluoroketone compounds, hydrofluoroaromatic compounds, and hydrofluoroolefin compounds. Hydrofluorocarbon compounds also include compounds in which one or more optional substituents can be selected from one or more of bromine, chlorine, and iodine. Table 1 provides illustrative azeotropic mixtures. In the embodiments, the azeotropic mixture comprises pentafluoroethane (R-125). In the embodiments, the azeotropic mixture comprises difluoromethane (R-32). In the embodiments, the azeotropic mixture comprises pentafluoroethane (R-125) and difluoromethane (R-32). In the embodiments, the azeotropic mixture comprises pentafluoroethane (R-125) and 1,1,1-trifluoroethane (R-143a). In the embodiments, the azeotropic mixture comprises pentafluoroethane (R-125), 1,1,1-trifluoroethane (R-143a), and 1,1,1,2-tetrafluoroethane (R-134a). In these forms, the azeotropic mixture is R-410a (50% by mass of R-32 and 50% by mass of R-125). In these forms, the azeotropic mixture is R-507 (50% by mass of R-125 and 50% by mass of R-143a). In these forms, the azeotropic mixture is R-404a (44% by mass of R-125, 52% by mass of R-143a, and 4% by mass of R-134a). In the present process, the azeotropic mixture is exposed to (in contact with) an ionic liquid at a temperature and pressure at which the ionic liquid absorbs (solubilizes) a greater amount of one of the (hydro)fluorocarbons in the azeotropic mixture than the other (or remaining) (hydro)fluorocarbons in the azeotropic mixture. Although existing processes have been developed for separating (hydro)fluorocarbons using certain ionic liquids, the current processes are based, at least in part, on new knowledge, as described immediately below. First, the inventors have determined that when selecting an ionic liquid for separation, a mass-basis selectivity ratio is preferable to a mole fraction selectivity ratio. The mass-basis selectivity ratio (Wi7) for (hydro)fluorocarbon i.e. (hydro)fluorocarbon j.a. at a selected temperature (7) and pressure (P) is provided by: where wMjy and w / y are the vapor and liquid mass fractions of the dissolved (hydro)fluorocarbon components iyj in the ionic liquid at the selected temperature and pressure, where wv1 and wvj = 1.0. (See also Equation 23 in Example 3 below.) As described in Example 3 below, a mole fraction selectivity ratio (in which mole fractions of the dissolved (hydro)fluorocarbon component in the ionic liquid are used instead of mass fractions) does not necessarily lead to the ionic liquid providing the most selective separation system. Secondly, the inventors have determined that ionic liquids comprising non-fluorinated anions can actually achieve more selective separation than ionic liquids comprising fluorinated anions. This is an unexpected discovery, as the prevailing view has been that fluorinated anions are favored for separating azeotropic mixtures of (hydro)fluorocarbons because they form the strongest hydrogen bonds. Furthermore, they form hydrogen bonds with numerous (hydro)fluorocarbons to varying degrees, enabling selective adsorption of the (hydro)fluorocarbons and their efficient separation. Consequently, existing approaches to separating azeotropic mixtures have relied on selecting ionic liquids containing fluorinated anions.The inventors' unexpected discovery of the superiority of ionic liquids comprising non-fluorinated anions is demonstrated in Example 3 below, using an azeotropic mixture composed of pentafluoroethane (R-125) and difluoromethane (R-32) as an illustrative example. Briefly, the mass basis selectivity ratio (Wi7) for pentafluoroethane (R-125) and difluoromethane (R-32) in the ionic liquid 1-hexyl-3-methylimidazolium chloride ([CeCiim][CI]) was found to be surprisingly high compared to the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([C4C1 im][PF6]) at room temperature (298.15 K) and a pressure of 1.0 MPa. Ionic liquids containing fluorinated anions such as [PFe] are known to strongly absorb difluoromethane (R-32) via hydrogen bonding and have therefore been suggested for separating azeotropic mixtures comprising R-32. However, the inventors found that in [CsCiim][CI], it is pentafluoroethane (not difluoromethane) that is the most intensely absorbed component, which was an unexpected result.Furthermore, it was found that the 5¾ for pentafluoroethane (R-125) and difluoromethane (R32) at room temperature and pressure was more than three times higher compared to sw¡7en ([C4C1im][PF6]). Both the opposite in the solubility behavior for R-125 and the high mass base selectivity value demonstrate the unexpected nature of the inventors' results. Similar results were found for the use of 1-butyl-3-methylimidazolium acetate ([C4C1 im][Ac]) compared to ([C4C1im][PF6]). Finally, it is also observed that the mole fraction selectivity ratio for pentafluoroethane (R-125) and difluoromethane (R-32) in [CgCiim][CI] at room temperature and 1.0 MPa is actually lower than the mole fraction selectivity ratio in [CiCiimjjPFe]. Therefore, without the inventors' insight regarding the importance of considering mass basis selectivity ratios, the ionic liquid [CeCi im][CI] would not have been selected to separate pentafluoroethane (R-125) and difluoromethane (R-32). In addition to these considerations, a variety of ionic liquids can be used. Ionic liquids are generally organic salts that are liquids with melting points below 100 °C. Ionic liquids comprise a cation and an anion. A variety of non-fluorinated cations and anions can be used. The ionic liquid may include more than one type of cation, more than one type of anion, or both. However, the ionic liquid may also include only one type of cation and one type of anion. In these modalities, the cation is selected from the group of cations represented by the structures of the formulas shown in Figures 1A-1C. The following rules apply to these formulas. Ί conditions: a) R1, R2, R3, R4, R5, R6, R12 and R13 are selected independently from the group consisting of: (i)H; (i) halogens such as F, Cl, Br, I; (iii) -CH3, -C2H5 or C3 to C25 straight-chain, branched or cyclic alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2, SH and SO3H; (iv) -CH3, -C2H5 or C3 to C25 straight-chain, branched or cyclic alkane or alkene groups comprising one to three heteroatoms selected from the group consisting of O, N, Si and S, and optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2 and SH; (v) unsubstituted aryl from Ce to C25, or unsubstituted heteroaryl from Ce to C25, groups having from one to three heteroatoms selected independently from the group formed by O, N, Si and S, wherein unsubstituted aryl or unsubstituted heteroaryl can be attached to the structure via an alkyl spacer group (e.g., -CH2-); (vi) substituted aryl from Ce to C25, or substituted heteroaryl from Ce to C25, groups having from one to three heteroatoms independently selected from the group consisting of O, N, Si and S; wherein substituted aryl or substituted heteroaryl may be attached to the structure through an alkyl spacer group (for example, -CH2-); and wherein substituted aryl or substituted heteroaryl has from one to three substituents independently selected from the group consisting of: (A) -CH3, -C2H5, or straight-chain, branched, or cyclic C3 to C25 alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2, and SH, (B) OH, (C) NH2, and (D) SH; and (vii) —(CH2)nS¡(CH2)mCH3, —(CH2)nS¡(CH3)3, —(CH2)nOS¡(CH3)m, where n is independently 1-4 and m is independently 0-4; (b) R7, R8, R9 and R10 are selected independently from the group consisting of: (i) -CH3, -C2H5 or C3 to C25 straight-chain, branched or cyclic alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2, SH and SO3H; (ii) -CH3, -C2H5 or C3 to C25 straight-chain, branched or cyclic alkane or alkene groups comprising one to three heteroatoms selected from the group consisting of O, N, Si and S, and optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2 and SH; (iii) unsubstituted aryl from Ce to C25, or unsubstituted heteroaryl from Ce to C25, groups