Process and methods for reclaiming flammable and non-flammable hydrofluoroolefin-containing refrigerants

Abstract

To provide a method and apparatus for reclaiming a refrigerant.SOLUTION: The method includes: transferring, an unreclaimed refrigerant composition, including one or more hydrofluoroolefins, from a source vessel to a receiving vessel; and transporting the receiving vessel to a recycling center. The unreclaimed refrigerant composition is analyzed to determine the composition of the unreclaimed refrigerant composition sample. A target composition is determined, based on the analyzed unreclaimed refrigerant composition, and one or more treatments are determined, based on the target composition. The unreclaimed refrigerant composition is treated, with the one or more treatments, to form a reclaimed refrigerant composition having the same composition as the target composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Patent Application No. 62 / 815,490, filed March 8, 2019, and U.S. Patent Application No. 62 / 952,667, filed December 23, 2019. The disclosures of U.S. Patent Application No. 62 / 815,490 and U.S. Patent Application No. 62 / 952,667 are incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to the recovery and reclamation of high value, low global warming potential refrigerants, including refrigerants that have some level of flammability. [Background technology]

[0003] Hydrofluoroolefins (HFOs) have been proposed as alternatives to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), which may damage the Earth's ozone layer and / or contribute to global warming. Hydrofluoroolefins do not contain chlorine and therefore do not deplete the Earth's ozone layer.

[0004] Hydrofluoroolefins (HFOs), such as HFO-1234yf, (2,3,3,3-tetrafluoropropene), which exhibit a Global Warming Potential (GWP) of less than 1, are replacing older, less environmentally friendly refrigerants. The olefin portion of the hydrofluoroolefin molecule can be reactive to substances encountered during use. Typically, HFO reactivity is encountered during misuse, such as extreme use conditions (i.e., conditions outside the normal operating conditions of the refrigerant and / or refrigerant blend), blending with incompatible products, introduction of counterfeit materials, or inadvertent contamination. Thus, the reactivity of the HFO portion of such refrigerants or refrigerant blends can cause decomposition in such a way as to produce undesirable by-products. The formation of such by-products introduces materials into the refrigerant composition that can reduce the desired or intended performance of the refrigerant. One source of impurities can be the result of side reactions acting on one or more of the refrigerants in the system. Side reactions can result from a variety of processes, including, for example, pyrolysis, polymerization, oxidation, or hydration. Side reactions can occur between materials in the system or as a result of external materials such as air or water entering the system. The resulting impurities can include, for example, alcohols, aldehydes, ketones, oligomers, or polymers resulting from the reaction of one or more refrigerants. Another source of impurities can result from side reactions acting on other materials present in the system, such as lubricants. These can include, for example, polyol esters, polyvinyl ethers, polyxylylene glycols, mineral oils, or alkylbenzene oils. In one embodiment, polyol ester lubricants can hydrolyze to the corresponding acids. The resulting impurities can exist as solids, liquids, or gases. In addition, materials such as thread locks can also produce undesirable by-products. Other sources of undesirable contaminants can include plasticizers from hoses, gaskets, and O-rings. Currently, refrigerants are considered degraded because they have unknown impurities in them that cannot be conveniently removed during recovery or recycling processes. Conventionally, the depleted refrigerant is discarded (destroyed) and the system is recharged with fresh, ie, new or unused, refrigerant or refrigerant blend.Such conventional methods result in unnecessary loss of valuable refrigerants or refrigerant blends. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent Application No. 62 / 815490 [Patent Document 2] U.S. Patent Application No. 62 / 952667 Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a need for methods to recycle and regenerate depleted refrigerant compositions for further use in existing systems or for reuse in entirely new systems. It would also be desirable to improve depleted refrigerants or refrigerant blends, remove contaminants, and re-blend neat or existing blends with other materials to form new blends or even blends with improved performance. [Means for solving the problem]

[0007] The present invention overcomes the problems of the prior art by providing compositions, equipment and methods for recycling and regenerating refrigerant-containing compositions.

[0008] definition Refrigerant recovery refers to the removal of a refrigerant from the facility that contains it to a separate vessel without remediating the refrigerant.

[0009] Refrigerant recycling means removing any contaminants using procedures or processes that reduce oil, water, acidity, and particulates. Refrigerants treated during recycling are not tested by analytical procedures such as GC-FID, GC-TCD, or GC MS. Recycled refrigerants, while somewhat improved, do not meet American Heating, Refrigeration, and Air-Conditioning Industry (AHRI) Standard 700. AHRI 700 (2017): Refrigerant standard indicates appropriate contaminant levels (purity requirements) for fluorocarbon, hydrocarbon, and carbon dioxide refrigerants, regardless of source, and lists acceptable test methods.

[0010] Refrigerant regeneration refers to the removal of oil, water, acidity, particulates, residues, and other impurities that can adversely affect the quality and therefore performance of the refrigerant. Regeneration involves reprocessing used (or recovered) refrigerants so that the reprocessed refrigerants meet AHRI 700 quality standards. Refrigerant quality is verified by analytical techniques such as GC-FID, GC-TCD, GC-MS, FTIR, Goetz Bub, Karl Fischer, Byk-Garner Color, and various other analytical methods.

[0011] In one embodiment, a method of regenerating a refrigerant includes transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source vessel (or facility) to a receiving vessel and transporting the receiving vessel to a recycling center. The unregenerated refrigerant composition is analyzed to determine a composition of the unregenerated refrigerant composition sample. A target composition is determined based on the analyzed unregenerated refrigerant composition, and one or more treatments are determined based on the target composition. The unregenerated refrigerant composition is treated with one or more treatments to form a regenerated refrigerant composition comprising the target composition.

[0012] In one embodiment, an apparatus for treating a flammable refrigerant composition includes a treatment unit having one or more treatment modules configured to treat a flammable refrigerant composition, the flammable refrigerant composition including hydrofluoroolefins, the treatment unit including one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, a caustic scrubbing module, or a decanting module.

[0013] In one embodiment, a method for recycling refrigerant includes receiving an analysis of an unregenerated refrigerant composition from a customer and determining a target composition based on the analysis. Based on the target composition, one or more treatments are determined. A mobile treatment unit is dispatched, the mobile treatment unit including one or more treatment modules configured to perform the one or more treatments. The mobile treatment unit processes the unregenerated refrigerant composition to form a regenerated refrigerant composition including the target composition. In some embodiments, the target composition includes at least one of 2,3,3,3-tetrafluoropropene (HFO-1234yf) or trans-1,3,3,3-tetrafluoro-1-propene (HFO-1234ze(E)), trans-1-chloro-3,3,3-trifluoropropene, trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane.

