Process and method for regenerating combustible and non-combustible hydrofluoroolefin-containing refrigerants

Abstract

The invention relates to a process and a method for regenerating combustible and non-combustible hydrofluoroolefin-containing refrigerants. The invention provides a method and apparatus for regenerating a refrigerant. The method includes transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source vessel to a receiving vessel, and transporting the receiving vessel to a recirculation center. The unregenerated refrigerant composition is analyzed to determine the 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 by one or more treatments to form a regenerated refrigerant composition having a composition equal to the target composition.

Description

[0001] This application is a divisional application of a patent application. The filing date of the parent application is March 6, 2020, the application number is 202080019707.0 (PCT / US2020 / 021387), and the invention title is "Processes and Methods for Recycling Combustible and Noncombustible Refrigerants Containing Hydrofluoroolefins".

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 815,490, filed Mar. 8, 2019, and U.S. Provisional Application No. 62 / 952,667, filed Dec. 23, 2019. The disclosures of U.S. Provisional Application Nos. 62 / 815,490 and 62 / 952,667 are hereby incorporated by reference. Technical Field

[0003] The present invention relates to the recovery and recycling of low global warming potential, high value refrigerants, including refrigerants having a degree of flammability. Background Art

[0004] Hydrofluoroolefins (HFOs) have been proposed as alternatives to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) that can potentially damage the Earth's ozone layer and / or contribute to global warming. Hydrofluoroolefins do not contain chlorine and thus cannot degrade the Earth's ozone layer.

[0005] Hydrofluoroolefins (HFOs) such as HFO-1234yf (2,3,3,3-tetrafluoropropene) that exhibit a global warming potential (GWP) of less than 1 have replaced older, less environmentally friendly refrigerants. The olefinic portion of the hydrofluoroolefin molecule can exhibit reactivity towards materials encountered during use. Generally, HFO reactivity is encountered during extreme use conditions (i.e., conditions outside the normal operating conditions of the refrigerant and / or refrigerant blend), misuse (such as blending with incompatible products or introducing counterfeit materials or accidental contamination). Thus, the resulting reactivity of the HFO portion of the refrigerant or refrigerant blend can be reduced in a manner that results in undesirable by-products. The resulting by-product formation introduces materials into the refrigerant composition, which can reduce the desired or expected performance of the refrigerant. One source of impurities can be the result of side reactions acting on one or more refrigerants in the system. Side reactions can be caused by various processes, including for example thermal degradation, 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 be generated by side reactions acting on other materials present in the system such as lubricating oils. These can include for example polyol esters, polyethylene ethers, polyalkylene 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. Additionally, materials such as thread lockers can also initiate undesirable by-products. Other sources of undesirable contaminants include plasticizers from hoses, gaskets and O-rings. Since there are now unknown impurities in the refrigerant, these impurities cannot be conveniently removed during the recovery or recycling process, and thus these refrigerants are considered degraded. Conventionally, degraded refrigerants are discarded (destroyed) and the system is refilled with fresh (i.e., new or unused) refrigerant or refrigerant blend. While this is a conventional operation, it results in an unnecessary loss of high-value refrigerant or refrigerant blend. Accordingly, there is a need for methods of recycling and regenerating degraded refrigerant compositions for further use in existing systems or reuse in brand new systems. It is also desirable to improve degraded refrigerants or refrigerant blends, remove contaminants, and re-blend the pure or existing blend with other materials to form new blends or even blends with improved properties. Summary of the Invention

[0006] The present invention can address problems associated with conventional practices by providing compositions, apparatuses, and methods for recycling and regenerating a composition containing a refrigerant.

[0007] Definitions

[0008] Refrigerant recovery involves moving refrigerant from a device containing refrigerant to another container without improving the refrigerant.

[0009] Refrigerant recirculation involves removing some contaminants using procedures or processes that reduce oil, water, acidity, and particles. The refrigerant processed during recirculation is not tested by analytical procedures such as GC-FID, GC-TCD, or GC MS. Although the refrigerant is improved to some extent, the recirculated refrigerant does not meet Air-Conditioning, Heating, and Refrigeration Institute (AHRI) Standard 700. AHRI 700 (2017): Refrigerant Standard indicates the reasonable levels (purity requirements) of contaminants for fluorocarbon, hydrocarbon, and carbon dioxide refrigerants, regardless of source, and lists acceptable test methods.

[0010] Refrigerant regeneration involves removing oil, water, acidity, particles, residues, and other impurities that can adversely affect the quality of the refrigerant and thus its performance. Regeneration involves reprocessing used (or recovered) refrigerant such that the reprocessed refrigerant meets the AHRI 700 quality standard. The quality of the refrigerant 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 refrigerant includes transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source container (or device) to a receiving container and transporting the receiving container to a recirculation center. The unregenerated refrigerant composition is analyzed to determine the composition of a sample of the unregenerated refrigerant composition. 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 by the one or more treatments to form a regenerated refrigerant composition having the target composition.