having from one to three heteroatoms selected independently from the group consisting of O, N, Si and S; and (iv) substituted aryl from Ce to C25, or substituted heteroaryl from Ce to C25, groups having from one to three heteroatoms selected independently from the group consisting of O, N, Si and S, and wherein the substituted aryl or substituted heteroaryl group has from one to three substituents selected independently from the group consisting of: (A) -CH3, -C2H5, or straight-chain, branched, or cyclic C3 to C25 alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, F, I, OH, NH2, and SH, (B) OH, (C) NH2, and (D) SH; and (V) —(CH2)nSi(CH2)mCH3, —(CH2)nSi(CH3)3, —(CH2)nOSi(CH3)m, where n is independently 1-4 and m is independently 0-4; and (C) optionally, at least two of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 may together form a cyclic or bicyclic alkyl or alkenyl group. In the embodiments, the ionic liquid comprises a cation selected from one or more members of the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, phosphonium, ammonium, benzyltrimethylammonium, choline, cholinium, dimethylimidazolium, guanidinium, choline, phosphonium, lactam, sulfonium, tetramethylammonium, and tetramethylphosphonium. In these embodiments, the ionic liquid comprises a non-fluorinated cation (which may be any of the above cations provided that fluorine is not present). In these embodiments, the ionic liquid comprises a non-halogenated cation (which may be any of the above cations provided that no halogen is present). In the embodiments, the ionic liquid comprises an anion selected from one or more members of the group consisting of: [CH3CO2]⁻, [HSO4]⁻, [CH3OSO3]⁻, [C2H5OSO3]⁻, [CH3CeH4SO3]⁻, [TSO₃]⁻, [AlCk]⁻, [Al2Cl₇], [ZnCk]²⁻, [Zn2Cl₆]²⁻, [Zn3Cl₈]²⁻, [FeCk]⁻, [GaCk]⁻, [Ga2Cl₇]⁻, [InCk]⁻, [In2Cl₇], [CO3]²⁻, [HCO3⁻], [NO2]⁻, [NO3]⁻, [SO4]²⁻, [PO3]³⁻, [HPO3]²⁻, [H2PO3]¹⁻, [PO4]³⁻, [HPO4]²⁻, [H2PO4]⁻, [HSO3]⁻, [CuCL]·, Cl-, Br, I-, SON-, carborates optionally substituted by alkyl or substituted alkyl; and carboranes optionally substituted by alkylamine, substituted alkylamine, alkyl or substituted alkyl. In the embodiments, the ionic liquid comprises an anion selected from one or more members of the group consisting of aminoacetate, ascorbate, benzoate, catecholate, citrate, dimethyl phosphate, formate, fumarate, gallate, glycolate, glyoxylate, iminodiacetate, isobutyrate, kojate, lactate, levulinate, oxalate, pivalate, propionate, pyruvate, salicylate, succinamate, succinate, tiglate, tropolonate, [CH3CO2]-, [HSO4]-, [CH3SO3]-, [CH3OSO3]-, [C2H5OSO3]-, [CH3C6H4SO3]-, [AlCk]', [Al2Cl7] , [ZnCk]2', [Zn2Cl6]2-, [Zn3Cl8]2-, [FeCk]-, [GaCk]-, [Ga2Cl7]-, [InCk]', [ln2Cl7]-, [CO3]2-, [HCO3]-, [NO2]-, [NO3]-, [SO4]2-, [PO3]3-, [HPO4]2-, [H2PO4]-, [HSOs]·, [CuCl2]·, Cl-, Br, I-, SCN, [N(CN)2]·, and anions represented by the structure of the following formula, [R1COO], where R1 is selected from the group consisting of: (i) -CH3, -C2H5 or C3a C10 straight-chain, branched or cyclic alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, I, OH, NH2 and SH; (i) -CH3, -C2Hs, or straight-chain, branched, or cyclic C3-C10 alkane or alkene groups containing one to three heteroatoms selected from the group consisting of O, N, Si, and S, and optionally replaced by at least one member selected from the group consisting of Cl, Br, I, OH, NH2, and SH; (iii) unsubstituted aryl from Ce to C10, or unsubstituted heteroaryl from Ce to C10, groups having from one to three heteroatoms independently selected from the group consisting of O, N, Si and S; and (iv) substituted aryl from Ce to C10, or substituted heteroaryl from Ce to C10, groups having from one to three heteroatoms independently selected from the group consisting of O, N, Si and S; and wherein the substituted aryl or substituted heteroaryl group has from one to three substituents independently selected from the group consisting of: (A) -CH3, -C2Hs, or C3a C10 straight-chain, branched, or cyclic alkane or alkene groups, optionally substituted by at least one member selected from the group consisting of Cl, Br, I, OH, NH2, and SH, (B) OH, (C) NH2, and (D) SH. The anion of the ionic liquid may be a sulfonate. The sulfonate may have the formula [R-SO3]', where R is an alkyl or aryl group. The alkyl group may be a linear alkyl group where the number of carbons may range from, for example, 1 to 12. The alkyl group may be unsubstituted, meaning that the alkyl group contains only carbon and hydrogen and no heteroatoms. The alkyl group may be substituted, meaning an unsubstituted alkyl group in which one or more bonds to a carbon or hydrogen atom are replaced by a bond to non-hydrogen and non-carbon atoms. Non-hydrogen and non-carbon atoms include, for example, a halogen atom other than fluorine (F). Aryl groups may be unsubstituted or substituted as described above with respect to alkyl groups. However, substituted aryl groups also refer to an unsubstituted monocyclic aryl group where one or more carbon atoms are bonded to an alkane.The alkane can be linear, have several carbon numbers, and can be unsubstituted or substituted as described above with respect to alkyl groups. The anion can be a carboxylate. The carboxylate can have the formula [R-CO2]', where R is an alkyl group as described above with respect to sulfonate. The carboxylate can be a dicarboxylate, a tricarboxylate, a tetracarboxylate, and so on. Other anions that can be used include [HSO4]·, dicyanamide; and a halide other than fluoride such as Cl, Br, or I. Illustrative anions are shown in Figure 2. In these forms, the ionic liquid comprises a non-halogenated anion (which can be any of the above anions as long as there is no halogen present). In these forms, the ionic liquid is not fluorinated (i.e., both the cations and anions are free of fluorine). In these forms, the ionic liquid is not halogenated (i.e., both the cations and anions are free of a halogen). In this process, the temperature and pressure can be selected to maximize the absorption of one of the (hydro)fluorocarbons in the azeotropic mixture into the selected ionic liquid compared to another of the (hydro)fluorocarbons. The exposure step forms an ionic liquid containing the (hydro)fluorocarbon (which has the highest amount of one of the (hydro)fluorocarbons) and a processed azeotropic mixture (which has a correspondingly decreased amount of the absorbed (hydro)fluorocarbon). The ionic liquid containing the (hydro)fluorocarbon can be recovered and, if desired, reused. The processed azeotropic mixture can be exposed to an additional amount of the ionic liquid to extract more of the more soluble (hydro)fluorocarbon from the processed azeotropic mixture.These collection steps and the additional ionic liquid exposure steps can be repeated as desired. A variety of extractive distillation systems can be used to carry out the disclosed methods. These systems and their use are generally known. The disclosed processes can allow different (hydro)fluorocarbons in an azeotropic mixture to be separated from each other with a high degree of purity, for example, to a purity of more than 95 mol%, 97 mol%, 99 mol% or more. Examples EXAMPLE 1: Ionic liquids with chloride anion dictate the successful separation of R-410a into R125 and R-32 The vapor-liquid equilibrium of R-125 and R-32 in three ionic liquids with non-fluorinated anions, namely 1-butyl-3-methylimidazolium acetate ([C4C11][Ac]), 1-hexyl-3-methylimidazolium chloride ([CeC11][C11]) and 1-butyl-3-methylimidazolium thiocyanate ([C4C11][SCN]) at 298.15 K and pressures up to 1.0 MPa were measured using a microgravimetric balance (Hiden Isochema Ltd., IGA 003, Warrington, UK). Experimental solubility data (T, p, wi) for R-32 and R-125 in [C4Ciim][Ac], [C4Ciim][SCN] and [CeCiim][CI] are briefly presented in Tables 2-4. Table 2. Experimental solubility data (7, P, wi) for R-32 (1) and R-125 (1) in [C4Ciim][Ac] (2) at 298.15 K. nzcccn / zznz / q / uιλι R-32 (1) + [C4Ciim][Ac] (2) R-125 (1) + [C4Ciim][Ac] (2) P (MPa) W; (wt%) P (MPa) Wi (wt%) 0.050 1.5 0.050 3.7 0.100 2.7 0.100 7.7 0.200 4.8 0.200 16.0 0.400 8.7 0.400 31.0 0.600 12.6 0.599 40.8 0.800 16.8 0.799 49.1 1,000 21.2 1,000 56.9 Table 3 Experimental solubility data (T, P, wi) for R-32 (1) and R-125 (1) in [C4Ciim][SCN] (2) at 298.15 K. R-32 (1) + [C4Ci¡m][SCN] (2) R-125 (1) +[C4Ciim][SCN] (2) P (MPa) Wi (% by weight) P (MPa) w> (% by weight) 0.050 0.1 0.050 0.0 0.100 0.6 0.100 0.3 0.200 1.6 0.200 0.8 0.400 3.7 0.400 1.9 0.600 6.6 0.599 3.2 0.800 9.3 0.799 4.7 1,000 12.4 1,000 6.5 Table 4. Experimental solubility data (T, P, wi) for R-32 (1) and R-125 (1) in [C6Ciim][CI] (2) at 298.15 K. R-32 (1) + [C6Ci¡m][CI] (2) R-125 (1) + [C6Ciím][CI] (2) P (MPa) Wl (% by weight) P (MPa) w> (% by weight) 0.050 0.5 0.050 2.4 0.100 1.2 0.100 4.8 0.200 2.5 0.200 10.2 0.400 5.6 0.400 19.5 0.600 8.8 0.599 29.6 0.800 11.9 0.799 41.3 1,000 15.2 1,000 52.9 The P, T, and wi data presented in Tables 2-4 show that the solubility of both R-32 and R-125 increases with increasing pressure. However, it is the large quantities of R-32 or R-125 that can dissolve in an ionic liquid that makes the binary system particularly useful for separating gas mixtures. For example, R-125 is 3.4 times more soluble than R-32 in [C6Ciim][Cl], while in [C4Ciim][Ac] R-125 is only 2.6 times more soluble than R-32. Interestingly, R-125 is much more soluble in [CeCiim][Cl] and [C4Ciim][Ac] than in [C4Ciim][SCN]. These solubility measurements show that the solubilities of gases in ionic liquids depend primarily on the strength of the interaction between the gas and the anion. EXAMPLE 2: Ionic liquids with fluorinated anions do not maximize the separation of R-410a into R-125 and R-32 The vapor-liquid equilibrium of R-125 and R-32 in two ionic liquids with fluorinated anions, namely 1-butyl-3-methylimidazolium tetrafluoroborate [C4Ciim][BF4] and 1-butyl-3-methylimidazolium hexafluorophosphate [C4Ciim][PF6], at 298.15 K and pressures up to 1.0 MPa, was measured using a microgravimetric balance. Experimental solubility data (T, p, wT) for R-32 and R-125 in [C4Ciim][BF4] and [C4Ciim][PF6] are briefly presented in Tables 5-6. Table 5. Experimental solubility data (T, P, wf) for R-32 (1) and R-125 (1) in [C4Ciim][BF4] (2) at 298.15 K. R-32 (1) + [C4Ciim][BF4] (2) R-125 (1) + [C4Ciim][BF4] (2) P (MPa) Wl (% by weight) P (MPa) Wl (% by weight) 0.050 0.6 0.050 0. 0.100 1.4 0.100 1.0 0.200 3.1 0.200 2.3 0.400 6.8 0.400 5.6 0.600 11.8 0.599 10.0 0.800 15.8 0.799 15.9 1,000 21.9 1,000 24.4 Table 6. Experimental solubility data (T, P, w,) for R-32 (1) and R-125 (1) in [C4Ciim][PF6] (2) at 298.15 K. R-32 (1) + [C4Ciim][PF6] (2) R-125 (1) + [C4Ciim][PF6] (2) P (MPa) Wl (% by weight) P (MPa) Wt (% by weight) 0.050 0.7 0.050 0.5 0.100 1.5 0.100 1.0 0.200 3.0 (0.0762) 0.200 2.1 0.400 6.4 0.400 4.4 0.600 10.3 0.599 7.2 0.800 14.6 0.799 11.0 1.000 19.8 1.000 16.1 It is more surprising that R-32 is more soluble than R-125 in [C4Ciim][BF4] and [C4Ciim][PF6], which is the opposite trend found for [CeCiim][CI], and much smaller differences in solubility were observed. For example, R-125 is 3.4 times more soluble than R-32 in [CeCiim][CI], while R-32 is more soluble than R-125 in [C4Ciim][BF4] at 298.15 K and 0.1 MPa. EXAMPLE 3: Separation of the azeotropic mixture of hydrofluorocarbons R-410a using ionic liquids Introduction Hydrofluorocarbons (HFCs) are a family of refrigerants widely used in air conditioning and refrigeration systems. HFCs were developed to replace chlorofluorocarbons, which were linked to the depletion of the Earth's ozone layer. HFCs have an ozone depletion potential (ODP) of zero, but some have a high global warming potential (GWP). The Kyoto Protocol of the United Nations Framework Convention on Climate Change (UNFCCC) has recommended the phase-out of HFCs under the Kigali Amendment to the Montreal Protocol. Furthermore, EU Regulation No. 517 / 2014, which requires a reduction of up to two-thirds of fluorinated greenhouse gas (GHG) emissions from 2010 by 2030. R-410A is a near-azeotropic HFC mixture composed of 50.0% by mass of HFC-32 (CH2F2, normal boiling point temperature (NBPT) = 221.3 K) and 50.0% by mass of HFC-125 (CHF2CF3, NBPT = 224.9 K) that was developed as a replacement for HCFC-22 (CHCIF2) in residential and commercial air conditioning and heat pump systems. Currently, no commercial technology is available for separating HFC-32 and HFC-125; therefore, if R-410A cannot be recycled in the future, it will have to be incinerated. The need for a sustainable process to separate R-410A so that HFC-32 can be used in low GWP blends with hydrofluoroolefins (HFOs) and HFC-125 can be used as a feedstock for future products is of vital importance given the pending and new regulations that will limit the use of HFCs. In this example, the vapor-liquid equilibrium (single-component absorption) of the R-410A components, namely HFC-32 and HFC-125, in 1-butyl-3-methylimidazolium acetate ([C4C1 im][CiCO2]), [C4C1 im][BF4], [C4C1 im][PFe], 1-butyl-3-methylimidazolium thiocyanate ([C4C1 im][SCN]), 1-hexyl-3-methylimidazolium chloride ([CeCiim][CI]), and 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([CeCiim][FAP]), were measured using a microgravimetric balance at 298.15 K and pressures up to 298.15 K and pressures up to 298.15 K and pressures up to 1.0 MPa. The Van der Waals equation of state (EoS) model was applied to correlate and predict the phase equilibrium for each HFC-32 / IL and HFC-125 / IL mixture using the experimental solubility data. In addition, the time-dependent behavior of the HFC / IL systems was analyzed using Fick's one-dimensional law.Finally, the ideal selectivity of R-410A separation for each IL was calculated by taking the ratio of Henry's law constants at 298.15 K and the mass absorption ratio at 1.0 MPa and 298.15 K. Materials and methods Materials HFC-32 (CAS# 75-10-5) and HFC-125 (CAS# 354-33-6) were obtained from The Chemours Company (Newark, DE) with a minimum purity of 99.9% by weight, and were used as received. The ionic liquids were purchased from commercial suppliers as follows: [C4Ciim][CiCO2] (assay, > 95 wt.%, CAS No. 284049-75-8, lot and fill code S25803 444041302), [C4Ciim][BF4] (assay, > 97 wt.%, CAS No. 174501-65-6, lot and fill code 1116280 23404335), [C4C1 im][PF6] (assay, > 96 wt.%, CAS No. 174501-64-5, lot and fill code 1242554 304070904), [C4Ciim][SCN] [C6Ciim][CI] (assay, >95% by weight, CAS No. 344790-87-0, lot and fill code, S25812 14804B3) and [C6Ciim][CI] (assay, >97% by weight, CAS No. 171058-17-6, lot and fill code, 1086333 41705081) were obtained from FlukaChemika (Switzerland). [CsCiim][FAP] (assay, >99% by weight, CAS No. 713512-19-7, lot and fill code S4872378 733) was purchased from EMD Millipore, Inc. (United States).The densities of HFC-32 and HFC-125 were obtained from the REFPROP V.10.0 database of the National Institute of Standards and Technology (NIST). (Lemmon, EW et al., NIST Reference Fluid Thermodynamic and Transponder Properties - REFPROP 10.0, Gaithersburg, n7CCQn / 77n7 / q / uili. Maryland, 2013). The densities and molecular weight of IL were obtained from the literature. (Shiflett, M. B. et al., AlChE J. 2006, 52, (3), 1205-1219; and Shiflett, M. B. et al., Fluid Phase Equilibr. 