[0014] The renewable hydrofluoroolefins may include at least one of the following hydrofluoroolefin refrigerants: 1,2,3,3,3-Pentafluoro-1-propene (CHF=CFCF3), 1,1,3,3,3-Pentafluoro-1-propene (CF2=CHCF3), 1,1,2,3,3-Pentafluoro-1-propene (CF2=CFCHF2), 1,2,3,3-Tetrafluoro-1-propene (CHF=CFCHF2), 2,3,3,3-Tetrafluoro-1-propene (CH2=CFCF3), 1,3,3,3-Tetrafluoro-1-propene (CHF=CHCF3), 1,1,2,3-tetrafluoro-1-propene (CF2=CFCH2F), 1,1,3,3-Tetrafluoro-1-propene (CF2=CHCHF2), 1,2,3,3-Tetrafluoro-1-propene (CHF=CFCHF2), 3,3,3-trifluoro-1-propene (CH2=CHCF3), 2,3,3-Trifluoro-1-propene (CHF2CF=CH2); 1,1,2-Trifluoro-1-propene (CH3CF=CF2); 1,2,3-Trifluoro-1-propene (CH2FCF=CF2); 1,1,3-Trifluoro-1-propene (CH2FCH=CF2); 1,3,3-Trifluoro-1-propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4-Octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-Octafluoro-1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-Heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-Heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-Heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-Tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C=CHF);1,1,3,3,4,4,4-Heptafluoro-1-butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-Heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4-Heptafluoro-1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-Hexafluoro-1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-Hexafluoro-1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4-Hexafluoro-1-butene (CHF=CFCHFCF3); 1,2,3,3,4,4-Hexafluoro-1-butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-Hexafluoro-2-butene (CHF2CF=CFCHF2); 1,1,1,2,3,4-Hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-Hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-Hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-Hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4-Hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-Trifluoro-2-(trifluoromethyl)-1-propene (CH2=C(CF3)2); 1,1,1,2,4-Pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4-Pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4-Pentafluoro-1-butene (CF3CF2CH=CH2); 1,1,1,4,4-Pentafluoro-2-butene (CHF2CH=CHCF3); 1,1,1,2,3-Pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4-Pentafluoro-1-butene (CH2=CFCF2CHF2); 1,1,2,4,4-Pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3-Pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-Pentafluoro-2-butene (CH2FCF=CFCHF2); 1,1,3,3,3-Pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(Difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3)), 2,3,4,4,4-pentafluoro-1-butene (CH2=CFCHFCF3); 1,2,4,4,4-Pentafluoro-1-butene (CHF=CFCH2CF3); 1,3,4,4,4-Pentafluoro-1-butene (CHF=CHCHFCF3); 1,3,3,4,4-Pentafluoro-1-butene (CHF=CHCF2CHF2); 1,2,3,4,4-Pentafluoro-1-butene (CHF=CFCHFCHF2); 3,3,4,4-Tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-Difluoro-2-(difluoromethyl)-1-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF=C(CF3)(CH3)); 3,3-Difluoro-2-(difluoromethyl)-1-propene (CH2=C(CHF2)2); 1,1,1,2-Tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3-Tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5-Decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-Decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-Hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-Nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-Nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-Nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-Nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-Nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-Nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-Hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-Hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3)2); 1,1,1,4,4,4-Hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-Hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-Octafluoro-1-pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-Octafluoro-1-pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-Pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCH(CF3)2); 1,3,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF3)2); 1,1,4,4,4-Pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-Tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-Heptafluoro-1-pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-Heptafluoro-1-pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-Heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-Heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-Tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-Tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF3)2); 1,1,1,4-Tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-Tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-Hexafluoro-2-pentene (CF3CF2CF=CHCH3); 1,1,1,4,4,4-Hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3); 3,3,4,5,5,5-Hexafluoro-1-pentene (CH2=CHCF2CHFCF3); 4,4,4-Trifluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6-Dodecafluoro-1-hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-Dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-Octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-Octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-Hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-Hexafluoro-4-(trifluoromethyl)-1-pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-Nonafluoro-3-methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-Hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6-Octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-Octafluoro-1-hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-Pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-Pentafluoro-2-(trifluoromethyl)-1-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5-Heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6-Heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-Heptafluoro-1-hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-Heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-Tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-Heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-Tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-Tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-Tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-Tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-Tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5); Pentafluoroethyl trifluorovinyl ether (CF2=CFOCF2CF3); Trifluoromethyl trifluorovinyl ether (CF2=CFOCF3) and combinations thereof.

[0015] One embodiment of the present invention relates to a method for regenerating a refrigerant containing any combination of the aforementioned hydrofluoroolefins, the method comprising: transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source vessel (or facility) to a treatment vessel; transporting the receiving container to a processing center; performing an analysis on the unregenerated refrigerant composition selected from the group consisting of gas chromatography, mass spectrometry, atomic absorption spectrometry, flame emission spectrometry, infrared spectrometry, and combinations thereof to determine the composition of the unregenerated refrigerant composition sample; determining a target composition based on the analyzed unregenerated refrigerant composition; determining one or more treatments based on the target composition; performing at least one process selected from the group consisting of transferring, blending, distilling, nitrogen purging, filtering, dehydrating, caustic scrubbing, decanting, and combinations thereof to form a partially regenerated or regenerated refrigerant composition; Includes.

[0016] In one embodiment of the present invention, the composition is a regenerated refrigerant composition, Any combination of the preceding embodiments, wherein the regenerated refrigerant composition is equal to the target composition.

[0017] Another embodiment of the present invention comprises: adding an additive to the regenerated refrigerant composition; The additive is present in a concentration of less than 0.4% by weight based on the regenerated refrigerant composition. Any combination of the preceding embodiments.

[0018] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the target composition comprises at least one primary component and at least one secondary component.

[0019] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the secondary component comprises a non-condensable material at a concentration greater than 1.5% by volume at 25° C. according to AHRI 700.

[0020] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the non-condensable material comprises a fluorinated oligomer.

[0021] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the non-condensable material comprises an oxidized polyol ester.

[0022] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein at least one treatment increases the concentration ratio of at least one primary component to at least one secondary component based on the total weight of the unregenerated refrigerant composition.

[0023] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the processing includes transferring unregenerated refrigerant from a receiving vessel to a processing vessel.

[0024] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the processing includes blending and transferring unregenerated refrigerant from a receiving vessel to a processing vessel.

[0025] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the unregenerated refrigerant composition comprises at least one of 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoro-1-propene, trans-1-chloro-3,3,3-trifluoropropene, trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane.

[0026] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the unregenerated refrigerant composition comprises 2,3,3,3-tetrafluoropropene and at least one of trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane.

[0027] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the unregenerated refrigerant composition comprises oil.

[0028] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the oil comprises a polyol ester, a polyalkylene glycol, or a polyvinyl ether.

[0029] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the one or more processes include transferring, blending, filtering, and combinations thereof.

[0030] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the unregenerated refrigerant composition comprises at least two immiscible compounds.

[0031] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the treatment comprises decanting.

[0032] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the purity of the regenerated refrigerant composition is greater than 99.5 wt.%, based on the total weight of the refrigerant composition.

[0033] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the one or more processes comprises at least two processes.

[0034] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the first treatment increases the concentration ratio of at least one primary component to at least one secondary component based on the total weight of the unregenerated refrigerant composition.

[0035] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the partially regenerated refrigerant composition is treated in at least one second treatment to form a regenerated refrigerant composition.

[0036] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the at least one second treatment increases a concentration ratio of the at least one primary component to the at least one secondary component based on a total weight of the partially regenerated refrigerant composition.

[0037] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the second treatment comprises filtration through a 0.1 micron or smaller screen.

[0038] Another embodiment of the present invention is a refrigerant composition comprising a refrigerant mixture comprising: a) a refrigerant composition having an oil concentration of at least 0.5 wt. %, based on the total weight of the unregenerated refrigerant composition; and b) a refrigerant composition having an oil concentration of at least 0.5 wt. %, based on the total weight of the unregenerated refrigerant composition. The oil concentration is reduced to less than 0.5 wt. %, based on the total weight of the partially regenerated refrigerant composition. Any combination of the preceding embodiments.

[0039] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the second treatment comprises dehydration.

[0040] Another embodiment of the present invention is to contact the unregenerated refrigerant composition with a desiccant, the water concentration of the unregenerated refrigerant composition is reduced by at least 0.5 wt. %, based on the total weight of the unregenerated refrigerant composition; The water concentration is reduced to less than 0.5 wt. %, based on the total weight of the partially regenerated refrigerant composition. Any combination of the preceding embodiments.

[0041] One embodiment of the present invention relates to a partially regenerated refrigerant composition formed by any combination of the aforementioned methods.

[0042] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the first processing comprises transferring or blending.

[0043] One embodiment of the present disclosure is an apparatus for treating a flammable refrigerant composition, comprising: a treatment unit having one or more treatment modules configured to treat a flammable refrigerant composition; the flammable refrigerant composition comprises a hydrofluoroolefin; The processing unit includes one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dewatering module, a caustic scrub module, or a decant module; Regarding the device.

[0044] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the hydrofluoroolefin comprises 2,3,3,3-tetrafluoropropene.

[0045] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein one or more of the processing modules are electrically grounded.

[0046] One embodiment of the present invention is a method for regenerating a refrigerant, comprising the steps of: receiving an analysis of the unregenerated refrigerant composition from a customer; determining a target composition based on the analysis results; determining one or more treatments based on the target composition; dispatching a mobile processing unit including one or more processing modules configured to perform one or more processes; processing the unregenerated refrigerant composition with a mobile processing unit to form a regenerated refrigerant composition comprising a target composition; Including, the target composition comprises at least one of 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoro-1-propene, trans-1-chloro-3,3,3-trifluoropropene, trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane; It concerns the method.

[0047] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the one or more processing modules include one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dewatering module, a caustic scrub module, or a decant module.

[0048] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein one or more of the processing modules are electrically grounded.

[0049] Another embodiment of the present invention relates to any combination of the preceding embodiments, wherein the target composition is at least 99.5% pure.

