Drop-in recycled refrigerant compositions having no net GWP

Abstract

A refrigerant composition includes about 90-92 wt % difluoromethane and about 8-10 wt % pentafluoroethane. The refrigerant composition is formed from all recycled materials, and the refrigerant composition has a net global warming potential of about 0. A method of preparing the refrigerant composition includes injecting a mixture of recovered refrigerants into the center of a distillation column, the mixture of injected refrigerants being difluoromethane, pentafluoroethane and chlorodifluoromethane, removing from the top of the distillation column a refrigerant composition of about 90-92 wt % difluoromethane and about 8-10 wt % pentafluoroethane, and removing chlorodifluoromethane from a bottom of the distillation column.

Claims

1. A 2-component fluorocarbon refrigerant composition, consisting essentially of: about 90-92 wt % difluoromethane; and about 8-10 wt % pentafluoroethane, wherein the composition is formed from all recycled materials.

2. The refrigerant composition of claim 1, wherein the refrigerant composition consists essentially of: about 91 wt % difluoromethane; and about 9 wt % pentafluoroethane.

3. The refrigerant composition of claim 1, wherein the refrigerant composition has a theoretical boiling point of about −61° F.

4. The refrigerant composition of claim 1, wherein the refrigerant composition has a liquid phase pressure of about 221 psia at 70° F.

5. The refrigerant composition of claim 1, wherein the refrigerant composition has a vapor phase pressure of about 221 psia at 70° F.

6. The refrigerant composition of claim 1, wherein the refrigerant composition has a liquid phase density of about 0.99 g/cm.sup.3 at 70° F.

7. The refrigerant composition of claim 1, wherein the refrigerant composition has a vapor phase density of about 0.045 g/cm.sup.3 at 70° F.

8. The refrigerant composition of claim 1, wherein the refrigerant composition has a liquid phase enthalpy of about 0.24 kJ/g at 70° F.

9. The refrigerant composition of claim 1, wherein the refrigerant composition has a vapor phase enthalpy of about 0.5 kJ/g at 70° F.

10. The refrigerant composition of claim 1, wherein the refrigerant composition has a liquid phase entropy of about 6.3×10.sup.−4 kJ/gR at 70° F.

11. The refrigerant composition of claim 1, wherein the refrigerant composition has a vapor phase entropy of about 1.1×10.sup.−3 kJ/gR at 70° F.

12. The refrigerant composition of claim 1, wherein the refrigerant composition has lower flammability than difluoromethane.

13. A refrigerant mixture, comprising: about 95-99.99 wt % of the refrigerant composition of claim 1; and about 0.01-5 wt % lubricant selected from the group consisting of mineral oil, alkylbenzene oil and polyol ester.

14. The refrigerant mixture of claim 13, wherein the lubricant is an ester of at least one neopentyl polyol represented by the structural formula: ##STR00004## in which each R is independently selected from CH.sub.3, C.sub.2H.sub.5 or CH.sub.2OH.

15. The refrigerant mixture of claim 13, wherein the refrigerant mixture further comprises at least one of an ultraviolet dye or a sealant.

16. A method of preparing a refrigerant composition, comprising: injecting a mixture of reclaimed refrigerants into a center of a distillation column, the mixture of reclaimed refrigerants comprising difluoromethane, pentafluoroethane and chlorodifluoromethane; removing from a top of the distillation column a refrigerant composition of about 90-92 wt % difluoromethane and about 8-10 wt % pentafluoroethane; and removing chlorodifluoromethane from a bottom of the distillation column, wherein the refrigerant composition is formed from all recycled materials.

17. The method of claim 16, wherein the refrigerant composition comprises about 91 wt % difluoromethane, and about 9 wt % pentafluoroethane.

18. The method of claim 16, wherein the mixture of reclaimed refrigerants further comprises 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane and hydrocarbon.

19. The method of claim 16, wherein the mixture of reclaimed refrigerants comprises: about 15.5 wt % 1,1,1,2-tetrafluoroethane; about 12.5 wt % pentafluoroethane; about 12.5 wt % difluoromethane; about 6.5 wt % 1,1,1-trifluoroethane; about 50 wt % chlorodifluoromethane; and about 3 wt % hydrocarbon.

20. A 2-component fluorocarbon refrigerant composition, consisting essentially of: about 90-92 wt % difluoromethane; and about 8-10 wt % pentafluoroethane, wherein the composition is formed from all recycled materials, and the refrigerant composition is a drop-in replacement for difluoromethane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure are shown. However, this disclosure should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Like numbers refer to like elements throughout.

(2) FIG. 1 depicts the liquid phase pressure-temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(3) FIG. 2 depicts the vapor-phase pressure-temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(4) FIG. 3 depicts the liquid density-temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(5) FIG. 4 depicts the vapor density-temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(6) FIG. 5 depicts the liquid phase enthalpy versus temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(7) FIG. 6 depicts the vapor phase enthalpy versus temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(8) FIG. 7 depicts the liquid phase entropy versus temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(9) FIG. 8 depicts the vapor phase entropy versus temperature curve of the refrigerant compositions of the disclosure compared to R-32, R-410A and R-454B;

(10) FIG. 9 shows the ODS refrigerant reclamation totals by year;

(11) FIG. 9A shows HCF refrigerant reclamation totals by year, mixed refrigerant received totals by year and total refrigerant received totals by year;

(12) FIG. 10 depicts the R-22 phase-out schedule;

(13) FIG. 11 depicts the HFC phasedown schedule; and

(14) FIG. 12 is a schematic diagram of a distillation apparatus according to an embodiment of the disclosure.

DETAILED DESCRIPTION

(15) For simplicity and illustrative purposes, the present disclosure is described by referring mainly to exemplary embodiments thereof. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be readily apparent to one of ordinary skill in the art that the present disclosure may be practiced without limitation to these specific details.