2006, 242, (2), 220-232). Figure 3 provides the chemical structures and acronyms of the HFC and IL refrigerants studied in this example. Experimental Methodology Gas absorption measurements were performed using a microgravimetric balance (Hiden Isochema Ltd., IGA 003, Warrington, UK). The experimental equipment and protocols for gas solubility measurements have been described in detail previously; therefore, only a brief description is provided here (Shiflett et al., 2006). Approximately 50 mg of IL was loaded into a flat-bottomed Pyrex sample container and degassed under vacuum (1010 MPa) at 348.15 K for 12 hours to remove any trace amounts of water and / or other volatile impurities before measurements. To ensure sufficient time to reach vapor-liquid equilibrium at 298.15 K, each pressure set point was held for a minimum of 8 hours.The kinetic sorption profile and equilibrium stability were monitored using HISorp software to ensure that the HFC / IL mixtures had reached thermodynamic equilibrium. Gas sorption measurements were performed in static mode, where setpoint pressures were maintained constant within the system through simultaneous adjustments to the intake and exhaust valves. Sample and counterweight temperatures were measured using an in-situ type K thermocouple with an uncertainty of ±0.1 K. Both the temperature and pressure transducers on the microbalance were calibrated using NIST-certified reference instruments. The in-situ thermocouple was calibrated using a standard platinum resistance thermometer (Hart Scientific SPRT model 5699 and Hart Scientific Blackstack model 1560 readout with an SPRT 2560 module) with an accuracy of ±0.005 K.Vacuum pressures (10.1° to 10.5 MPa) were measured using a Pfeiffer vacuum gauge (model PKR251), and pressures from vacuum (105 MPa) to the highest pressure (2.0 MPa) were measured using a Druck pressure transducer (model PDCR4010) with an accuracy of ±0.0008 MPa. The IGA microbalance had a mass resolution of 0.0001 mg for absorption and desorption measurements at any given temperature and pressure. Gas sorption data were corrected for buoyancy and volume expansion as described above. (Minnick, DL et al., J. Vac. Sci. Technol A 2018, 36, (5)). State modeling equation A generic Van der Waals equation of state (EoS) has been shown to accurately predict the solubilities of gases such as CO2, NH3, SO2, and hydrofluorocarbons such as HFC-134a in room-temperature ionic liquids (RTILs). (Yokozeki, A. et al., J. Supercrit. Fluids 2010, 55, (2), 846-851). In this example, the parameters have been fitted to the same generic Van der Waals model for the studied HFC-32 and HFC-125 mixtures in RTILs. The Van der Waals equation of state (EoS) is modeled by the following equations: RT a(T) V - b V2(1) 0.421875 / ?2Tr2¿«¿(O ° ^Ci 0.125RTci(2) (3) (4) nzcccn / zznz / q / υιλι where a represents the temperature dependence of parameter a. The critical constant, β, the critical temperature, Tc, and the critical pressure, Pc, for HFC-32 and HFC-125 were obtained from previous calculations by Yokozeki and are shown in Table 7. (Yokozeki, A., Int. J. Thermophys. 2001, 22, (4), 10571071). Table 7. Critical parameters of HFC Compound Tc(K) Pc (kPa) ^HFC, A JShfc, b / ?HFC, c ^HFC, D HFC-32 351.26 5782 1.0019 0.48333 -0.07538 0.00673 HFC-125 339.19 3637 1.0001 0.47736 -0.01977 -0.0177 The following temperature dependence for the parameter a for IL has been proposed: a(T) = 1+ pILA^--TrJL} (5) V r,lL / where pIL is an adjustable and calculated fitting parameter for each IL. In this example, Tcy Pc used for all ILs were set to 1000 K and 2.5 MPa. The model fit is extremely insensitive to the choice of Tcy Pc of IL as shown below. The following mixing rules were originally developed for coolant-lubricant mixtures involving large molecular size differences and / or asymmetric interactions with respect to compositions and were extended to coolant / ionic liquid mixtures: ΣΝ - k^x^·(6) i,j=i fij(.T) = l+Y(7) líil¡í(xí + x¡} ku= —----------,where kü= 0(8)7ΙμΧ, + IíjXj b = 0.5 Y (bi + bj^l-kij^-mt^XiXj(9) A—= l In this document, I, my, and τ are binary interaction parameters, x¡ is the mole fraction of species i, and R is the universal gas constant. It is assumed that / «= / ¿=1, mij-mji and m„=0, and ti¡=t¡¡ and t¡¡=0, which leaves only four of these parameters (Iμ lj¡, m¡¡, and T¡j) to be estimated through nonlinear regression. With β^ and the four binary interaction parameters, a total of five parameters were fitted in this model. Many combinations are possible for the parameters i, ij, m, τ, and β / L for which the model predictions closely match the experimental data; therefore, the choice of binary interaction parameters has a negligible impact on the quality of the fit. The fugacity coefficient is defined as: / RT \ b- a': + atl0)where: ?V - ktj(11) W'j7iV11(ljiXi +li¡xX \ Σν, . . . ( I, ίΙα(ΐί i — ln)xiXf) (bi+bjXl-m^Xj(12) >=1( (ljiXi+ líjXj) J and the equilibrium between the liquid and vapor phases are determined by: <ML= (y^r (13) The amount of IL in the vapor phase is assumed to be zero, due to the negligible vapor pressure of ILs; therefore, the vapor mole fraction of HFC is unity (yHFC= 1) and its phase equilibria are modeled by: χηρ€Φηρ€ ~ Φπρε (14) To adjust the critical parameter of the ionic liquid and the binary interaction parameters for each mixture, nonlinear regression was used to solve the following: min (PvdW ^exp) ίίρίμ,πι,τ,βπ, (15) limited by equations (1) - (14) to calculate Pváw. Pexpson are the experimentally measured pressures at equilibrium. Henry's law constant at infinite dilution Henry's law constants (kH) were used to evaluate refrigerant absorption in liquid-liquids (IL) at infinite dilution concentrations, where lower kH values ​​indicate greater refrigerant solubility in the solvent. (Shiflett, M. B. et al., Ind. Eng. Chem. Fies. 2006, 45, (18), 6375-6382). In this example, the solubilities of both HFC-32 and HFC-125 increased linearly with increasing pressure up to approximately 0.2 MPa, indicating the Henry's law regime; therefore, the partial pressure of the refrigerant was directly proportional to its liquid composition in the liquid phase under dilute conditions. The Henry's law constant can be calculated from experimental refrigerant solubility data (PTx) assuming that hydrostatic pressure correction is not required (Krichevsky-Kasarnovsky equation): lim fi(T,P,yi) (16) where is the vapor-phase fugacity of HFC-32 and HFC-125 (^ = 1) absorbed in IL, which was calculated using an EoS model at given temperature and pressure. (Lemmon, EW et al., 2013). Henry's law constants were calculated by determining the slope of a linear regression, fitting the experimental solubility data to approximately 0.2 MPa, including the theoretical point with no refrigerant in IL at zero pressure. Fickian diffusion analysis In addition to equilibrium solubility, time-dependent absorption data for HFC32 and HFC-125 in IL were also measured using the microgravimetric balance at 298.15 K and pressures ranging from 10.05 to 1.0 MPa. Details on how to apply Fick's law to the actual physical situation have been reported previously; therefore, only some important assumptions and conditions will be provided herein. (Minnick, DL et al., 2018).In this simplified Fickian diffusion model, the following assumptions were applied for the dissolving refrigerant in IL: (i) the interactions between HFC and IL are physical; (ii) HFC dissolves through a one-dimensional (vertical) diffusion process, and there is no convective flow in IL; (iii) a thin boundary layer exists between HFC and IL at Ty Pdadas, where thermodynamic equilibrium is established at the saturation concentration (Cs); (iv) the HFC / IL mixture is a dilute solution, and the thermophysical properties do not change at Ty Pdadas. (Shiflett, MB et al., 2006). These assumptions allow the dissolution of HFC in IL to be described based on one-dimensional mass diffusion, due to the local concentration difference: dC 52C =d dtoz. Initial condition: t = 0.0 < z < L, and C = Co(18) Boundary conditions ( / y i): (i) t > 0, z = 0, and C = Cs(19) dC (ii) t > 0, z = £, and — = 0(20) dz where C is the concentration of HFC in IL as a function of time (t), z is the vertical location, z = n7CCQn / 77n7 / q / υιλι corresponds to the vapor-liquid boundary, L is the depth of IL in the sample container, and Des is the diffusion coefficient that was assumed to be constant. The depth (L) was estimated by knowing the cylindrical geometry of the sample container, the mass and average weight fraction density of the HFC / IL mixture at the initial concentration (Co) and saturation (Cs) at a given Ty P. Equation 17 was solved analytically by applying the appropriate initial and boundary conditions (equations 18-20), and separation of variables or Laplace transform methods to obtain the following: (Yokozeki, A., Int. J. Refrig. 