[0050] The embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. [Brief description of the drawings]

[0051] [Figure 1] FIG. 1 is a schematic diagram of a refrigerant regeneration system according to one embodiment. [Diagram 2] FIG. 1 is a block diagram of a method for regenerating refrigerant, according to one embodiment. [Diagram 3] FIG. 1 is a block diagram of a method for regenerating refrigerant, according to one embodiment. [Figure 4] FIG. 1 is a front view of a vertical ton tank according to one embodiment. [Diagram 5] FIG. 1 is a side view of a vertical ton tank according to one embodiment. [Figure 6] FIG. 2 is an enlarged side view of the internal piping of a vertical ton tank according to one embodiment. [Figure 7] 1 illustrates a piping joint for a vertical ton tank according to one embodiment. [Figure 8] FIG. 2 is a bottom view of a vertical ton tank according to one embodiment. [Figure 9] FIG. 13 is an enlarged top view of a valve configuration for a vertical ton tank, according to one embodiment. [Figure 10] FIG. 13 is an enlarged side view of a valve arrangement for a vertical ton tank, according to one embodiment. [Figure 11] FIG. 1 illustrates a vertical ton tank with a bottom protective collar, according to one embodiment. [Figure 12] 1 illustrates a door as part of a bottom protective collar for a vertical ton tank, according to one embodiment.

[0052] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same parts. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0053] Methods are provided for recovering, recycling, and regenerating depleted or used refrigerants. Embodiments of the present disclosure include, for example, recovering a refrigerant composition from a site of use, testing the refrigerant composition to determine impurities, altering a property of the refrigerant composition beyond a predetermined threshold, and transporting the refrigerant composition to the site of use.

[0054] A refrigerant regeneration system 100 is depicted in FIG. 1. In the example of FIG. 1, a source tank 110 containing an unregenerated refrigerant composition 115 is communicatively connected to a receiving tank 120 and configured to allow some or all of the unregenerated refrigerant composition 115 to be transferred to the receiving tank 120. One or more samples of the unregenerated refrigerant composition 115 may be collected from the source tank 110 or the receiving tank 120 or a combination thereof. The samples may be analyzed to determine the level of one or more components in the unregenerated refrigerant composition 115. The level of one or more components may cause the unregenerated refrigerant composition 115 to be outside of a desired composition specification. In some embodiments, the unregenerated refrigerant composition 115 may be a non-azeotropic composition. In other embodiments, the unregenerated refrigerant composition 115 may be an azeotropic composition.

[0055] In some embodiments, the unregenerated refrigerant composition 115 may include components resulting from the polymerization or decomposition of one or more hydrofluoroolefin refrigerants. In some embodiments, the components may include polymers, oligomers, phthalates, adipates, fluorinated hydrocarbons, or other reaction products. In one embodiment, the unregenerated refrigerant composition may include homopolymers resulting from the polymerization of one or more refrigerant components of the unregenerated refrigerant composition 115. In some embodiments, the unregenerated refrigerant composition 115 may include acid components that may reduce the cycle performance of the unregenerated refrigerant composition 115. In some embodiments, the unregenerated refrigerant composition 115 may include chlorine-containing or oxidized species that may be harmful to refrigeration system components such as hoses, gaskets, or fittings. In some embodiments, the unregenerated refrigerant composition 115 may include other components such as water, oil (e.g., mineral oil or polyol ester), or dyes.

[0056] The presence and concentration of various components of the unregenerated refrigerant composition 115 may be analyzed using various analytical techniques including gas chromatography, mass spectrometry, infrared spectroscopy, moisture levels, acid levels, non-condensable levels, high boiling point residues, and / or color measurements. If the levels of one or more components are outside of one or more predetermined threshold ranges for those components, a treatment plan (or procedure) for the unregenerated refrigerant composition 115 is determined.

[0057] The treatment plan includes steps to change the composition of the unregenerated refrigerant composition 115 to match the target composition. The treatment plan may include one or more treatments of the unregenerated refrigerant composition 115. In some embodiments, the target composition is a regenerated refrigerant composition that meets composition specifications and is suitable for use in a refrigeration system. In some embodiments, the target composition includes at least one of 2,3,3,3-tetrafluoropropene (HFO-1234yf) or trans-1,3,3,3-tetrafluoro-1-propene (HFO-1234ze(E)). In some embodiments, the target composition includes 2,3,3,3-tetrafluoropropene (HFO-1234yf) or trans-1,3,3,3-tetrafluoro-1-propene (HFO-1234ze(E)) in an amount of at least 99.5% or more of the refrigerant composition.

[0058] In some embodiments, one or more of the refrigerants of the unregenerated refrigerant composition 115 may be a flammable refrigerant, where flammable means a gas having a concentration in the flammable range in air at 60° C. and a pressure of 101.3 kilopascals, according to ASTM E-681-09, “Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases).”

[0059] Vertical Ton Tank (VTT) In one embodiment, an aspect of the process is the use of a convenient container that allows for easy recovery, recycling, and reclamation of the used refrigerant. In the exemplary embodiment described herein, the container is a 500L-1000L, or more specifically 750L-950L, or more specifically 850L-950L, vertical cylinder designed to hold, transport, or convey flammable compositions during recovery, recycling, and reclamation, and is vertically oriented to help facilitate the processing of the used refrigerant. It is noted that any vertical cylinder designed for flammable refrigerants may be conveniently used for non-flammable refrigerants. The vertical ton tank (VTT) of the present invention has certain design parameters that are uniquely useful in combination with other reclamation processes described above in combinations described below. One or more vertical ton tanks, including the source tank 110 and / or the receiving tank 120, may be used in the refrigeration distribution system 100 in various roles.

[0060] Orientation The VTT cylinder is designed with a vertical pressure vessel orientation, meaning that the cylinder is upright (vertical) during use, transport and storage. This particular orientation helps to reduce the physical footprint at the anticipated collection site, as the footprint (m2) near the recovery / recycle / refill (R / R / R) operation may be limited. In addition, the vertical design is advantageous for the actual transportation of the vertical ton tank. The vertical ton tank can be conveniently loaded onto a forklift without gravity losses and misalignment as occurs with horizontal ton tanks. The design of the base of the vertical ton tank is also designed to improve product transportation. In one design option, the bottom of the vertical ton tank has an integral pallet with openings for the tines of the forklift. Thus, the VTT of the present disclosure can be safely and conveniently used to physically move flammable refrigerants to remote collection and processing sites.

[0061] Pressure, flammability and volume follow the appropriate design code depending on the refrigerant used in the R / R / R process. In the US for example, vertical ton tanks follow ASME design, construction and pressure standards, while in the EU, vertical ton tanks follow ADR and in Japan, vertical ton tanks follow HPGL.

[0062] Dip tube orientation Another embodiment of an improved VTT is the dip tube placement and orientation. While the dip tube is fundamental to the cylinder design, the dip tube placement in combination with the flanges and the orientation of the dip tube relative to the top and bottom flanges, as described in the next section, provides a unique product transport to the R / R / R of the spent refrigerant. Figures 4 and 5 show front and side views of an embodiment of a vertical ton tank (VTT) with a dip tube. Shown are dip tubes 62 and 65 with 1 / 2 inch and 1 inch connections at the top and bottom of the tank. Also shown are the attachments of the dip tubes 62 and 65 to the top flange 60 and bottom flange 61. Note the orientation of the dip tubes 62 and 65 and how they mate with the top and bottom flanges.

[0063] Bottom and Top Flanges Another embodiment of the usefulness of the redesigned VTT is the addition and placement of flanges that also aid in the R / R / R process. While the process refrigerant can be transported from the VTT to another VTT or another storage vessel, it may be desirable to be able to penetrate into the VTT to see what residues remain in the VTT. Therefore, the VTT is designed to include two larger flanges, designated as (top flange 60) and (bottom flange 61). The bottom and top flanges aid in opening the VTT tank for easy inspection by visual inspection or scoping methods such as borescopes. The flanges also aid in easy removal of any debris that may have collected from the spent refrigerant impurities. The flanges are shown in Figures 4 and 5.

[0064] Piping from flange to valve Another embodiment in the redesigned VTT is the placement and design of the piping / connections from the flanges to the valves. As can be seen, the bottom flange has both a larger and smaller drain pipe from the flange. Figure 6 shows the placement and orientation of the drain pipes.

[0065] Figures 7 and 8 are top and side views of the bottom of the (VTT). These figures show the elements in more detail and how they fit together into the main bottom flange. The smaller piping details are shown as elements 83, 84, 85 (smaller flanges) that connect to the 1 / 2 inch pipe 64 and then to the connector. The larger piping details are shown as elements 87, 88 and 89 that connect to the 1 inch pipe 63.

[0066] Parts List

[0067] [Table 1]

[0068] gasket Another design element is the addition of a PTFE gasket as shown in the figure, which prevents further contamination from the gasket. PTFE gaskets have been found to be non-hazardous in HFO type products and therefore should be used in conjunction with this design.