(16) The disclosure relates to a refrigerant mixture distilled from recovered refrigerants that is a drop-in replacement for R-32 and has a net GWP of zero. A typical mixture of recovered HFC refrigerants coming back to refrigerant reclamation facilities can be introduced to a distillation process to produce an HFC blend that will work as an R-32 substitute with equivalent levels of performance, reduced flammability characteristics, and net-zero GWP.

(17) The nomenclature of the materials used in the disclosure is set forth in Table. 1.

(18) TABLE-US-00001 TABLE 1 Description of Refrigerant Materials Chemical Name Formula Designation 1, 1,1,2-tetrafluoroethane CF.sub.3CH.sub.2F R-134A pentafluoroethane CF.sub.3CHF.sub.2 R-125 difluoromethane CHF.sub.3 R-32  chlorodifluoromethane CF.sub.3Cl R-22  1,1,1,-trifluoroethane CF.sub.3CH.sub.3 R-143A 2,3,3,3-tetrafluoropropene H.sub.2C═CFCF.sub.3 R-1234YF 1,3,3,3-tetrafluoropropene CF.sub.3CH═CHF R-1234ZE 50:50 R-32:R-125* R-410A 68.9:31.1 R-32:1234YF* R-454B Hydrocarbon CH.sub.3(CH2.sub.n)CH.sub.3 HC *Proportions in wt %.

(19) R-32 is a replacement for R-410A primarily in home cooling applications like multi-family living and impacts nearly every person in the United States. There are 3 classifications of flammability in AHRI with R-32 receiving a “mildly” flammable application compared to the A1 “non-flammable” category of R-410A (combination of R-32 and R-125). There will be no need for additional flammability consideration because the disclosed formulation will be a direct drop-in for R-32 in new applications as well as make-up gas for the installed equipment base at lower flammability considerations.

(20) The disclosed formulation is shown in Table 2 below as a direct replacement for R-32 and compared to R-410A. The 91:9 R-32:R-125 product has no ASHRAE designation or close formulations because there is no known manufacturing process until now to make this product.

(21) TABLE-US-00002 TABLE 2 Formulations of the Disclosure Compared to R-32, R-410A and R-454B. 91:9 R- 20:80 R- 32:R-125 32: R-125 Product Mixture Mixture R-32 R-410A R-454B R-125 9.00 wt % 20.0 wt % 0.00 wt % 50.00 wt % 0.00 wt % R-32  91.00 wt % 80.0 wt % 100.0 wt % 50.00 wt % 68.90 wt % R-1234YF 0.00 wt % 0.00 wt % 0.00 wt % 0.00 wt % 31.0 wt % Total 100.0 wt % 100.0 wt % 100.0 wt % 100.0 wt % 100 wt % Pressure at 221 212 221 216 198 70° F. (psia) GWP 929.3 1240 675 2087 465.7 100% 0 — — — — Reclaim GWP Theoretical −61.0 −60.2 −61.6 −58.0 −49.3 BP(° F.) *These formulas have a variation of up to ± 2%. The values were generated using the NIST REFPROP program.

(22) It should be noted that the typical compressor is sized for R-32 and most people will erroneously believe that R-410a can be used in an R-32 system. However, the calculations are clear that there will be a 35% loss on vapor density feed. This variance can be easily viewed in FIG. 4. This 91:9 R-32:R-125 product is less flammable and we will demonstrate below that all curves will line up essentially perfectly to R-32 as will be discussed below (generated using REFPROP NIST formulas). The GWP of the product, if made from virgin materials, is 929.3 versus R-32 at 675 GWP, but the product will be made from reclaimed material in fractionation columns (demonstrated below) from mixed reclaim material in large supply at zero GWP. This growing category of highly mixed refrigerant has no known solutions in either legacy or new refrigerant applications and is accumulating around the U.S.

(23) FIG. 1 shows the liquid pressure (psia versus temperature) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen, there is a close correlation with the 91:9 R-32:R-125 product having a close overlap with R-32, especially at temperatures lower than 70° F.

(24) FIG. 2 shows the vapor phase pressure (psia) versus temperature (° F.) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen there is almost complete overlap over the entire temperature range from −60° F. to 125° F., with the exception of R-454B.

(25) FIG. 3 shows the liquid phase density (g/cm.sup.3) versus temperature (° F.) of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. There is an almost complete overlap over the entire temperature range, with the exception of R-410A having a slightly higher density range.

(26) FIG. 4 shows the vapor phase density (g/cm.sup.3) versus temperature (° F.) of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. There is an almost complete overlap over the entire temperature range, with the exception of R-410A having a higher density range.

(27) FIG. 5 shows the liquid phase enthalpy (kJ/g) versus temperature (° F.) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen, there is a close correlation over the temperature range with some variance for at the ends of the range.

(28) FIG. 6 shows the vapor phase enthalpy (kJ/g) versus temperature (° F.) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen, there is a close correlation over the temperature range for 91:9 R-32:R-125 and R-32.

(29) FIG. 7 shows the liquid phase entropy (kJ/gR) versus temperature (° F.) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen, there is a close correlation over the entire temperature range with a very tight overlap in the 0° F. to 70° F. range used in air conditioning and refrigeration.

(30) FIG. 8 shows the vapor phase entropy (kJ/gR) versus temperature (° F.) relationship of the 91:9 R-32:R-125 product compared to R-32, R-410A and R-454B. As can be seen, there is a close correlation between the 91:9 R-32:R-125 product and R-32, which is higher than the vapor entropy of R-410A and R-454B.

(31) The thermodynamic properties of the 91:9 R-32:R-125 mixture at 70° F. compared to R-32, R-410A and R-454B are shown in Table 3.