2002, 25, (6), 695-704). oc / co\ V βχρ^-λί,Οΐ) n=0n(21) where λη= [n+ (1 / 2)](π / ί). Although equation 21 has an infinite sum term, only the first ten terms were applied in this analysis. The diffusion coefficient (D) and the equilibrium solubility limit (Cs) for each HFC in the IL dataset were calculated by nonlinear regression of equation 21 using MATLAB software, and the best model fit was obtained by selecting the appropriate Co value. Results and analysis Vapor-liquid equilibrium results The solubility of HFCs in IL depends on the strength of the interaction between the refrigerant and the anion of For example, the relatively high solubility of HFC-32 in ILs containing fluorinated anions is thought to be due to hydrogen bonding between the hydrogen in the refrigerant and the fluorine in the anion. Large differences in solubility have also been found for HFC-32 compared to HFC-125 in [C4Ciim][PF6]. Specifically, HFC-32 / [C4Ciim][PF6] had a Henry's law constant of 8.8 ± 0.7 bar (0.88 ± 0.07 MPa), while HFC-125 / [C4Ciim][PF6] had a Henry's law constant of 23.1 ± 2.3 bar (2.31 ± 0.23 MPa) at 298.15 K. In this example, experimental solubility data for HFC-32 and HFC-125 in three ILs with fluorinated anions ([C4Ciim][BF4], [C4Ciim][PF6], and [C6Ciim][FAP]) and in three ILs with non-fluorinated anions ([C4Ciim][CiCO2], [C4Ciim][SCN], and [C6Ciim][CI]) at pressures ranging between 0.05 and 1.0 MPa and 298.15 K (Tables 8 to 13) and were correlated using the Van der Waals EoS model as shown in Figure 4 and Figure 5. Table 8. Experimental VLE for mixtures of HFC-32 / [C4Ciim][BF4] and HFC-125 / [C4Ciim][BF4] at 298.15 K. nzcccn / zznz / q / uιλι HFC-32 (1) + [C4Ciim][BF4] (2) HFC-125 (1) + [C4Ciim][BF4] (2) P (MPa) 100xí (mol%) Wi (wt%) P (MPa) 100x / (mol%) Wi {wt%) 0.05 2.4 0.6 0.05 0.8 0.4 0.1 5.8 1.4 0.1 1.9 1.0 0.2 12.2 3.1 0.2 4.3 2.3 0.4 23.9 6.8 0.4 10.1 5.6 0.6 36.5 11.8 0.6 17.2 10.0 0.8 44.6 15.8 0.8 26.3 15.9 1.0 54.5 21.9 1.0 37.8 24.4 P - Pressure; 100x; and Wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7) = 0.1SC; u(P) = 0.0008 MPa and u(100xj) = 0.5 molar %. Table 9. Experimental VLE for mixtures of HFC-32 / [C4Ciim][PF6] and HFC-125 / [C4Ciim][PF6] at 298.15 K. HFC-32 (1) + [C4Ciim][PF6] (2) HFC-125 (1) + [C4Ciim][PF6] (2) P (MPa) 100χ, (mol%) Wi (wt%) P (MPa) 100x / (mol%) Wi (wt%) 0.05 3.9 0.7 0.05 1.2 0.5 0.1 7.6 1.5 0.1 2.4 1.0 0.2 14.6 3.0 0.2 4.8 2.1 0.4 27.3 6.4 0.4 9.9 4.4 0.6 38.4 10.2 0.6 16.0 7.2 0.8 48.3 14.6 0.8 23.2 11.0 1.0 57.4 19.8 1.0 32.3 16.1 P- Pressure; 100x; and Wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7j = 0.1eC; u(F) = 0.0008 MPa yu(100xr) = 0.5 % molar. Table 10. Experimental LV for mixtures of HFC-32 / [C6Ciim][FAP] and HFC-125 / [C6Ciim][FAP] 1298.15 K. HFC-32 (1) + [C6Ciim][FAP] (2) HFC-125 (1) + [C6Ciim][FAP] (2) P (MPa) 100x / (% mol) Wf (% wt) P (MPa) 100x, (% mol) Wi (% wt) 0.05 6.7 0.6 0.05 3.8 0.8 0.1 12.6 1.2 0.1 7.4 1.5 0.2 23.3 2.5 0.2 14.2 3.1 0.4 40.2 5.4 0.4 26.7 6.6 0.6 53.1 8.8 0.6 38.0 10.7 0.8 63.4 12.9 0.8 48.2 15.3 1.0 72.0 18.1 1.0 57.8 20.9 P- Pressure; 100χ / and wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7) = 0.1SC; u(P) = 0.0008 MPa yu(100xy) = 0.5 % molar. nzcccn / zznz / q / uιλι Table 11. Experimental VLE for mixtures of HFC-32 / [C4Ciim][CiCO2] and HFC-125 / [C4Ciim][CiCO2] at 298.15 K. HFC-32 (1) + [C4Ciim][CiCO2] (2) HFC-125 (1) + [C4Ciim][CiCO2] (2) P (MPa) 100x, (mol %) Wi (wt %) P (MPa) 100X; (% mol) Wi (% by weight) 0.05 5.4 1.5 0.05 6.0 3.7 0.1 9.7 2.7 0.1 12.2 7.7 0.2 16.1 4.8 0.2 24.0 16.0 0.4 26.8 8.7 0.4 42.9 31.0 0.6 35.7 12.6 0.6 53.6 40.8 0.8 43.8 16.8 0.8 62.0 49.1 1.0 51.0 21.2 1.0 69.2 56.9 P- Pressure; 100xr and wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7) = 0.1SC; u(P) = 0.0008 MPa yu(100x;) = 0.5 % molar. TABLE 12. Experimental VLE for mixtures of HFC-32 / [C4Ciim][SCN] and HFC-125 / [C4Ciim][SCN] at 298.15 K. HFC-32 (1) + [C4C1 ¡m][SCN] (2) HFC-125 (1) + [C4Ciim][SCN] (2) P 100x, Wi P 100xí Wl (MPa) (mol %) (wt %) (MPa) (mol %) (wt %) 0.05 0.4 0.1 0.05 < 0.1 < 0.1 0.1 2.4 0.6 0.1 0.4 0.3 0.2 5.7 1.6 0.2 1.3 0.8 0.4 12.7 3.7 0.4 3.1 1.9 0.6 21.2 6.6 0.6 5.3 3.2 0.8 28.0 9.3 0.8 7.7 4.7 1.0______________34.9_______________12.4 | 1.0_______________10.5________________6.5 P- Pressure; 100xr and Wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7) = 0.1SC; u(P) = 0.0008 MPa yu(100xj) = 0.5 % molar. nzcccn / zznz / q / uιλι Table 13. Experimental VLE for mixtures of HFC-32 / [C6Ciim][CI] and HFC-125 / [CeCr im][CI] a 298.15 K. HFC-32 (1) + [CeCiimKCI] (2) HFC-125 (1) + [C6Ciim][CI] (2) P (MPa) 100xí (mol %) Wi (wt %) P (MPa) 100xr (mol %) Wi (wt %) 0.05 2.1 0.5 0.05 4.0 2.4 0.1 4.4 1.2 0.1 7.9 4.8 0.2 9.2 2.5 0.2 16.0 10.2 0.4 18.6 5.6 0.4 29.0 19.5 0.6 27.2 8.8 0.6 41.4 29.6 0.8 34.5 11.9 0.8 54.3 41.3 1.0 41.0 15.2 1.0 65.4 52.8 P - Pressure; 100x / and Wi - HFC composition (molar % and weight %) in IL. Standard uncertainties: u(7) = 0.1SC; u(P) = 0.0008 MPa and u(100xr) = 0.5 molar %. It should be mentioned that the absorption equilibrium isotherms shown in Figure 4 and Figure 5 were measured up to 1.0 MPa so as not to exceed the saturation vapor pressure at 298.15 K of the HFCs studied in this document, i.e., 1.69 and 1.38 MPa for HFC-32 and HFC-125, respectively. (Lemmon, EW et al., 2013). As expected, the solubility of HFC-32 and HFC-125 increased with increasing pressure for any given IL. However, the relative differences in solubility between HFC-32 and HFC-125 are more important, particularly for the selective separation of R-410A. For example, HFC-32 is 44.2% (mole fraction basis) more soluble than HFC-125 in [C4Ciim][BF4] at 298.15 K and 1.0 MPa. However, the inventors have realized that the most relevant comparison for designing separation systems is the difference in solubility on a mass fraction basis. In this case, due to the molecular weight differences (HFC-32 MW = 52.024 g-mol·1 and HFC-125 MW = 120.02 g-mol·1), HFC-125 is only 11.4% more soluble than HFC-32 at 298.15 K and 1.0 MPa. Similar differences in solubility were found for the other ILs with fluorinated anions, [C4Ciim][PF6] and [C6Ciim][FAP], as shown in Tables 9 and 10, respectively. In addition to the anionic fluorination of imidazolium-based ILs, a longer alkyl chain length for the cation played a role in the increased absorption of HFC-32 and HFC-125 on [C6Ciim][FAP]. Deviation from ideality (Raoult's law) To evaluate the non-ideality of HFC-32 and HFC-125 in liquid-in-glass (LI) fluids, the normalized fugacity was evaluated as a function of the molar compositions of HFC in the liquid phase. The normalized fugacity was expressed as fv / fsat, where fv refers to the vapor-phase fugacity of the HFC resulting from the negligible vapor pressure of the LI, such that yref = 1, and y / corresponds to the fugacity of the HFC at saturated vapor pressure with a temperature of 298.15 K. (Street Jr, KW et al., Tribal. Trans. 