[0069] valve Another unique design element is the addition of a dry bulk coupler (DBC) that limits the amount of refrigerant that may be released during refrigerant transfer. The dry bulk coupler has a specific locking mechanism that stops product transfer until the unlocking mechanism is engaged. The product is transferred after the unlocking mechanism is engaged. This mechanism reduces the release of flammable products to less than 1 gram, which is highly desirable in this VTT design. The DBC also aids in the sustainable transport of refrigerant since less than 1 gram of refrigerant is typically released during coupling and uncoupling of the DBC. The incorporation of the DBC into this process facilitates product transfer, improves safety, and limits unintentional exposure of refrigerant and / or contaminants. These are elements 122, 124, and 125 in the drawing. Element 123 is the metal piping to DBC adapter. The DBC brand is commonly known as Denver Gardner TODO, Econosto valves, and Dixon valves.

[0070] Bottom Color Specially designed VTTs have a bottom collar that latches into place to protect the bottom valve associated with the VTT. The collar protects the product by preventing forklift tines from striking the lower valve and / or flange. Additionally, the bottom collar can be locked with a ziplock to aid in anti-counterfeit detection. An authenticated ziplock lock may indicate that the product may have been tampered with.

[0071] For an illustration of how the collar fits onto the valve, see Figure 9. Figure 10 shows a protective door that can further protect the valve when the tank is not connected to the outside world.

[0072] 1, the unregenerated refrigerant composition 115 may be transferred from the receiving tank 120 to a treatment unit 130. The treatment unit 130 includes one or more treatment modules that act on the unregenerated refrigerant composition 115 to reduce the concentration of one or more unregenerated refrigerant composition 115 components in the unregenerated refrigerant composition 115 below a predetermined threshold. In some embodiments, the unregenerated refrigerant composition 115 may be treated in a first process to form a partially regenerated refrigerant composition.

[0073] In one embodiment, the processing unit 130 includes a blending module 131. The blending module 131 adds compositions to the unregenerated refrigerant composition 115 or the partially regenerated refrigerant composition to modify the concentration of one or more components. The modification may change the concentration of one or more components in the unregenerated refrigerant composition 115 to below one or more predetermined thresholds. In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.5% by weight based on the total weight of the refrigerant composition.

[0074] In one embodiment, the processing unit 130 includes a transfer module 132. The transfer module 132 transfers at least a portion of the unregenerated refrigerant composition 115 or the partially regenerated refrigerant composition to a regeneration tank. The transfer of the refrigerant composition changes the concentration of one or more components of the unregenerated refrigerant composition 115. In some embodiments, the transfer partially fills the regeneration tank.

[0075] In some embodiments, a method for charging a refrigerant mixture including a non-azeotropic (or azeotropic) refrigerant into a regeneration tank includes adjusting the proportion of at least one component of a refrigerant composition in the liquid phase of the refrigerant mixture prior to transfer to a specific range. In some embodiments, the refrigerant composition may be processed by a blending module 131 prior to processing by the transfer module 132.

[0076] Mix ratios are described below for partially regenerated or unregenerated refrigerant composition 115 prior to transfer from a refrigerant composition source to a regeneration vessel that is filled with an amount of refrigerant composition less than 100% by weight of the maximum charge of the refrigerant mixture.

[0077] As used herein, the term "maximum fill" (100% by weight of maximum fill) refers to the maximum amount that can be filled into a container as determined by regulatory agencies such as, for example, the United States Department of Transportation (US DOT), the European Union ADR, the European Agreement on the International Carriage of Dangerous Goods by Road (ADR), and the High Pressure Gas Safety Act of Japan. According to these transportation regulations, the maximum fill is calculated as follows: G=V / C G: Mass of fluorocarbon (kg) V: Volume of the container (L) C: A constant depending on the type of fluorocarbon contained in the container and the temperature or pressure limits defined by regulations.

[0078] When the unregenerated refrigerant composition 115 partially fills the regeneration vessel, a portion of each component vaporizes to fill the remaining space in the regeneration vessel. For non-azeotropic compositions, the relative proportion of low boiling components in the vapor is greater than the proportion of low boiling components in the liquid unregenerated refrigerant composition 115. Thus, the ratio of low to high boiling components of the liquid unregenerated refrigerant composition is altered by transfer.

[0079] In some embodiments, the target composition comprises a non-azeotropic composition. In some embodiments, the target composition comprises at least one primary component. The unregenerated refrigerant composition 115 may comprise at least one secondary component in addition to the at least one primary component. In some embodiments, the at least one primary component is a desired material of the target composition. In some embodiments, the at least one secondary component is an undesirable component of the target composition. In some embodiments, the at least one secondary component may exhibit a lower boiling point than the at least one primary component. During processing by the transfer module 132, the ratio of the at least one primary component to the at least one secondary component may be increased based on the liquid unregenerated refrigerant composition 115.

[0080] In one embodiment, the processing unit 130 includes a decant module 133. The decant module 133 can separate one or more immiscible materials from the partially regenerated or unregenerated refrigerant composition 115. For example, the decant module 133 can separate a plurality of immiscible liquids by discharging and / or flowing one or more of the liquids from the decant module 132. In one embodiment, the liquids separated are impurities and are therefore separated from the unregenerated refrigerant composition 115 remaining in the decant module 133. In one embodiment, the liquids separated may comprise a desired refrigerant composition and thus separate the desired materials from one or more impurities remaining in the decant module 132. Decanting can alter the concentration of one or more components in the unregenerated refrigerant composition 115 below one or more predetermined thresholds. In one embodiment, the ratio of at least one primary component to at least one secondary component can be increased based on the liquid unregenerated refrigerant composition 115. In some embodiments, the concentration of non-condensable materials may be modified to a concentration of less than 1.5% by volume at 25° C. per AHRI 700 (American Heating, Refrigeration and Air-Conditioning Industry Standard, "Fluorocarbon Refrigerants Specification", AHRI 700, September 2016). In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.5% by weight based on the total weight of the refrigerant composition.

[0081] In one embodiment, the processing unit 130 includes a distillation module 133. The distillation module 134 can separate one or more materials from the partially regenerated or unregenerated refrigerant composition 115. For example, the distillation module 134 can separate one or more impurities from the unregenerated refrigerant composition 115 by distilling one or more materials from the distillation module 134. In one embodiment, the separated materials are impurities and are therefore separated from the unregenerated refrigerant composition 115 remaining in the distillation module 134. In one embodiment, the separated materials can include a desired refrigerant composition and therefore separate the desired materials from one or more impurities remaining in the distillation module 134. The distillation can alter the concentration of one or more components in the unregenerated refrigerant composition 115 below one or more predetermined thresholds. In one embodiment, the ratio of at least one primary component to at least one secondary component can be increased based on the liquid unregenerated refrigerant composition 115. In some embodiments, the concentration of the non-condensable materials can be altered to a concentration of less than 1.5% by volume at 25° C. in accordance with AHRI 700. In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.5 wt. %, based on the total weight of the refrigerant composition.

[0082] In one embodiment, the processing unit 130 includes a filtration module 135. The filtration module 135 can separate one or more insoluble particulates from the partially regenerated or unregenerated refrigerant composition 115. For example, the filtration module 135 can separate a plurality of insoluble particles from the unregenerated refrigerant composition 115 by filtration. In some embodiments, the unregenerated refrigerant composition 115 is filtered through at least a 0.01 micrometer screen, at least a 0.03 micrometer screen, at least a 0.05 micrometer screen, at least a 0.08 micrometer screen, at least a 0.1 micrometer screen, or at least a 0.15 micrometer screen. In one embodiment, the unregenerated refrigerant composition 115 is filtered through a 0.1 micrometer screen. The filtration can change the concentration of one or more components in the unregenerated refrigerant composition 115 to below one or more predetermined thresholds. In one embodiment, the ratio of at least one primary component to at least one secondary component can be increased based on the liquid unregenerated refrigerant composition 115. In one embodiment, the concentration of one or more components may be altered to provide an oil concentration of less than 0.5 wt%, preferably less than 0.05 wt%, and even more preferably less than 0.0025 wt%, less than 22 parts per million (ppm) by weight. In one embodiment, the concentration of one or more components may be altered to provide a reduced concentration of dyes. In one embodiment, the color of the unregenerated refrigerant composition 115 is altered to a Gardner color value of less than 3.