(32) TABLE-US-00003 TABLE 3 Thermodynamic Properties of 91:9 R-32:R-125 compared to R-32 and R-410A at 70° F. Liquid Vapor Liquid Vapor Liquid Vapor Liquid Vapor Phase Phase Phase Phase Phase Phase Phase Phase Pressure Pressure Density Density Enthalpy Enthalpy Entropy Entropy Material (psia) (psia) (g/cm.sup.3) (g/cm.sup.3) (kJ/g) (kJ/g) (kJ/gR) (kJ/gR) FF- 221 221 0.99 0.045 0.24 0.50 6.3 × 10.sup.−4 1.1 × 10.sup.−3 32/125- 91/9 R32 221 221 0.98 0.042 0.24 0.52 6.3 × 10.sup.−4 1.2 × 10.sup.−3 R410A 216 216 1.08 0.059 0.23 0.43 6.2 × 10.sup.−4 1.0 × 10.sup.−3 R454B 205 198 1.00 0.045 0.24 0.47 6.2 × 10.sup.−4 1.1 × 10.sup.−3

(33) As can be seen, the 91:9 R-32:R-125 has properties similar to R-32 and is thus an excellent drop-in replacement for R-32. Also, the 91:9 R-32:R-125 has properties comparable to R-410A.

(34) The data in Table 3 can be compared to the properties at 0° F. shown in Table 4:

(35) TABLE-US-00004 TABLE 4 Thermodynamic Properties of 91:9 R-32:R-125 compared to R-32 and R-410A at 0° F. Liquid Vapor Liquid Vapor Liquid Vapor Liquid Vapor Phase Phase Phase Phase Phase Phase Phase Phase Pressure Pressure Density Density Enthalpy Enthalpy Entropy Entropy Material (psia) (psia) (g/cm.sup.3) (g/cm.sup.3) (kJ/g) (kJ/g) (kJ/gR) (kJ/gR) FF- 64.0 64.0 1.13 0.013 0.17 0.49 4.9 × 10.sup.−4 1.2 × 10.sup.−3 32/125- 91/9 R32 64.0 64.0 1.11 0.012 0.17 0.51 4.9 × 10.sup.−4 1.2 × 10.sup.−3 R410A 63.1 63.0 1.24 0.017 0.17 0.41 5.0 × 10.sup.−4 1.0 × 10.sup.−3 R454B 60.0 57.4 1.14 0.013 0.17 0.45 5.0 × 10.sup.−4 1.1 × 10.sup.−3

RECLAMATION STREAMS AND BACKGROUND

(36) FIG. 9 and FIG. 9A is a reclamation summary of data by the U.S. EPA for the reclamation history of ODS (ozone-depleting substances) as well as HFCs. One can observe the category of the growing quantities of HFCs that are classified as “mixed”. These highly mixed HFCs that can also contain ODS streams is a growing environmental category of carbon pollution with no known uses. The virgin manufactured solutions that are formulated HFC/HFO blends (like the R-454B benchmark enclosed) to have lower GWP will continue to grow the mixed category or will be vented into the atmosphere at the end of life without appropriate technology for recycling and decarbonization.

(37) Although ODS (R-22) was phased out on the schedule shown in FIG. 10, with an allocation of 0 pounds scheduled for 2020. R-22 is still the largest reclaimed product in the U.S. and based on history, will take many years to completely phase out. R-22 is a single molecule and much easier to reclaim with single plate distillation than complex HFCs. HFC blends and mixed HFCs require a much more complicated technology in order to reprocess.

(38) FIG. 11 depicts the AIM ACT HFC phasedown schedule from 2022 to 2037. Over this time frame, the phasedown goes from a 90% reduction in 2022 down to 15% in 2037.

(39) Components of the refrigerant formulation of the disclosure contain reclaimed material. The EPA defines refrigerant reclamation as a means to reprocess refrigerant to at least the purity specified in Appendix A of 40 C.F.R. § 82, subpart F (based on AHRI Standard 700-1993, Specifications for Fluorocarbon and Other Refrigerants) and to verify this purity using the analytical methodology prescribed in appendix A. The EPA requires that refrigerant be reclaimed when a certified technician recovers refrigerant and puts it in a special DOT container and has no intention of putting it back in the same system from which it was recovered.

(40) In the disclosure, the refrigerant must be reclaimed to the AHRI Standard 700 of purity by a certified reclaimer. This requirement protects the integrity of used refrigerant to prevent damage to air-conditioning and refrigeration equipment. Contaminated refrigerants can lead to increased repair costs, shortened maintenance intervals, decreased equipment lifespan, increased leak rates, and a reduction in consumer confidence in reclaimed refrigerants. Once the reclaimed refrigerant is brought up to standard, it can be used at least partially or wholly in the formulations of the disclosure.

(41) Formulations with reclaimed material results in a dramatic reduction in GWP, because the reclaimed material is not being released into the atmosphere. Formulations with all reclaimed material results in a net GWP of about 0 and reduces the requirement to run virgin HFC/HFO plants in various parts of the world.

(42) Another issue for refrigerants is flammability. The most well-established classification for this is the ASHRAE classification. Refrigerants such as R-410A, R-407A and R-404A are class 1 in their flammability, so do not show flame propagation when tested at 100° C. and 101.3 kPa in air. Class 2 refrigerants are those with flammability lower than 0.10 kg/m.sup.3 at 100° C. and 101.3 kPa and a heat of combustion of less than 19 kJ/kg. Class 3 refrigerants have flammability over this boundary and this includes many hydrocarbons.

Lubricants

(43) Optionally, lubricants can be added to the formulations of the disclosure. The lubricants can be mineral oil, alkylbenzene oil or polyol ester (POE).

(44) In another embodiment, the POE can be a synthetic POE compatible for use in refrigeration and air-conditioning compressors using HFC refrigerants, as well as for original equipment manufacturing (OEM) retrofitting operations. The POE forms a single clear phase, i.e., is miscible with the formulations of the disclosure. Miscibility lowers the viscosity of the lubricant carried through the system, so that the lubricant can more efficiently return to the compressor. In contrast, existing mineral oil lubricants are not miscible with HFCs. The composition of the present disclosure is compatible with all types of compressors, including reciprocating and rotary in residential air conditioning, and centrifugal, reciprocating and scroll in industrial and commercial refrigeration and air conditioning.