2011, 54, (6), 911-919). Figure 6 and Figure 7 show the normalized fugacity for HFC-32 and HFC-125 in the LI fluids studied in this example as a function of molar compositions at 298.15 K. It is very interesting that these refrigerants within the same HFC family exhibit quite different solubility behaviors depending on the choice of ionizing agent (IL). For example, HFC-32 showed a strong negative deviation from Raoult's law at [C6Ciim][FAP] across the entire refrigerant composition range, suggesting that phase behavior was dominated by stronger Van der Waals interactions between HFC-32 and this IL. Furthermore, HFC-32 showed near-ideal solubility behavior at [C4Ciim][CiCO2] and [C4Ciim][PF6] for lower refrigerant compositions (up to 0.3 mole fractions), while at higher refrigerant mole fractions, it showed a slightly positive deviation from Raoult's law. HFC-32 showed positive deviations at all compositions at [C4Ciim][SCN], [C4Ciim][BF4], and [CeCiim][CI].As noted previously, the strong adsorption mechanism of HFC-32 in ILs with fluorinated anions is believed to be due to hydrogen bonding between the electronegative fluorinated anion of the IL (BF4, PFe, and FAP) and the acidic hydrogen atoms on the fluorocarbon (CH2F2). Unlike HFC-32, HFC-125 showed a pronounced positive deviation from Raoult's law in ILs with fluorinated anions (BF4, PFe, and FAP), possibly indicating that the cohesive forces between HFC-125 and IL are weaker than the cohesive forces between HFC / HFC and / or IL / IL. Surprisingly, HFC-125 in [C4Ciim][CiCO2] showed mixed negative and positive deviations from Raoult's law depending on the molar concentration of the refrigerant. For example, HFC-125 showed a negative deviation for lower refrigerant mole fractions (down to approximately 0.6), while at higher refrigerant compositions, it showed a positive deviation from Raoult's law.These results suggest that the carboxylate group in the IL anion plays an important role in increasing the solubility of HFC-125. This is surprising given the existing knowledge that H-bonding with fluorinated anions is critical for high solubility. Van der Waals EoS modeling Figure 4 and Figure 5 (lines) show the Van der Waals EoS model predictions for the solubilities of HFC-32 and HFC-125 in the ILs using the best-fit parameters reported in Tables 14 and 15, respectively. Table 14. Van der Waals EoS model parameters for HFC-32 n7CCQn / 77n7 / q / υιλι Ionic Liquid - Van der Waals Parameters for HFC-32 / IL li¡ ¡ii m T PlL [C6Ciim][FAP] 0.76263 0.76227 -3.1790 1070.6 0.80407 [C4.F46404]1 -5.2491 1492.4 0.25646 [C4Ciim][PF6] 0.77015 0.76988 -3.3283 1079.2 0.96279 [C4Ciim][CiCO2] 0.6215-6825 0 4.9624 [C6Ciim][CI] 0.86666 0.85663 -5.8300 1500.0 0.24679 [C4Ciim][SCN] 0.90109 0.87156 -6.72538 10.99 Table 15. Parameters of the Van der Waals EoS model for HFC-125 Ionic liquid - in Van der Waals Parameters for HFC-125 / IL PlL Iji m τ [C6Ciim][FAP] 0.75724 0.75777 -3.1236 1096.9 0.84396 [B0.F78] im] -9.7377 1495.6 -0.19398 [C4Ciim][PFe] 0.63148 0.63317 -1.7454 1187.0 4.9560 [C4C1 and][ C1CO2] 0.411-207262 0.61 0.053203 [C6Ciim][CI] 0.79991 0.80272 -4.0687 1440.3 0.83820 [C4Ciim][SCN] 0.96174 0.92967 -9.97343 1.67343 1.67 nzcccn / zznz / q / υιλι Because ILs decompose before reaching their critical temperatures and the actual critical points cannot be determined experimentally, hypothetical values ​​(pseudocritical points) were used for ILs in this analysis. (Rebelo, LP et al., J. Phys. Chem. B 2005, 109, (13), 6040-6043; and Raí, N. et al., Faraday discuss. 2012, 154, 53-69). Multiple studies have attempted to predict pseudocritical points for ILs. For the IL [C4Ciim][PF6], methods for estimating pseudocritical properties include empirical equations based on density and surface tension, group contribution methods, Gibbs Monte Carlo ensembles, and the Vetere method based on critical volume. (Rebelo, LP et al., 2005; Valderrama, JO et al., Ind. Eng. Chem. Res. 2009, 48, (14), 6890-6900; Raí, N. et al., 2012; and Yokozeki, A. et al., 2010).However, these various methods result in estimates for pseudocritical temperatures and pressures [C4Ciim][PF6] ranging from 600–1300 K and 0.39–3.0 MPa, respectively. Previous analyses suggested that the generic van der Waals model was not sensitive to the critical properties of ILs (Yokozeki, A. et al., 2010; Yokozeki, A., 2001). To verify this, a systematic analysis of the model fit, quantified by the sum of squared residuals, was performed with respect to Tc from 600 to 1400 K and Pc from 0.1 to 5.0 MPa for the HFC-32 mixture in [C4Ciim][PF6] (data not shown). The results showed that the van der Waals EoS model is insensitive to Tc and Pc for ILs. Therefore, it is unnecessary to determine high-precision pseudocritical IL properties when fitting the Van der Waals EoS model parameters to the binary mixture solubility data. Any critical point estimate can be used if its critical pressure is greater than 0.5 MPa. As mentioned above, Tcy Pc for each IL were set at 1000 K and 2.5 MPa, respectively. A Monte Carlo uncertainty analysis was also performed for the adjusted parameters of the HFC-32 mixture in [C4C1][PF6]. To summarize, a normally distributed random error for the experimental values ​​x, T, and P in Table 9 was added to create a new set of simulated experimental data. The error values ​​were chosen to correspond to experimental accuracy for x, T, and P, and the normal distribution over which the errors were randomly selected was located within the standard uncertainty of each measurement: ±0.005 (unitless) for mole fraction, ±0.1 K for temperature, and ±0.0008 MPa for pressure. Using the simulated data, the Van der Waals parameters l1, l1, T, and β1 were recalibrated, and the results were recorded. This procedure was repeated one thousand times.Therefore, one thousand simulated experimental datasets were generated, with x, T, and P values ​​varying within experimental accuracies, and the Van der Waals parameters were fitted to each simulated dataset. This provided a multivariate distribution of the fitted parameters, shown in Figure 8. The Monte Carlo procedure provides the expected deviation in the fitted results if the experiments were repeated hundreds of times. Three important ideas about the experimental data and the fitted model can be obtained from Figure 8. The graphs along the diagonal of Figure 8 are histograms for the five fitted parameters. The first idea is that the parameter β / L has a variability of 0.785%, ltl has a variability of 0.454%, m has a variability of 2.66%, τ has a variability of 2.44%, and βα has a variability of 25.0%. This variability is induced by random errors of a magnitude similar to the experimental precision. In other words, at least this large variability would be expected if the experiments were repeated with the same equipment. The variability of the fitted parameter β / L is one to two orders of magnitude greater than the other parameters. This provides the second idea: β / L is an unsystematic parameter, which means that it cannot be uniquely determined from these data. (Chis, O.-T. et al., Math. biosc. 2016, 282, 147-161).This is because the quality of fit (sum of squared residuals) is insensitive to β^. The scatter plots below the diagonal in Figure 8 show pairwise variability in the fitted parameters. The tallest histogram bars (on the diagonal) correspond to the best-fitting groups of parameters in the scatter plots (off the diagonal). The dark gray squares mark the parameter values ​​for HFC-32 in [C4C11][PF6] reported in Table 14, which were calculated from the original experimental data in Table 9. In each scatter plot, this dark gray square lies in the densest parameter regions. A third key insight emerges from these scatter plots: the parameters l1j, l1j1, m, and βα are correlated. This suggests that there exists an alternative thermodynamic model with one or more fitted parameters that provides a similar quality of fit (sum of squared residuals). Ideal selectivity based on the Henry's law constants The most suitable IL for a specific gas separation process depends on its gas absorption capacity, its ability to preferentially absorb one gas over another in a mixture, and its ability to facilitate gas diffusion (as discussed previously). In this context, ideal selectivity is a parameter that can be used to evaluate the ability of a given pure IL to separate HFC-32 and HFC-125 in R-410A. Ideal selectivity can be defined as the ratio of the Henry's law constants of the HFC refrigerants at a given temperature, as follows: (Sosa, JE et al., Ind. Eng. Chem. Res. 2019, 58, (45), 20769-20778). í ku¡\ = (22) where kHiy kHj are the Henry's law constants calculated for HFC refrigerants, i = HFC-32 and j = HFC-125, respectively. The Henry's law constants for HFC-32 and HFC-125 in the ILs were calculated using the method described above, and the results are briefly presented in Table 16. Table 10. Henry's law constants (MPa) for HFC-32 and HFC-125 in IL at 298.15 