[0083] In one embodiment, the treatment unit 130 includes a scrubbing module 136. The scrubbing module 136 can treat the unregenerated refrigerant composition 115 by contacting the unregenerated refrigerant composition 115 with a treatment composition. In some embodiments, the treatment composition can be a caustic / basic scrubber. For example, the scrubbing module 136 can contact the unregenerated refrigerant composition 115 with a caustic solution to remove components containing acid moieties. In one embodiment, the unregenerated refrigerant composition 115 is contacted with an aqueous sodium hydroxide solution using a Venturi scrubber. Scrubbing can alter the concentration of one or more components in the unregenerated refrigerant composition 115 to below one or more predetermined thresholds. In one embodiment, the concentration of one or more components can be altered to provide a total acid number (TAN) of the unregenerated refrigerant composition 115 below 2 milligrams KOH per 2 grams. In one embodiment, the concentration of one or more components can be altered to provide an acidity level of less than 1 ppm by weight as HCl according to AHRI 700. In some embodiments, the resulting scrubbed unregenerated refrigerant composition 115 may be further collected and dried to remove residual water.

[0084] In one embodiment, the processing unit 130 includes a dehydration module 137. The dehydration module 137 may be used to remove water from the unregenerated refrigerant composition 115. For example, the dehydration module 137 may contact the unregenerated refrigerant composition 115 with a desiccant, such as a molecular sieve. The dehydration may reduce the concentration of one or more impurities in the unregenerated refrigerant composition 115 below one or more predetermined thresholds. In one embodiment, the scrubbed unregenerated refrigerant composition 115 may be dehydrated by passing the scrubbed unregenerated refrigerant composition 115 through the dehydration module 137. In some embodiments, the moisture concentration may be modified to achieve a moisture level of less than 20 ppm by weight in accordance with AHRI 700. In one embodiment, the moisture concentration may be modified to achieve a moisture level of less than 10 ppm by weight in accordance with AHRI 700, or less than 5 ppm by weight in accordance with AHRI 700.

[0085] In one embodiment, the processing unit 130 includes an inert gas purge module 138. The inert gas purge module 138 may contact the unregenerated refrigerant composition 115 with an inert gas, such as nitrogen, argon, or xenon, to replace dissolved reactive gases in the unregenerated refrigerant composition 115. In one embodiment, the inert gas may include dry nitrogen. The inert gas purge may modify the concentration of one or more components in the unregenerated refrigerant composition 115 below one or more predetermined thresholds. In one embodiment, the concentration of non-condensable gases (NCG) or non-absorbable gases (NAG) may be modified to a concentration of less than 1.5% by volume at 25° C. per AHRI 700, preferably less than 0.9% by volume at 25° C. per AHRI 700. NAG typically includes air (typically composed of 78% nitrogen, 21% oxygen, and about 1% argon) that accumulates in the gas phase of refrigerants where the solubility of air in the refrigerant liquid phase is very low. While it can be important to reduce the total amount of NAG contained within the refrigerant, it is typically more desirable to preferentially reduce the oxygen-containing portions of the NAG over the nitrogen-containing portions, which may, under certain circumstances, increase the tendency of the refrigerant to decompose or form undesirable polymeric materials.

[0086] In one embodiment, the processing unit 130 includes a non-absorbing gas (NAG) reduction unit 139 .

[0087] The NAG reduction unit 139 may contact the unregenerated refrigerant composition with a reducing agent, such as a metal powder, that may react with oxygen or other oxidizable components of the unregenerated refrigerant composition. In one embodiment, the reducing agent may include iron powder. Treatment with the NAG reduction unit 139 may reduce the concentration of one or more components of the unregenerated refrigerant composition in the unregenerated refrigerant composition below one or more predetermined thresholds. In one embodiment, the concentration of non-condensable materials may be modified to be less than 1.5% by volume at 25° C. per AHRI 700, preferably less than 0.9% by volume at 25° C. per AHRI 700.

[0088] In another embodiment, a condenser is used with a cooling medium cold enough to condense the refrigerant and pass it through the NAG with minimal refrigerant loss. A compressor may be used in conjunction with the condenser to increase the pressure and facilitate condensing the refrigerant at a higher temperature.

[0089] In yet another embodiment, the NAG is separated from the refrigerant by positioning the membrane such that the NAG can pass through and be removed, but the refrigerant cannot.

[0090] The modules of the processing unit 130 can be used alone or in combination. The unregenerated refrigerant composition 115 may be processed one or more times by any of the modules of the processing unit 130. One or more processes by one or more modules of the processing unit 130 may turn the unregenerated refrigerant composition 115 into a regenerated refrigerant composition, in which the concentration of all of the one or more impurities may be reduced below one or more predetermined thresholds. In some embodiments, the regenerated refrigerant composition exhibits impurity levels comparable to virgin material. In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.5% by weight based on the total weight of the refrigerant composition. In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.7% by weight based on the total weight of the refrigerant composition. In some embodiments, the purity of the regenerated refrigerant composition is greater than 99.9% by weight based on the total weight of the refrigerant composition.

[0091] As shown in FIG. 1, the regenerated refrigerant composition may be transferred from the processing unit 130 to a use tank 140. The use tank 140 may contain both regenerated and virgin materials. The use tank 140 may be directly connected to a refrigeration system and configured to supply the refrigerant to the refrigeration system. Alternatively, the use tank 140 may be connected to a distribution tank 150. The use tank 140 may supply the refrigerant to the typically smaller distribution tank 150. The distribution tank 150 may then be transported to a use location and used to supply the refrigerant to a refrigeration system or a customer storage tank. In some embodiments, the purity of the refrigerant composition in the use tank 140 or distribution tank 150 is greater than 99.5% by weight based on the total weight of the refrigerant composition. In some embodiments, the purity of the refrigerant composition in the use tank 140 or distribution tank 150 is greater than 99.7% by weight based on the total weight of the refrigerant composition. In some embodiments, the purity of the refrigerant composition in the use tank 140 or distribution tank 150 is greater than 99.9% by weight based on the total weight of the refrigerant composition.

[0092] In some embodiments, an additive may be added to the regenerated refrigerant composition. In one embodiment, the additive is present at a concentration of less than 0.4% by weight based on the regenerated refrigerant composition. In one embodiment, the additive may include an inhibitor. In one embodiment, the inhibitor may include at least one of limomen, alpha-terpinene, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, or benzene 1,4-diol. In one embodiment, the inhibitor includes a material having a melting point of -70°C to 180°C.

[0093] In some embodiments, the regenerated refrigerant compositions provided herein may include one or more optional lubricants, dyes (including UV dyes), solubilizers, compatibilizers, stabilizers, tracers, antiwear agents, extreme pressure additives, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof. In some embodiments, the optional non-refrigerant compositions may also be referred to as additives. Indeed, many of these optional non-refrigerant components may fit one or more of these categories and may themselves have qualities that aid in achieving one or more performance characteristics.

[0094] In some embodiments, one or more non-refrigerant components are present in a small amount relative to the overall composition. In some embodiments, the amount of concentration of additive(s) in the disclosed compositions is less than about 0.1% by weight to as much as about 5% by weight of the total composition. In some embodiments of the present invention, the additive is present in the disclosed compositions in an amount of about 0.1% to about 5% by weight or about 0.1% to about 3.5% by weight of the total composition. In one embodiment, the additive is present in a concentration of less than 0.4% by weight based on the regenerated refrigerant composition. The additive component(s) selected for the disclosed compositions are selected based on practicality and / or requirements of the individual equipment components or systems.

[0095] In one embodiment, the lubricant is selected from the group consisting of mineral oil, alkylbenzenes, polyol esters, polyalkylene glycols, polyvinyl ethers, polycarbonates, perfluoropolyethers, silicones, silicate esters, phosphate esters, paraffins, naphthenes, polyalpha-olefins, and combinations thereof.

[0096] The lubricant disclosed herein may be a commercially available lubricant. For example, the lubricant may be a paraffinic mineral oil sold by BVA Oil under the trade name BVM 100N, naphthenic mineral oil sold by Crompton Co. under the trade name Suniso® 1GS, Suniso® 3GS, and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkyl benzene sold by Shrieve Chemicals under the trade name Zerol® 75, Zerol® 150, and Zerol® 500, branched alkyl benzene sold by Nippon Oil under the trade name HAB22, polyol ester (POE) sold by Castrol, United Kingdom under the trade name Castrol® 100, Dow (Dow Oil), or similar lubricant. The polymer may also be a polyalkylene glycol (PAG), such as RL-488A from Qualcomm Chemical, Midland, Michigan, and mixtures thereof (meaning any mixtures disclosed in this section).