(45) The POE of the present disclosure can be obtained by introducing neopentyl polyol material, aliphatic monocarboxylic acid material and a catalytic quantity of acid catalyst material into a reaction zone, whereby a reaction mixture is formed, the neopentyl polyol material being at least one neopentyl polyol represented by the structural formula:

(46) ##STR00002##
in which each R is independently selected from —CH.sub.3, —C.sub.2H.sub.5 and —CH.sub.2OH. The aliphatic monocarboxylic acid material is at least one aliphatic hydrocarbon monocarboxylic acid, and the acid catalyst material is at least one acid esterification catalyst, wherein the initial concentration of the aliphatic monocarboxylic acid material in the reaction mixture is such as to provide an initial mole ratio of carboxyl groups to hydroxyl groups in the reaction mixture of from about 0.25:1 to about 0.5:1, and, while the reaction mixture is established and maintained at about 338-392° F. (170-200° C.), aliphatic monocarboxylic acid vapor and water vapor are withdrawn from the reaction zone.

(47) Another approach would be to produce a poly(neopentyl polyol) ester composition by (i) reacting a neopentyl polyol having the formula:

(48) ##STR00003##

(49) wherein each R is independently selected from CH.sub.3, C.sub.2H.sub.5 and CH.sub.2OH and n is a number from 1 to 4, with at least one monocarboxylic acid having 2 to 15 carbon atoms in the presence of an acid catalyst and at an initial mole ratio of carboxyl groups to hydroxyl groups of greater than 0.5:1 to 0.95:1 to form a partially esterified poly(neopentyl polyol) composition; and (ii) reacting the partially esterified poly(neopentyl polyol) composition produced in (i) with additional monocarboxylic acid having 2 to 15 Carbon atoms to form a final poly(neopentyl polyol) ester composition.

(50) The properties of the POE of the present disclosure can be in the viscosity range of about 20 to 68 cSt at 40° C. (104° F.) and about 3 to 7 cSt at 100° C. (212° F.). The viscosity index should be in the range of about 100 to 130. The pour point should be in the range of about −40 to −50° C. (−40 to −58° F.). The density at 20° C. (68° F.) should be in the range of about 0.97 to 0.98 g/ml. The flash point should be in the range of about 240 to 270° C. (about 464 to 518° F.). The acid value should be less than about 0.05 mg KOH/g.

(51) The disclosure is not restricted to POE lubricant. Other lubricants can include mineral or hydrocarbon oil, alkylbenzene oil, white or paraffinic oil and mixtures thereof. The amount of lubricating oil is an amount effective in providing acceptable lubrication to the compressor parts for its longevity. An effective amount of these conventional lubricating oils is the amount recommended by the equipment manufacturer. Typically, the conventional lubricating oil is present in an amount from about 1 to about 60 wt %. The present disclosure has unexpectedly found the amount of POE to be less than about 1 wt %, as little as about 0.67 wt %, with even 0.4 wt % giving excellent lubrication. The range in which POE can be present can be from about 0.1 to about 5 wt %.

Additives

(52) The compositions of the disclosure may also contain one or more additives such as oxidation resistance and thermal stability enhancers, corrosion inhibitors, metal deactivators, lubricity additives, viscosity index enhancers, pour and/or floc point depressants, detergents, dispersants, antifoaming agents, anti-wear agents, UV dyes, sealants and extreme pressure resistant additives. Many additives are multifunctional. For example, certain additives may impart both anti-wear and extreme pressure resistance properties, or function both as a metal deactivator and a corrosion inhibitor. Cumulatively, all additives preferably do not exceed about 8 wt %, or more preferably do not exceed about 5 wt %, of the total composition.

(53) An effective amount of the foregoing additive types is generally in the range from about 0.01 to 5 wt % for the antioxidant component, about 0.01 to 5 wt % for the corrosion inhibitor component, from about 0.001 to 0.5 wt % for the metal deactivator component, from about 0.5 to 5 wt % for the lubricity additives, from about 0.01 to 2 wt % for each of the viscosity index enhancers and pour and/or floc point depressants, from about 0.1 to 5 wt % for each of the detergents and dispersants, from about 0.001 to 0.1 wt % for antifoam agents, and from about 0.1-2 wt % for each of the anti-wear and extreme pressure resistance components. All these percentages are by weight and are based on the total composition. It is to be understood that more or less than the stated amounts of additives may be more suitable to particular circumstances, and that a single molecular type or a mixture of types may be used for each type of additive component. Also, the examples listed below are intended to be merely illustrative and not limiting.

(54) Examples of oxidation resistance and thermal stability enhancers suitable for use in the present disclosure include, for example: diphenyl-, dinaphthyl-, and phenylnaphthyl-amines, in which the phenyl and naphthyl groups can be substituted, e.g., N,N′-diphenyl phenylenediamine, p-octyldiphenylamine, p,p-dioctyldiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, N-(p-dodecyl)phenyl-2-naphthylamine, di-1-naphthylamine, and di-2-naphthylamine; phenothiazines such as N-alkyl-phenothiazines; imino(bisbenzyl); hindered phenols such as 6-(t-butyl) phenol, 2,6-di-(t-butyl) phenol, 4-methyl-2,6-di-(t-butyl) phenol, 4,4′-methylenebis(2,6-di-{t-butyl}phenol); combinations of two or more thereof, and the like.