Ka Ionic liquid Henry's law constants Selectivity nzcccn / zznz / q / υιλι (kH) (kH, MPa) Smj HFC-32 HFC-125 [C4Ciim][BF4] 1.54±0.06 4.19±0.17 0.37 [C4Ciim][PF6] 1.34±0.01 4.05±0.06 0.33 [C6Ciim][FAP] 0.84±0.03 1.37±0.01 0.61 [C4Ciim][CiCO2] 1.20±0.11 0.81±0.00 1.48 [C4Ciim][SCN] 3.11±0.37 13.32±2.44 0.23 [C6Ciim][CI] 2.00±0.00 1.16±0.03 1.72 aThe uncertainties are the standard error of the coefficient obtained in the linear regression. Comparing the Henry's law constants calculated for HFC-32 in IL at 298.15 K shows that kH(MPa) follows the order: [CeCiimKFAP] < [C4Ciim][CiCO2] < [C4Ciim][PF6] < [C4Ciim][BF4] < [C6Ciim][CI] < [C4Ciim][SCN]. However, for HFC-125, kH(MPa) follows the order: [C4Ciim][CiCO2] < [C6Ciim][CI] < [CeCiimKFAP] < [C4Ciim][PFe] < [C4Ciim][BF4]. Based on this analysis, the ILs with the highest solubility (i.e., the lowest Henry's law constants) for HFC-32 and HFC-125 are [CeCiimKFAP] and [C4Ciim][CiCO2], respectively. Ideal selectivity can also be defined as the ratio of the solubilities of the pure refrigerant on a molar or mass basis in the IL. As discussed earlier, the mass basis is more relevant for the design of separation systems; therefore, selectivity can be defined as follows: where wviJy Wnj are the vapor and liquid mass fractions of the dissolved refrigerants ( / = HFC-32 andj = HFC-125) in IL at T= 298.15 Ky P= 1.0 MPa, respectively (where iv„ and wv¡ = 1.0). In both cases (SHljand SwiJ), the IL with the highest overall selectivity for the separation of R-410A, based on the ratio of Henry's law constants (Smj) or the ratio of mass fractions (Swlj), was [C6Ciim][CI]. The ideal selectivity trends obtained with equations 22 and 23 are shown in Figure 9. It is emphasized again that the prevailing wisdom has been to compare mole fraction solubility as a function of Ty P in selecting an IL for the most efficient separation (Figures 10A-10F). However, the most relevant comparison for designing a separation process is to evaluate the difference in mass fraction solubility as a function of Ty P (Figures 11A-11F). In some cases, such as for [C4Ciim][BF4], [C4Ciim][PF6], and [C6Ciim][FAP], what appears to be a large difference in mole fraction solubility for HFC-32 and HFC-125 turns out to be only a small or negligible difference in mass fraction solubility. Therefore, selecting these interfering agents (ILs) would not result in efficient separation. Conversely, small differences in mole fraction solubility for HFC-32 and HFC-125 in [C4Ciim][CiCO2] and [C6Ciim][CI] result in larger differences in mass fraction solubility, and thus these two ILs are actually superior candidates for R-410A separation. Fickian diffusion coefficients The diffusivity of the HFCs in the ILs also affects the time-dependent absorption behavior of HFC-32 and HFC-125 in the ILs, which was analyzed using a simplified Fickian diffusion model (see above). The diffusion coefficients calculated for HFC-32 and HFC-125 in each IL at 0.05 MPa and 298.15 K are shown in Table 17, along with the viscosity of the ILs at 298.15 K. Table 17. Estimated Fickian diffusion coefficients for HFC-32 / IL and HFC-125 / IL systems 298.15 K and 0.05 MPa and viscosities reported for IL at 298.15 K and 0.1 MPa.a Ionic liquid Viscosity (Pas) HFC-32 (1) / IL(2) HFC-125 (1) / IL (2) D(10·11 m2s'1) Cs (wt %) D(10'11 m2s·1) Cs (wt %) [C6Ciim][CI] 18.1 ± 1.8 1.5 0.5 0.4 3.2 [C4Ciim][CiCO2] 0.448 ±0.019 0.5 1.5 1.3 3.7 [C4Ci¡m][PF6] 0.271 ±0.021 8.5 0.7 1.7 0.5 [C4Ciim][BF4] 0.1014 ±0.0027 7.8 0.6 2.4 0.4 [CeCiim][FAP] 0.0882 ±0.0021 19.6 0.6 5.5 0.8 [C4Ciim][SCN] 0.0517 ±0.00055 - - - - The uncertainty of the estimated diffusivity was estimated to be within a factor of two of the calculated diffusivity.13 The diffusion coefficient (D) of HFCs in liquid liquefiers (LLs) depends on the refrigerant's solubility (Cs), the LL viscosity, and the molecular radius of the solute molecule, according to the Stokes-Einstein equation. (Yokozeki, A., 2002; and Reid, RC et al., The Properties of Gases and Liquids. McGraw Hill: New York, USA, 1987). The largest D values ​​for HFC-32 and HFC-125 were found in [CeCiimjfFAP] (HFC-32 D = 19.6 x 10⁻¹¹ m²-s¹ and HFC-125 D = 5.5 x 10⁻¹¹ m²-s¹), which has one of the lowest viscosities of the LLs tested. The diffusion coefficient of HFC-32, 3.5 times greater in [C6Ciim][FAP], can be attributed to the approximately 22% smaller molecular radius for HFC-32 (0.18 nm) relative to HFC-125 (0.23 nm). (Yokozeki, A. et al., Inter. J. Thermophys. 1998, 19, (1), 89-127; and Moráis, AR et al., AlChE J. 2020).The diffusion coefficients for HFC-32 and HFC-125 in ILs are of the same order of magnitude, i.e., between 10¹¹ and 10⁻¹⁰ m²-S⁻¹, as those previously reported for other fluorinated ILs (Shiflett et al., 2006). Furthermore, the diffusion coefficient for R-22 (chlorodifluoromethane, CHCIF₂) in [C₄C₋₁][BF₄] and [C₄C₋₁][PF₆] is also within the same order of magnitude (10¹⁰ to 10¹¹ m²-S⁻¹) as the data reported herein (Minnick, D.L. et al., Ind. Eng. Chem. Res. 2019, 58, (25), 1107211081). The trend in the diffusion coefficient with the inverse of viscosity (D ~ 1 / μ) is generally true for HFC-32 and HFC-125, except for HFC-32 + [C4Ciim][CiCO2], which could indicate some chemical interaction between HFC-32 and the acetate anion [C1CO2]. Molecular modeling studies are underway to elucidate this effect. Conclusions A separation process for recycling R-410A is important so that HFC-32 can be reused in new HFCs containing low-GWP refrigerant blends, and HFC-125 can be used as a fluorine-containing feedstock. The adsorption of HFC-32 and HFC-125 in six imidazolium-based ILs containing fluorinated and non-fluorinated anions was accurately measured using a microbalance at 298.15 K and pressures ranging from 0.05 to 1.0 MPa. HFC-32 was found to be more soluble in ILs with fluorinated anions than HFC-125, likely due to hydrogen bonding between the refrigerant (CH2F2) and the fluorinated anions ([BF4], [PFe], and [FAP]). However, HFC-125 was found to be more soluble in ILs with non-fluorinated anions ([C1CO2] and [Cl]). [C4Ciim][SCN] had low solubility for both HFC-32 and HFC-125 compared to the other ILs tested.The experimental VLE datasets were successfully correlated using Van der Waals EoS, and the model was insensitive to the choice of critical parameters (600 < Tc < 1400 K and 0.5). <pc< 5.0 mpa). los il [ceci im][ci] y [c4ciim][cico2] proporcionaron la selectividad ideal más alta (2.7 a 3.5 en masa) para separar r-410a 298.15 k entre los estudiados este ejemplo. el modelo de difusión unidimensional se aplicó datos absorción dependientes del tiempo cada sistema binario hfc il. hfc-32 hfc-125 tuvieron un coeficiente alto [ceciimjifap] con relación otros debido su menor viscosidad. tuvo (hasta [c6ciim][fap]) radio molecular pequeño (0.18 nm comparación 0.25 nm). presente ejemplo proporciona información importante sobre solubilidad, difusividad, el modelado eos diseño proceso separación reciclaje r-410a.The word "illustrative" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as illustrative should not necessarily be construed as preferred or advantageous over other aspects or designs. Furthermore, for the purposes of this disclosure and unless otherwise specified, "one" means one or more. The foregoing description of illustrative embodiments of the invention has been presented for illustrative and descriptive purposes. It is not intended to be exhaustive nor to limit the invention to the precise form disclosed, and modifications and variations are possible in light of prior learning or may be acquired from the practice of the invention. The embodiments were chosen and described to explain the principles of the invention and as practical applications of the invention to enable a person skilled in the art to use the invention in various embodiments and with various modifications as appropriate to the particular use contemplated. The scope of the invention is intended to be defined by the appended claims hereto and their equivalents.