[0097] In compositions of the present invention that include a lubricant, the lubricant is present in an amount of less than 40.0% by weight of the total composition. In other embodiments, the amount of lubricant is less than 20% by weight of the total composition. In other embodiments, the amount of lubricant is less than 10% by weight of the total composition. In other embodiments, the approximate amount of lubricant is about 0.1% to 5.0% by weight of the total composition.

[0098] Notwithstanding the above weight ratios of the compositions disclosed herein, it is understood that in some heat transfer systems, additional lubricant may be obtained from one or more equipment components of such heat transfer systems while the compositions are in use. For example, in some refrigeration, air conditioning and heat pump systems, lubricant may be filled into the compressor and / or compressor lubrication sump. Such lubricant is present in the refrigerant of such systems in addition to any lubricant additives. During use, when in the compressor, the refrigerant composition may pick up an amount of equipment lubricant, changing the refrigerant-lubricant composition from the starting ratio.

[0099] The non-refrigerant components used with the compositions of the present invention may include at least one dye. The dye may be at least one ultra-violet (UV) dye. The UV dye may be a fluorescent dye. The fluorescent dye may be selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives of the dyes and combinations thereof (meaning any mixture of the dyes or derivatives thereof disclosed in this section).

[0100] In some embodiments, the disclosed compositions contain from about 0.001% to about 1.0% by weight of the UV dye, in other embodiments the UV dye is present in an amount from about 0.005% to about 0.5% by weight, and in other embodiments the UV dye is present in an amount from 0.01% to about 0.25% by weight of the total composition.

[0101] Ultraviolet dyes are useful components in detecting leaks of compositions because the fluorescence of the dye can be observed at or near the point of the leak in an appliance (e.g., a refrigeration unit, air conditioner, or heat pump). The ultraviolet emission (e.g., fluorescence from the dye) may be observed under ultraviolet light. Thus, if a composition containing such an ultraviolet dye leaks from a given point in the device, the fluorescence can be detected at or near the point of the leak.

[0102] Another non-refrigerant component that may be used with the compositions of the present invention may include at least one solubilizing agent selected to improve the solubility of one or more dyes in the compositions of the present disclosure. In some embodiments, the weight ratio of dye to solubilizing agent ranges from about 99:1 to about 1:1. The solubilizing agent may include at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes and mixtures thereof (meaning mixtures of any solubilizing agents disclosed in this section).

[0103] In some embodiments, the non-refrigerant component includes at least one compatibilizer to improve compatibility of one or more lubricants with the disclosed compositions. The compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof (meaning mixtures of any of the compatibilizers disclosed in this section).

[0104] The solubilizer and / or compatibilizer may be selected from the group consisting of hydrocarbon ethers consisting of ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME), and mixtures thereof (meaning any mixture of hydrocarbon ethers disclosed in this section).

[0105] The compatibilizer may be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing 3 to 15 carbon atoms. The compatibilizer may be at least one hydrocarbon selected from the group consisting of at least propane, including propylene and propane, butane, including n-butane and isobutene, pentane, including n-pentane, isopentane, neopentane and cyclopentane, hexane, octane, nonane, and decane, among others. Commercially available hydrocarbon compatibilizers include, but are not limited to, those sold under the trade name Isopar® H by Exxon Chemical (USA), undecane (C 11 ) and dodecane (C 12 ) mixture (high purity C 11 ~C 12 Isoparaffin), Aromatic 150 (C9~C 11 Aromatic 200(C9~C 15 Aromatic) and Naptha 140 (C5-C 11 mixtures of paraffinic, naphthenic and aromatic hydrocarbons) and mixtures thereof, meaning mixtures of any of the hydrocarbons disclosed in this section.

[0106] The compatibilizer may alternatively be at least one polymeric compatibilizer. The polymeric compatibilizer may be a random copolymer of a fluorinated acrylate and a non-fluorinated acrylate, the polymer having the formula CH2=C(R 1 )CO2R 2 , CH2=C(R 3 )C6H4R 4 , and CH2=C(R 5 )C6H4XR 6 (wherein X is oxygen or sulfur; R 1 , R 3 , and R 5 is independently selected from the group consisting of H and C1-C4 alkyl radicals, and R 2 , R 4 , and R 6are independently selected from the group consisting of carbon chain-based radicals containing C and F, which may further contain H, Cl, ether oxygen, or sulfur in the form of thioether, sulfoxide, or sulfone groups and mixtures thereof. Examples of such polymeric compatibilizers include those available commercially under the trade name Zonyl® PHS from EI du Pont de Nemours and Company, Wilmington, DE, 19898, USA. Zonyl® PHS is a mixture of 40% by weight CH2=C(CH3)CO2CH2CH2(CF2CF2)mF (also referred to as Zonyl® fluoromethacrylate or ZFM), where m is 1-12, primarily 2-8, and 60% by weight lauryl methacrylate (CH2=C(CH3)CO2(CH2) 11 It is a random copolymer made by polymerizing CH3 (also called LMA) with

[0107] In some embodiments, the compatibilizer component contains about 0.01 to 30 weight percent (based on the total weight of the compatibilizer) of an additive that reduces the surface energy of metallic copper, aluminum, steel, or other metals and their alloys found in heat exchangers in a manner that reduces the adhesion of the lubricant to the metal. Examples of additives that reduce metal surface energy include those available from DuPont under the trade names Zonyl® FSA, Zonyl® FSP, and Zonyl® FSJ.

[0108] Another optional non-refrigerant component that may be used with the compositions of the present invention may be a metal surface deactivator. The metal surface deactivator may be selected from the group consisting of areoxalyl bis(benzylidene)hydrazide (CAS Registry Number 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS Registry Number 32687-78-8), 2,2,-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CAS Registry Number 70331-94-1), N,N-(disalicyclidene)-1,2-diaminopropane (CAS Registry Number 94-91-7), and ethylenediaminetetra-acetic acid (CAS Registry Number 60-00-4) and its salts, and mixtures thereof (meaning any mixture of metal surface deactivators disclosed in this chapter).

[0109] The optional non-refrigerant components used with the compositions of the present invention may alternatively be stabilizers selected from the group consisting of hindered phenols, thiophosphates, butylated triphenyl phosphorothioates, organophosphates or phosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkyl silanes, benzophenone derivatives, aryl sulfides, divinyl terephthalic acid, diphenyl terephthalic acid, ionic liquids, and mixtures thereof, including mixtures of any of the stabilizers disclosed in this paragraph.

[0110] The stabilizer may be selected from the group consisting of tocopherol; hydroquinone; t-butylhydroquinone; monothiophosphates, and dithiophosphates (available from Ciba Specialty Chemicals, Basel, Switzerland (hereinafter "Ciba") under the trade name Irgalube® 63); dialkylthiophosphates (available from Ciba under the trade names Irgalube® 353 and Irgalube® 350, respectively); butylated triphenyl phosphorothioates (available from Ciba under the trade name Irgalube® 232); amine phosphates (available from Ciba under the trade name Irgalube® 349 (Ciba)). ba); hindered phosphite (commercially available as Irgafos® 168 from Ciba); and tris-(di-tert-butylphenyl) phosphite (commercially available as Irgafos® OPH from Ciba); (di-n-octyl phosphite), and iso-decyl diphenyl phosphite (commercially available as Irgafos® DDPP from Ciba); trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, and trialkyl phosphates, such as tri(2-ethylhexyl) phosphate, and tri(2-ethylhexyl) phosphate; triaryl phosphates, including triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate, and mixed alkylaryl phosphates, including isopropylphenyl phosphate (IPPP) and bis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenyl phosphates, such as those commercially available under the trade name Syn-O-Ad®, such as Syn-O-Ad® 8784; phosphates; tert-butylated triphenyl phosphates, such as those sold under the trade name Durad® 620; isopropyl triphenyl phosphates, such as those sold under the trade names Durad® 220 and Durad® 110; anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; myrcene, alloocimene, limonene (especially d-limonene); retinal; pinene; menthol; geraniol; farnesol;Phytol; Vitamin A; Terpinene; δ-3-carene; Terpinolene; Phellandrene; Fenthen; Dipentene; Caratenoids such as lycopene, xanthophylls such as beta-carotene, and zeaxanthin; Retinoids such as hepaxanthin and isotretinoin; Bornane; 1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether; Trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane; 3-ethyl-3-hydroxymethyl-oxetane (e.g., OXT-101 (Toagosei Co., Ltd.)); 3-ethyl-3-((phenoxy)methyl)-oxetane (e.g., OXT-211 (Toagosei Co., Ltd.)); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane (e.g., OXT-212 (Toagosei Co., Ltd.)); Co.,Ltd);Ascorbic acid;Methanethiol (methyl mercaptan);Ethanethiol (ethyl mercaptan);Coenzyme A;Dimercaptosuccinic acid (DMSA);Grapefruit mercaptan ((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol);Cysteine ​​((R)-2-amino-3-sulfanyl-propanoic acid);Lipoamide (1,2-dithiolane-3-pentanamide);5,7-bis(1,1-dimethylethyl)-3-[2,3(or 3,4)-dimethylphenyl]-2(3H)-benzofuranone (available from Ciba under the trade name Irganox® HP-136);Benzyl phenyl sulfide;Diphenyl ether diisopropylamine; dioctadecyl 3,3'-thiodipropionate available from Ciba under the trade name Irganox® PS802 (Ciba); didodecyl 3,3'-thiopropionate available from Ciba under the trade name Irganox® PS800; di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate available from Ciba under the trade name Tinuvin® 770; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate available from Ciba under the trade name Tinuvin® 622LD (Ciba); methylbistarylamine;Vistaroamine;phenol-α-naphthylamine;bis(dimethylamino)methylsilane (DMAMS);tris(trimethylsilyl)silane (TTMSS);vinyltriethoxysilane;vinyltrimethoxysilane;2,5-difluorobenzophenone;2',5'-dihydroxyacetophenone;2-aminobenzophenone;2-chlorobenzophenone;benzyl phenyl sulfide;diphenyl sulfide;dibenzyl sulfide;ionic liquids and mixtures and combinations thereof.;