(55) Examples of cuprous metal deactivators suitable for use in the present disclosure include: imidazole, benzimidazole, 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, salicylidine-propylenediamine, pyrazole, benzotriazole, tolutriazole, 2-methylbenzimidazole, 3,5-dimethyl pyrazole, and methylene bis-benzotriazole. Benzotriazole derivatives are preferred. Other examples of more general metal deactivators and/or corrosion inhibitors include organic acids and their esters, metal salts, and anhydrides, e.g., N-oleyl-sarcosine, sorbitan mono-oleate, lead naphthenate, dodecenyl-succinic acid and its partial esters and amides, and 4-nonylphenoxy acetic acid; primary, secondary, and tertiary aliphatic and cycloaliphatic amines and amine salts of organic and inorganic acids, e.g., oil-soluble alkyl ammonium carboxylates; heterocyclic nitrogen containing compounds, e.g., thiadiazoles, substituted imidazolines, and oxazolines; quinolines, quinones, and anthraquinones; propyl gallate; barium dinonyl naphthalene sulfonate; ester and amide derivatives of alkenyl succinic anhydrides or acids, dithiocarbamates, dithiophosphates; amine salts of alkyl acid phosphates and their derivatives.

(56) Examples of suitable lubricity additives include long chain derivatives of fatty acids and natural oils, such as esters, amines, amides, imidazolines, and borates.

(57) Examples of suitable viscosity index enhancers include polyacrylates, polymethacrylates, copolymers of vinyl pyrrolidone, as well as, acrylates, methacrylates, polybutenes, and styrene-acrylate copolymers.

(58) Examples of suitable pour point and/or floc point depressants include polymethacrylates such as methacrylate-ethylene-vinyl acetate terpolymers; alkylated naphthalene derivatives; and products of Friedel-Crafts catalyzed condensation of urea with naphthalene or phenols.

(59) Examples of suitable detergents and/or dispersants include poly butenyl succinic acid amides; polybutenyl phosphonic acid derivatives; long chain alkyl substituted aromatic sulfonic acids and their salts; and metal salts of alkyl sulfides, of alkyl phenols, and of condensation products of alkyl phenols and aldehydes.

(60) Examples of suitable antifoam agents include silicone polymers and acrylates.

(61) Examples of suitable anti-wear and extreme pressure resistance agents include sulfurized fatty acids and fatty acid esters, such as sulfurized octyl tallate; sulfurized terpenes; sulfurized olefins; organopolysulfides; organophosphorus derivatives including amine phosphates, alkyl acid phosphates, dialkyl phosphates, anime dithiophosphates, trialkyl and triaryl phosphorothioates, trialkyl and triaryl phosphines, and dialkylphosphites, e.g., amine salts of phosphoric acid monoethyl ester, amine salts of dinonylnaphthalene sulfonate, triphenyl phosphate, trinaphthyl phosphate, diphenyl cresyl and cresyl diphenyl phosphates, naphthyl diphenyl phosphate, triphenyl phosphorothionate; dithiocarbamates, such as an antimony dialkyl dithiocarbamate; chlorinated and/or fluorinated hydrocarbons, and xanthates.

(62) Fluorescent dyes may be added to the refrigerant mixture in order to detect leaks. One preferred leak detection or dye additive is a fluorescent, alkyl substituted perylene dye compound dissolved in an oil which is the same as the system lubricating oil, or which is otherwise compatible with the refrigerant and oil. The dye may be soluble in polyhalogenated hydrocarbon refrigerants and fluoresces a brilliant yellow-green under illumination by long wave ultraviolet light. In an automobile air conditioner system that has a fully-charged capacity of thirty-three ounces of R-134A refrigerant and seven ounces of lubricating oil, an amount of about 0.014 ounces dye additive is effective to locate leaks without adversely affecting the operation of the system.

(63) In an embodiment, the dye is a fluorescent dye which is a solid compound or composition soluble in both the refrigerant and refrigeration or system lubricant. The dyes could be naphthoxanthene, perylene and naphthalene compounds, such as: naphtho{3,2,1-kl}xanthene-2,8-dialkyl, naphtho{3,2,1-kl}xanthene-2,8-dimethyl 3,9-perylene dialkyl acetate, 3,9-perylene dimethyl acetate, 4-alkylamino-n-alkyl-naphthalimide, 4-alkylamino-n-methyl-naphthalimide, and dinaphtho(1,2,3-cd; 1′2′3-Im)perylene-9,18-dione, alkyl derivatives.

(64) Dye concentrates can be used which includes a lubricant and at least about 3 weight percent of a leak detection dye, wherein the dye concentrate is a suspension or a semi-solid material, the dye concentrate has a viscosity of at least 10 cP at room temperature, the leak detection dye includes a naphthalimide, a perylene, a thioxanthene, a coumarin, or a fluorescein, and the leak detection dye includes a plurality of particles in which greater than 60 percent of the particles have a particle size of less than 40 microns.

(65) Similar to the liquid dyes, the fluorescent solid dye must be stable at operating temperatures of the A/C or refrigeration system, and should not change the properties of the refrigerant or the system lubricant or adversely affect components and parts of the system.

(66) Sealants may also be added to the refrigerant mixture in order to seal leaks of refrigerant. Leaks allow refrigerants and other working fluids to escape into the atmosphere, contaminating the environment and decreasing the efficiency and cooling capacity of the unit. If large amounts of cooling working fluids such as refrigerants escape, the system may overheat and the service life of the unit will thereby be shortened. Further, the unit may suffer mechanical failure from the loss of the working fluid. In general, leaks in heating and cooling systems also decrease the heat transfer efficiency of these systems.

(67) One example of a sealant is a composition of about 60% by volume of vinyltrimethoxysilane, about 30% by volume of n-beta(aminoethyl)-gamma-aminopropyltrimethoxysilane; and about 10% by volume of methyltrimethoxysilane, a water scavenger. The methyltriethoxysilane is a water scavenger and the vinyl trimethylsilane is a metal bonding material in which the n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane is for cross linking.