Claims

1. A process for separating an azeotropic mixture, comprising exposing an azeotropic mixture comprising a first (hydro)fluorocarbon and a second (hydro)fluorocarbon to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of the first and second (hydro)fluorocarbon than the other of the first and second (hydro)fluorocarbon determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a processed azeotropic mixture.

2. The process according to claim 1, wherein the ionic liquid is a non-fluorinated ionic liquid.

3. The process according to claim 1, wherein the non-fluorinated anion is chloride.

4. The process according to claim 1, wherein the ionic liquid is a non-halogenated ionic liquid.

5. The process according to claim 1, wherein the non-fluorinated anion is a carboxylate.

6. The process according to claim 5, wherein the carboxylate is acetate.

7. The process according to claim 1, wherein the cation is an imidazolium and the non-fluorinated anion is chloride.

8. The process according to claim 1, wherein the cation is an imidazolium and the non-fluorinated anion is a carboxylate.

9. The process according to claim 8, wherein the carboxylate is acetate.

10. The process according to claim 1, wherein the azeotropic mixture comprises difluoromethane, pentafluoroethane, or both.

11. The process according to claim 1, further comprising the collection of the ionic liquid containing (hydro)fluorocarbon.

12. The process according to claim 11, further comprising exposing the processed azeotropic mixture to an additional amount of the ionic liquid.

13. A process for separating an azeotropic mixture, the process comprising exposing an azeotropic mixture comprising difluoromethane and pentafluoroethane to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of difluoromethane and pentafluoroethane than the other of difluoromethane and pentafluoroethane determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a processed azeotropic mixture.

14. The process according to claim 13, wherein the ionic liquid is a non-fluorinated ionic liquid.

15. The process according to claim 13, wherein the non-fluorinated anion is chloride.

16. The process according to claim 13, wherein the ionic liquid is a non-halogenated ionic liquid.

17. The process according to claim 13, wherein the non-fluorinated anion is a carboxylate.

18. The process according to claim 17, wherein the carboxylate is acetate.

19. The process according to claim 13, wherein the cation is an imidazolium and the non-fluorinated anion is chloride.

20. The process according to claim 13, wherein the cation is an imidazolium and the non-fluorinated anion is a carboxylate.

21. The process according to claim 20, wherein the carboxylate is acetate.

22. A process for separating an azeotropic mixture, comprising exposing an azeotropic mixture comprising pentafluoroethane and 1,1,1-trifluoroethane to an ionic liquid comprising a cation and a non-fluorinated anion at a temperature and pressure at which the ionic liquid absorbs more of one of pentafluoroethane and 1,1,1-trifluoroethane than another of pentafluoroethane and 1,1,1-trifluoroethane determined on a mass basis to form an ionic liquid containing (hydro)fluorocarbon and a processed azeotropic mixture.

23. The process according to claim 22, wherein the azeotropic mixture further comprises 1,1,t,2-tetrafluoroethane and the ionic liquid absorbs more of one of pentafluoroethane, 1,1,1-trifluoroethane and 1,1,2-tetrafluoroethane than another of pentafluoroethane, 1,1,1-trifluoroethane and 1,1,1,2-tetrafluoroethane determined on a mass basis.