[0111] Any non-refrigerant composition used with the composition of the present invention may alternatively be an ionic liquid stabilizer. The ionic liquid stabilizer may be selected from the group consisting of organic salts that are liquid at room temperature (approximately 25° C.), and the salts contain a cation selected from the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, and triazolium, and mixtures thereof; and an anion selected from the group consisting of [BF4]-, [PF6]-, [SbF6]-, [CF3SO3]-, [HCF2CF2SO3]-, [CF3HFCCF2SO3]-, [HCClFCF2SO3]-, [(CF3SO2)2N]-, [(CF3CF2SO2)2N]-, [(CF3SO2)3C]-, [CF3CO2]-, and F-, and mixtures thereof. In some embodiments, the ionic liquid stabilizer is selected from the group consisting of: emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate), bmim BF4 (1-butyl-3-methylimidazolium tetraborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma-Aldrich).

[0112] In some embodiments, the stabilizer may be a hindered phenol, such as 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; tocopherol; hydroquinone and alkylated hydroquinones, including t-butylhydroquinone, other derivatives of hydroquinone, and the like; hydroxylated thiodiphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert-butylphenol); 4,4 '-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); alkylidene-bisphenols including 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenol diol derivatives; 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert Phenol; 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiol (2,2'-methylenebis(4-ethyl-6-tert-butylphenol) etc.); acylaminophenols such as 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-alpha-dimethylamino-p-cresol; 4,4-thiobis(6-tert-butyl-m-cresol); sulfides such as bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;Any substituted phenolic compound, such as phenol containing one or more substituted or cyclic straight or branched chain aliphatic substituents, such as bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, as well as mixtures thereof (meaning any mixture of phenols disclosed in this section);

[0113] In some embodiments, the stabilizing agent may be a single stabilizing compound from those detailed above, while in other embodiments, the stabilizing agent may be a mixture of two or more of these stabilizing compounds, whether from the same class of compounds detailed above or from different classes of compounds.

[0114] Any non-refrigerant composition used with the compositions of the present invention may alternatively be a tracer. The tracer may be a single compound, but may also be two or more tracer compounds of the same class of compounds or different classes of compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 1 parts per million (ppm) by weight to about 5000 ppm based on the weight of the total composition. In other embodiments, the tracer is present at a total concentration of about 10 ppm to about 1000 ppm. In other embodiments, the tracer is present at a total concentration of about 20 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of about 25 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0115] The tracer may be selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, chlorofluorocarbons (CFCs), hydrofluorochlorocarbons (HCFCs), chlorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodate compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof. Alternatively, the tracer may be selected from the group consisting of trifluoromethane (HFC-23), dichlorodifluoromethane (CFC-12), chlorodifluoromethane (HCFC-22), methyl chloride (R-40), chlorofluoromethane (HCFC-31), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), chloropentafluoroethane (CFC-115), 1,2-difluoroethane (HFC-122a ... 1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3,3-hexafluoroethane 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea), 1,1,1,2,2,3,3-Heptafluoropropane (HFC-227ea), 1,1,1,3,3-Pentafluoropropane (HFC-245fa), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 1,1,1,2,3-Pentafluoropropane (HFC-245eb), 1,1,2,2 -Tetrafluoropropane (HFC-254cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1-trifluoropropane (HFC-263fb), 1,1-difluoro-2-chloroethylene (HCFC-1122), 2-chloro-1,1,2-trifluoroethylene (CFC-1113), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,The tracer may be selected from the group consisting of 5-decafluoropentane (HFC-43-10mee), 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-trifluoropropyne, iodotrifluoromethane, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, nitrous oxide (NO), and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or one hydrofluorocarbon combined with one or more perfluorocarbons. In other embodiments, the tracer is a blend of at least one CFC and at least one HCFC, HFC, or PFC.

[0116] Tracers may be added to the compositions of the present invention in predetermined amounts to allow for the detection of any dilution, contamination, or other alteration of the composition. Tracers may also allow for the detection of products that infringe existing patent rights by identifying the patentee's product against a competing infringing product. Additionally, in one embodiment, tracer compounds may allow for the detection of the manufacturing process that produces the product, and thus the detection of patent infringement of a particular manufacturing process chemistry.

[0117] Additives that may be used with the compositions of the present invention may alternatively be perfluoropolyethers, as described in detail in U.S. Patent Application Publication No. 2007 / 0284555, which is incorporated herein by reference.

[0118] It will be understood that the particular additives described above as suitable for the non-refrigerant components are identified as possible refrigerants. However, in accordance with the present invention, these additives, if used, are not present in amounts that may affect the novel and fundamental characteristics of the refrigerant mixtures of the present invention. The refrigerant mixtures of the present invention and compositions containing them preferably contain no more than about 0.5% by weight of refrigerants other than HFC-32, HFO-1234yf, and CO2.

[0119] In some embodiments, the transfer, treatment, and storage of the refrigerant composition may be performed using equipment and processes that meet ATEX guidelines. In some embodiments, the equipment and processes meet one or more of Directive 99 / 92 / EC (ATEX 137) and / or Directive 94 / 9 / EC (ATEX 95). In one embodiment, some or all of the modules of the treatment unit 130 meet one or more of Directive 99 / 92 / EC (ATEX 137) and / or Directive 94 / 9 / EC (ATEX 95). In one embodiment, all of the modules of the treatment area 130 meet one or more of Directive 99 / 92 / EC (ATEX 137) and / or Directive 94 / 9 / EC (ATEX 95). In some embodiments, sources of ignition may be reduced by reducing static charge / discharge. In one embodiment, the equipment may be electrically grounded. In some embodiments, the transfer, treatment, and storage of the refrigerant composition may be performed using equipment and processes that meet NFPA guidelines. In some embodiments, the equipment and processes meet one or more of the requirements of NFPA 497 / NFPA 90 and / or NFPA 69. In one embodiment, some or all of the modules of the processing unit 130 meet one or more of the requirements of NFPA 497 / NFPA 90 and / or NFPA 69.

[0120] A method 200 for regenerating a refrigerant is depicted in FIG. 2. In block 210, an unregenerated refrigerant composition is transferred from a source vessel to a receiving vessel. In block 220, the receiving vessel is transported to a recycling center. In block 230, the unregenerated refrigerant composition is analyzed to determine that the impurity level of one or more impurities in the unregenerated refrigerant composition sample is above one or more predetermined thresholds. In block 240, a target composition is determined based on the analyzed unregenerated refrigerant composition. In block 250, one or more treatments are determined based on the target composition and the one or more impurity levels. In block 260, the unregenerated refrigerant composition is treated with one or more treatments to form a regenerated refrigerant composition. During the treatment, the one or more impurity levels of the regenerated refrigerant composition are reduced below one or more predetermined thresholds.