(68) An organosilane or components of the sealant mixture may include components that can be represented as (R.sub.1)(R.sub.2)Si(R.sub.3)(R.sub.4) where, R.sub.1 is an alkyl radical of 1-4 carbon atoms or vinyl or —OH, R.sub.2 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub.2 or —R.sub.1NHR.sub.1NH.sub.2, R.sub.3 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub.2 or —R.sub.1NHR.sub.1NH.sub.2, and R.sub.4 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub.2 or —R.sub.1NHR.sub.1NH.sub.2.

(69) A component of the sealant mixture may include components that can be represented as (R.sub.5)(R.sub.6)(R.sub.7)Si—O—Si(R.sub.5)(R.sub.6)(R.sub.7) R.sub.5, R.sub.6 or R.sub.7 are each any one of R.sub.1, R.sub.2,R.sub.3 or R.sub.4 where, R.sub.1 is an alkyl radical of 1-4 carbon atoms or vinyl or —OH, R.sub.2 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub.2 or —R.sub.1NHR.sub.1NH.sub.2, R.sub.3 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub.2 or —R.sub.1NH R.sub.1NH.sub.2, and R.sub.4 is R.sub.1 or —OR.sub.1 or —NH(R.sub.1) or —N(R.sub.1).sub..2 or —R.sub.1NHRR.sub.1NH.sub.2.

(70) Other components which can be included are oligomers of the monomeric silanes described. One such example are the siloxanes: (R.sub.5)(R.sub.6)(R.sub.7)Si—O—Si(R.sub.5)(R.sub.6)(R.sub.7) Where R.sub.5, R.sub.6 or R.sub.7 may be R.sub.1,R.sub.2,R.sub.3 or R.sub.4.

(71) The sealant mixture may also include a lubricant miscible with the organosilane and refrigerant for use in the system. The miscible mixture may include a lubricant selected from one or more of a polyol ester, polyalkylene glycol, mineral oil, polyalphaolefin and alkylbenzene. The miscible mixture may include a lubricant further formed from additives to enhance and refresh the performance of the lubricant in the compressor.

(72) The organosilane is chosen with several criteria in mind. The organosilane is miscible in the lubricant fluid; it is typically a monomer, but may contain oligomers capable of forming a solid polymer with itself or other chosen organosilanes in the presence of moisture under the conditions of the particular application. The reaction rate of the organosilane or mixture of organosilanes is sufficient to form an effective seal at the site of the leak. The polymeric seal is chosen to be sufficiently strong to maintain an effective barrier to prevent further leakage of refrigerant from the system. Also, the organosilanes are chosen to be stable in the absence of moisture, be non-corrosive and otherwise inactive to the components of the system and be generally environmentally acceptable. Further, the nature and quantity injected of the organosilanes are chosen, to the extent that it would interfere with the refrigerant and/or lubricant, so that such interference remains consistent with the normal operation of the refrigerant fluid e.g. vaporization and liquefaction characteristics.

(73) An effective amount of the foregoing additive types is generally in the range from about 0.01 to about 5 wt % for the antioxidant component, about 0.01 to about 5 wt % for the corrosion inhibitor component, from about 0.001 to about 0.5 wt % for the metal deactivator component, from about 0.5 to about 5 wt % for the lubricity additives, from about 0.01 to about 2 wt % for each of the viscosity index enhancers and pour and/or floc point depressants, from about 0.1 to about 5 wt % for each of the detergents and dispersants, from about 0.001 to about 0.1 wt % for antifoam agents, and from about 0.1 to about 2 wt % for each of the anti-wear and extreme pressure resistance components. All these percentages are by weight and are based on the total composition. It is to be understood that more or less than the stated amounts of additives may be more suitable to particular circumstances, and that a single molecular type or a mixture of types may be used for each type of additive component. As used herein, the term “effective amount” means the amount of each component which upon combination with the other component or components, results in the formation of the present compositions.

(74) Many of the aforementioned additives are multifunctional. For example, certain additives may impart both anti-wear and extreme pressure resistance properties, or function both as a metal deactivator and a corrosion inhibitor. Cumulatively, all additives preferably do not exceed about 8% by weight, or more preferably do not exceed about 5% by weight, of the total composition.

Government Mandates and Refrigerant Reduction

(75) FIGS. 9 and 9A are a reclamation summary of data by the U.S. EPA for reclamation data of ODS (ozone-depleting substances) as well as HFCs. In addition, you can see the category of the growing quantities of HFCs that are classified as “mixed”. This is a growing environmental category with no known uses. In looking at all of the data, a few thoughts can be clearly seen:

(76) Although ODS (R-22) was phased out on the schedule shown in FIG. 10, R-22 is still the largest reclaimed product in the U.S. and based on history, will take many years to completely phase out. R-22 is a single molecule and much easier to reclaim with single plate distillation than complex HFCs.

(77) As shown in FIG. 9A, in 2020, 2.4 MM pounds of R.sub.410A of the total sold into the market were reclaimed.

(78) The most difficult stream that exists is the category of “mixed” refrigerant that as the EPA explains is a combination of ODS (R-22) and various HFC streams that cannot be reprocessed and represents nearly 1 million pounds per year, but it is being stockpiled because of complexity.

(79) From a mass balance perspective, it is clear from all data presented that reclamation of refrigerants is severely lacking with the majority of refrigerants vented back into the atmosphere and contributing to global warming.

(80) The manufacturers of next-generation HFC/HFO blends do not participate in reclaim and focus on selling virgin materials back into the market at lower GWP without lifecycle management of the refrigerants that have already been sold.

MANUFACTURE AND USE

(81) The refrigerant composition of the present disclosure can be used as an original OEM refrigerant or as a drop-in replacement for equipment using R-32.

(82) FIG. 12 is a schematic diagram of a distillation apparatus configured to produce an R-32:R-125 mixture that can be utilized as a 0 net GWP replacement for R-32.

(83) In FIG. 12, a reclaimed refrigerant mixture is injected into the center of a distillation column 100 equipped with a reflux condenser 110 and a reboiler 120. The column 100 is packed with a material, such as steel Pall rings, configured to provide sufficient theoretical plates. A lighter fraction is distilled off the top of column 100. A heavier fraction is drained from the bottom of column 100. The heavier fraction is stored in storage tank 130 until it can be re-distilled in distillation column 100.

(84) The heavier fraction can alternately be distilled in an optional second column 200 fitted with a reflux condenser 210 and a reboiler 220. This optional second column 220 provides the possibility to distill the refrigerant mixture in either batch or continuous modes. Not shown in FIG. 12 are temperature sensors, pressure sensors, pressure regulators, temperature regulators, mass flow controllers, process control hardware, process control software and other process details known in the art.

(85) There are numerous streams of reclaimed materials that can be fed into the distillation process according to the disclosure. Many of the reclaimed materials are consolidated by contractors reclaimed in gas stations, HVAC shops and other small businesses where minimal or no efforts are made to isolate the different types of refrigerants including HFCs and ODS materials. Some of the more common reclaimed streams are set forth in Table 5.

(86) TABLE-US-00005 TABLE 5 Reclaimed Mixed Materials. Feed Zero Feed 1 Feed 2 Feed 3 Feed 4 Components (wt %) (wt %) (wt %) (wt %) (wt %) R-134A 15.5 1.20 2.50 7.50 11.0 R-125 12.5 5.00 5.00 11.00 21.5 R-32 12.5 5.00 5.00 11.0 21.5 R-143A 6.50 1.30 0.00 5.50 13.0 R-22 50.0 87.5 87.5 65.0 33.0 HC 3.00 0.00 0.00 0.00 0.00 Total 100 100 100 100 100

(87) The following observations can be made regarding the reclaimed mixed materials set forth in Table 5: R-22 is the most common ODS (ozone depleting substance) because many replacement HFC products have been improperly put into systems “topping off” with HFC blends. Feed zero represents the most likely and worst-case scenario for much of the mixed refrigerant in the U.S. market with high content of R.sub.143a that has a boiling point very similar to R-22 and is difficult to manage in the fractionation process. Highly flammable substances like butane, Isobutane and propane have been used as lubricants in a variety of refrigerant applications to replace R-22. Dealing with class 3 flammables is critical. Mixed materials in many cases contain R-143A (from R-404A) that is mixed at the contractor level, making fractionation very difficult and requiring unique technical solutions in fractionation and forcing the high purity R-32:R-125 mix in order to extract the components.

(88) The distillation column(s) of the disclosure have been designed using ASPEN models and then verified by Koch-Glitsch. ASPEN is a process simulation software package used in industry. Given a process design and an appropriate selection of thermodynamic models, ASPEN uses mathematical models to predict the performance of the process. The process of the disclosure can make the 91:9 material directly off of a single first pass, utilizing waste streams of material that would otherwise be vented, and are being stored around the country or ultimately require CO.sub.2 to burn in a rotary kiln.

Example 1—Feed Zero

(89) Feed Zero is fed into the center of the distillation column at a temperature about 140-150° F. and a pressure of about 400-420 psia. The top fraction is taken off at a temperature of about 95-105° F. and about 370-380 psia. The bottom fraction is taken off at a temperature of about 140-150° F. and a pressure of about 375-385 psia. The composition of the top and bottom fractions is shown in Table 6.

(90) TABLE-US-00006 TABLE 6 Top and bottom fractions of Feed-0 Case (wt %). Top Fraction Bottom Fraction Component (%) (%) R-32 0.913 0.0695 R-125 0.085 0.128 R-143 0.00264 0.0693 R-22 4.93 × 10.sup.−5  0.535 R-134 6.23 × 10.sup.−9  0.166 Oils 2.11 × 10.sup.−15 0.0321 Water 1.95 × 10.sup.−25 5.32 × 10.sup.−5

(91) With the system of the disclosure, and considering high volumes of R-143a in the feedstock, a final product of about 91% R-32, about 9% R-125 that has zero moisture can be packaged and sold directly into new equipment as a net zero GWP replacement for R-32. Likewise, the technology can handle nearly all legacy mixed streams and using the 91:9 formula, which is a direct drop-in for R-32, can move nearly all past refrigerants into new equipment. Table 6 showing the 91:9 formulation is highlighted from the top of the column and achieves>99.5% purity, with no moisture content. The bottom fraction can be subjected to further distillation steps to obtain nearly pure R-22 that can be used in R-22 compatible equipment with a net GWP of zero.

Example 2.—Feed 1

(92) Feed 1 is fed into the center of the distillation column at a temperature of about 145-155° F. and a pressure of about 400-420 psia. The top fraction is taken off at a temperature of about 95-105° F. and about 370-380 psia. The bottom fraction is taken off at a temperature of about 140-150° F. and a pressure of about 375-385 psia. The composition of the top and bottom fractions is shown in Table 7.

(93) TABLE-US-00007 TABLE 7 Top and bottom fractions of Feed-1 Case (wt %). Top Fraction Bottom Fraction Component (%) (%) R-32 0.653 0.000392 R-125 0.336 0.0265 R-143 0.00726 0.0135 R-22 0.00375 0.947 R-134  2.30 × 10.sup.−8  0.0130 Oils 0 0 Water 9.029 × 10.sup.−21 5.41 × 10.sup.−6

(94) In this case, the top fraction yields a ratio of about 6:3 R-32:R-125, which is not suitable as a direct replacement for R-32. Further distillation steps can further isolate components, including an 0.9998 fraction of R-22 that can be used in R-22 compatible equipment with a net GWP of zero.

Example 3.—Feed 2

(95) Feed 2 is fed into the center of the distillation column at a temperature of about 145-155° F. and a pressure of about 400-420 psia. The top fraction is taken off at a temperature of about 95-105° F. and about 370-380 psia. The bottom fraction is taken off at a temperature of about 140-150° F. and a pressure of about 375-385 psia. The composition of the top and bottom fractions is shown in Table 8.