[0121] A method 300 for regenerating a refrigerant is depicted in Figure 3. At block 310, an analysis of the unregenerated refrigerant composition is received from a customer. At block 320, a target composition is determined based on the analysis. At block 330, one or more treatments are determined based on the target composition. At block 340, a mobile treatment unit including one or more treatment modules configured to perform the one or more treatments is dispatched. At block 350, the unregenerated refrigerant composition is treated by the mobile treatment unit to form a regenerated refrigerant composition comprising the target composition. In some embodiments, the target composition comprises at least one of 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoro-1-propene, trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane. In one embodiment, the target composition comprises 2,3,3,3-tetrafluoropropene.

[0122] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0123] A sample of HFO-1234yf refrigerant was tested for non-volatile residues and found to have residue levels (residues >100 ppm by weight). In this HFO-1234yf sample, the residue only appeared when all the refrigerant had evaporated, so the residue was not a hard particulate material, but some sort of dissolved material, and could not be removed through a mesh screen. However, the residue can be separated from the refrigerant based on the residue's limited solubility in the refrigerant vapor phase. The residue can be separated from the refrigerant by transferring the vapor phase of the HFO-1234yf refrigerant using a gas compressor. The refrigerant gas is conveyed to a new vessel, leaving the residue in the original vessel. The heel or refrigerant remaining in the original vessel may be destroyed by incineration. Typically, in a vapor recovery process, the yield of "reclaimed refrigerant" can be about 80-90% depending on the refrigerant composition. The gas compressor used for refrigerant vapor movement or transport can be any type of oil-free industrial gas compressor (vertical or horizontal) capable of adequately transporting fluorinated refrigerants based on the flammability and pressure of the refrigerant being regenerated. Single or two stage compressors, or a combination of multiple gas compressors, can be used as desired.

[0124] Refrigerant was transferred from one ISO vessel to the cleaned and purged ISO vessel using a Corken brand single stage oil-free industrial gas compressor having the following specifications:

[0125] [Table 2]

[0126] The compressor was set to a maximum temperature cutout setting of 100C.

[0127] Data from the vapor recovery process are shown below: Example 1

[0128] [Table 3]

[0129] The regenerated refrigerant product was found to have an NVR<50 ppm by weight and was determined to be acceptable for use as a refrigerant. The regenerated refrigerant should have an NVR<20 ppm by weight, taking into account various contaminant densities. The regenerated refrigerant was then analyzed in accordance with AHRI 700 and determined to meet the required specifications for HFO-1234yf, thereby confirming that the regeneration process did not affect the purity, moisture, acid, color, or other emission characteristics of the product. EXAMPLES

[0130] Refrigerants can be treated by re-blending neat or existing blends with other materials to form new blends, or in some cases blends with improved performance, either in conjunction with other processes mentioned herein or separately if the composition of the refrigerant blend is not compatible with the target composition.

[0131] Blending to achieve the product composition change requires transferring the regenerated refrigerant such that the undesirable materials (high MW lubricants or dissolved polymers such as grease) remain in the original vessel in "heel" form. The regenerated refrigerant, designated as component "A", may be liquid transferred such that the undesirable heel (containing the lubricants or dissolved polymers) remains in the vapor heel portion of the original ISO. New, unused component "B" may then be added to the new ISO vessel such that the resulting blend is some composition of "A" and "B" with properties that meet the new specifications. EXAMPLES

[0132] Additionally, it may be desirable to remove moisture from the regenerated refrigerant by passing the regenerated refrigerant through molecular sieves (desiccant) and trapping the moisture within the sieve.

[0133] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. In addition, all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified.

Claims

1. 1. A method for regenerating a refrigerant, comprising: transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source vessel to a treatment vessel; determining a target composition; determining one or more treatments based on the target composition; performing at least one process selected from the group consisting of transferring, blending, distilling, nitrogen purging, filtering, dehydrating, caustic scrubbing, decanting, and combinations thereof to form a partially regenerated or regenerated refrigerant composition; A method comprising:

2. transporting the receiving vessel to a processing center; and performing an analysis on the unregenerated refrigerant composition selected from the group consisting of gas chromatography, mass spectrometry, atomic absorption spectrometry, flame emission spectrometry, infrared spectroscopy, and combinations thereof to determine a composition of the unregenerated refrigerant composition sample, wherein the composition is the regenerated refrigerant composition, and the regenerated refrigerant composition is equal to the target composition. The method of claim 1.

3. adding an additive to the regenerated refrigerant composition; the additive is present at a concentration of less than 0.4% by weight based on the regenerated refrigerant composition; The method of claim 2.

4. The method of claim 2 , wherein the target composition comprises at least one primary component and at least one secondary component.

5. 5. The method of claim 4, wherein the secondary component comprises non-condensable materials at a concentration greater than 1.5% by volume at 25°C in accordance with AHRI 700.

6. The method of claim 5 , wherein the non-condensable material comprises at least one of a fluorinated oligomer and an oxidized polyol ester.

7. 5. The method of claim 4, wherein the at least one treatment increases a concentration ratio of the at least one primary component to the at least one secondary component based on a total weight of the unregenerated refrigerant composition.

8. The method of claim 1 , wherein the processing comprises blending and / or transferring the unregenerated refrigerant from the receiving vessel to a processing vessel.

9. 2. The method of claim 1, wherein the unregenerated refrigerant composition comprises: (i) 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoro-1-propene, trans-1-chloro-3,3,3-trifluoropropene, trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane; or (ii) 2,3,3,3-tetrafluoropropene and trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane.

10. The method of claim 1 , wherein the unregenerated refrigerant composition comprises oil.

11. The method of claim 10 , wherein the oil comprises a polyol ester, a polyalkylene glycol, or a polyvinyl ether.

12. The method of claim 1 , wherein the one or more processes include transferring, blending, filtering, and combinations thereof.

13. 10. The method of claim 1, wherein the unregenerated refrigerant composition comprises at least two immiscible compounds.

14. The method of claim 13 , wherein the treating comprises decanting.

15. 10. The method of claim 1, wherein the purity of the regenerated refrigerant composition is greater than 99.5 wt.%, based on the total weight of the refrigerant composition.

16. 2. The method of claim 1, wherein the one or more processes include at least a first process to form the partially regenerated refrigerant composition and a second process to form the regenerated refrigerant composition.

17. 17. The method of claim 16, wherein the first treatment increases a concentration ratio of at least one primary component to at least one secondary component based on a total weight of the unregenerated refrigerant composition.

18. 20. The method of claim 17, wherein the at least one second treatment increases a concentration ratio of the at least one primary component to the at least one secondary component, based on a total weight of the partially regenerated refrigerant composition, to form the regenerated refrigerant composition.

19. 20. The method of claim 18, wherein the second treatment comprises filtration through a 0.1 micron or smaller screen.

20. the oil concentration of the unregenerated refrigerant composition is reduced by at least 0.5 wt. %, based on the total weight of the unregenerated refrigerant composition; The oil concentration is reduced to less than 0.5 wt. %, based on the total weight of the partially regenerated refrigerant composition.

17. The method of claim 16.

21. the second treatment comprising dehydrating the unregenerated refrigerant composition by contacting the unregenerated refrigerant composition with a desiccant; the water concentration of the unregenerated refrigerant composition is reduced by at least 0.5 wt. %, based on the total weight of the unregenerated refrigerant composition; The water concentration is reduced to less than 0.5 wt. %, based on the total weight of the partially regenerated refrigerant composition.

17. The method of claim 16.

22. 13. A partially regenerated refrigerant composition formed by the method of claim 1.

23. 1. An apparatus for treating a flammable refrigerant composition, comprising: a treatment unit having one or more treatment modules configured to treat the flammable refrigerant composition; the flammable refrigerant composition comprises a hydrofluoroolefin; The processing unit includes one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dewatering module, a caustic scrub module, or a decant module. Device.

24. 1. A method for regenerating a refrigerant, comprising: receiving an analysis of the unregenerated refrigerant composition from a customer; determining a target composition based on the analysis results; determining one or more treatments based on the target composition; dispatching a mobile processing unit including one or more processing modules configured to perform the one or more processes; processing the unregenerated refrigerant composition with the mobile processing unit to form a regenerated refrigerant composition comprising the target composition; Including, the target composition comprises 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoro-1-propene, trans-1-chloro-3,3,3-trifluoropropene, trans-dichloroethylene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, or 1,1-difluoromethane; method.

25. 25. The method of claim 24, wherein the one or more processing modules include one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dewatering module, a caustic scrubbing module, or a decanting module, and the target composition is at least 99.5% pure.

26. The method of claim 25 , wherein the one or more processing modules are electrically grounded.

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