(96) TABLE-US-00008 TABLE 8 Top and bottom fractions of Feed-2 Case (wt %). Top Fraction Bottom Fraction Component (%) (%) R-32 0.654 0.000385 R-125 0.343 0.0259 R-143 0 0 R-22 0.00335 0.947 R-134 4.15 × 10.sup.−8  0.0271 Oils 0 0 Water 6.71 × 10.sup.−21 5.41 × 10.sup.−6

(97) In this case, the top fraction yields a ratio of about 7:3 R-32:R-125, which is not suitable as a direct replacement for R-32. Further distillation steps can further isolate components, including purified fractions of R-22 and R-134A.

Example 4.—Feed 3

(98) Feed 3 is fed into the center of the distillation column at a temperature about 140-150° F. and a pressure of about 400-420 psia. The top fraction is taken off at a temperature of 95-105° F. and about 370-380 psia. The bottom fraction is taken off at a temperature of about 135-145° F. and a pressure of about 375-385 psia. The composition of the top and bottom fractions is shown in Table 9.

(99) TABLE-US-00009 TABLE 9 Top and bottom fractions of Feed-3 Case (wt %). Top Fraction Bottom Fraction Component (%) (%) R-32 0.910 0.0540 R-125 0.087 0.1116 R-143 0.00248 0.0587 R-22 6.95 × 10.sup.−5  0.695 R-134 3.26 × 10.sup.−9  0.0802 Oils 0 0 Water 2.28 × 10.sup.−25 5.35 × 10.sup.−5

(100) With the system of the disclosure, a final product of about 91% R-32, about 9% R-125 that has zero moisture and can be packaged and sold directly into new equipment as a replacement for R-32. Table 9 showing the 91:9 formulation is highlighted from the top of the column and achieves>99.5% purity, with no moisture content. The bottom fraction can be subjected to further distillation steps to obtain nearly pure R-22 and R-134 that can be used in R-22 and R-134 compatible equipment with a net GWP of zero.

Example 5—Feed 4

(101) Feed 4 is fed into the center of the distillation column at a temperature of about 130-140° F. and a pressure of about 400-420 psia. The top fraction is taken off at a temperature of about 95-105° F. and about 370-380 psia. The bottom fraction is taken off at a temperature of about 140-150° F. and a pressure of about 375-385 psia. The composition of the top and bottom fractions is shown in Table 10.

(102) TABLE-US-00010 TABLE 10 Top and bottom fractions of Feed-4 Case (wt %). Top Fraction Bottom Fraction Component (%) (%) R-32 0.498 0.000226 R-125 0.422 0.0575 R-143 0.0761 0.171 R-22 0.00381 0.578 R-134 4.28 × 10.sup.−7  0.194 Oils 0 0 Water 1.32 × 10.sup.−18 8.80 × 10.sup.−6

(103) In this case, the top fraction yields a ratio of about 5:4 R-32:R-125, which is not suitable as a direct replacement for R-32. Further distillation steps can further isolate components, including purified fractions of R-22 and R-134A.

(104) The 91:9 R-32:R-125 material is suitable as a drop-in replacement for R-32. Additional materials can be added to the 91:9 mixture, including but not restricted to lubricants, UV dyes and sealants as discussed above.

(105) In practice, charging the air conditioner or refrigerator with the R-32 replacement is performed using a charging cylinder designed to meter out a desired amount of a specific refrigerant by weight. Compensation for temperature variations is accomplished by reading the pressure on the gauge of the cylinder and dialing, using a calibrated chart, to the corresponding pressure reading for the refrigerant being used. When charging a refrigeration or air conditioning system with refrigerant, often the pressure in the system reaches a point where it is equal to the pressure in the charging cylinder from which the system is being charged. In order to get more refrigerant into the system to complete the charge, heat must be applied to the cylinder. In an exemplary embodiment, a standard 25 or 30 lb cylinder can be used, which is charged under pressure with the refrigerant composition of the current disclosure. This cylinder is fitted with an outlet compatible with R-32. The outlet is connected to a recharging manifold of the apparatus to be charged.

(106) Accordingly, the disclosure has shown that a drop-in replacement for R-32 unexpectedly produces a dramatic drop in net GWP to zero while not sacrificing performance in air conditioning or refrigeration systems. Every pound of the 91:9 R-32:R-125 material used as a replacement for R-32 represents a pound of R-32 that is not manufactured, thus eliminating the 675 GWP associated with newly manufactured R-32. The result is to reduce or prevent anthropogenic further emissions of greenhouse gases, in the framework of the Kyoto Protocol and the Paris Agreement. The technology of the disclosure will thus assist in the decarbonization of the atmosphere.

(107) Throughout the specification and the embodiments, the following terms take at least the meanings explicitly associated herein, unless the context clearly dictates otherwise. Relational terms such as “first” and “second,” and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The term “or” is intended to mean an inclusive “or” unless specified otherwise or clear from the context to be directed to an exclusive form. Further, the terms “a,” “an,” and “the” are intended to mean one or more unless specified otherwise or clear from the context to be directed to a singular form. The term “include” and its various forms are intended to mean including but not limited to. References to “one embodiment,” “an embodiment,” “example embodiment,” “various embodiments,” and other like terms indicate that the embodiments of the disclosed technology so described may include a particular function, feature, structure, or characteristic, but not every embodiment necessarily includes the particular function, feature, structure, or characteristic. Further, repeated use of the phrase “in one embodiment” does not necessarily refer to the same embodiment, although it may. The terms “substantially,” “essentially,” “approximately,” “about” or any other version thereof, are defined as being close to as understood by one of ordinary skill in the art, and in one non-limiting embodiment the term is defined to be within 10%, in another embodiment within 5%, in another embodiment within 1% and in another embodiment within 0.5%. A device or structure that is “configured” in a certain way is configured in at least that way, but may also be configured in ways that are not listed.