[0012] In one embodiment, an apparatus for processing a combustible refrigerant composition includes a processing unit having one or more processing modules configured to process the combustible refrigerant composition. The combustible refrigerant composition comprises a hydrofluoroolefin, and the processing unit includes one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, an alkali wash module, or a decantation module.

[0013] In one embodiment, a method of regenerating a refrigerant includes receiving an analysis of an unregenerated refrigerant composition from a customer and determining a target composition based on the analysis. One or more treatments are determined based on the target composition. 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 treats the unregenerated refrigerant composition to form a regenerated refrigerant composition having 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 can include at least one of the following hydrofluoroolefin refrigerants:

[0015] 1,2,3,3,3-pentafluoro-1-propene (CHF=CFCF3);

[0016] 1,1,3,3,3-pentafluoro-1-propene (CF2=CHCF3);

[0017] 1,1,2,3,3-pentafluoro-1-propene (CF2=CFCHF2);

[0018] 1,2,3,3-tetrafluoro-1-propene (CHF=CFCHF2);

[0019] 2,3,3,3-tetrafluoro-1-propene (CH2=CFCF3);

[0020] 1,3,3,3-tetrafluoro-1-propene (CHF=CHCF3);

[0021] 1,1,2,3-tetrafluoro-1-propene (CF2=CFCH2F);

[0022] 1,1,3,3-tetrafluoro-1-propene (CF2=CHCHF2);

[0023] 1,2,3,3-tetrafluoro-1-propene (CHF=CFCHF2);

[0024] 3,3,3-trifluoro-1-propene (CH2=CHCF3);

[0025] 2,3,3-trifluoro-1-propene (CHF2CF=CH2);

[0026] 1,1,2-Trifluoro-1-propene (CH3CF=CF2);

[0027] 1,2,3-Trifluoro-1-propene (CH2FCF=CF2);

[0028] 1,1,3-Trifluoro-1-propene (CH2FCH=CF2);

[0029] 1,3,3-Trifluoro-1-propene (CHF2CH=CHF);

[0030] 1,1,1,2,3,4,4,4-Octafluoro-2-butene (CF3CF=CFCF3);

[0031] 1,1,2,3,3,4,4,4-Octafluoro-1-butene (CF3CF2CF=CF2);

[0032] 1,1,1,2,4,4,4-Heptafluoro-2-butene (CF3CF=CHCF3);

[0033] 1,2,3,3,4,4,4-Heptafluoro-1-butene (CHF=CFCF2CF3);

[0034] 1,1,1,2,3,4,4-Heptafluoro-2-butene (CHF2CF=CFCF3);

[0035] 1,3,3,3-Tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C=CHF);

[0036] 1,1,3,3,4,4,4-Heptafluoro-1-butene (CF2=CHCF2CF3);

[0037] 1,1,2,3,4,4,4-Heptafluoro-1-butene (CF2=CFCHFCF3);

[0038] 1,1,2,3,3,4,4-Heptafluoro-1-butene (CF2=CFCF2CHF2);

[0039] 2,3,3,4,4,4-Hexafluoro-1-butene (CF3CF2CF=CH2);

[0040] 1,3,3,4,4,4-Hexafluoro-1-butene (CHF=CHCF2CF3);

[0041] 1,2,3,4,4,4-Hexafluoro-1-butene (CHF=CFCHFCF3);

[0042] 1,2,3,3,4,4-Hexafluoro-1-butene (CHF=CFCF2CHF2);

[0043] 1,1,2,3,4,4 - Hexafluoro - 2 - butene (CHF2CF=CFCHF2);

[0044] 1,1,1,2,3,4 - Hexafluoro - 2 - butene (CH2FCF=CFCF3);

[0045] 1,1,1,2,4,4 - Hexafluoro - 2 - butene (CHF2CH=CFCF3);

[0046] 1,1,1,3,4,4 - Hexafluoro - 2 - butene (CF3CH=CFCHF2);

[0047] 1,1,2,3,3,4 - Hexafluoro - 1 - butene (CF2=CFCF2CH2F);

[0048] 1,1,2,3,4,4 - Hexafluoro - 1 - butene (CF2=CFCHFCHF2);

[0049] 3,3,3 - Trifluoro - 2 - (trifluoromethyl) - 1 - propene (CH2=C(CF3)2);

[0050] 1,1,1,2,4 - Pentafluoro - 2 - butene (CH2FCH=CFCF3);

[0051] 1,1,1,3,4 - Pentafluoro - 2 - butene (CF3CH=CFCH2F);

[0052] 3,3,4,4,4 - Pentafluoro - 1 - butene (CF3CF2CH=CH2);

[0053] 1,1,1,4,4 - Pentafluoro - 2 - butene (CHF2CH=CHCF3);

[0054] 1,1,1,2,3 - Pentafluoro - 2 - butene (CH3CF=CFCF3);

[0055] 2,3,3,4,4 - Pentafluoro - 1 - butene (CH2=CFCF2CHF2);

[0056] 1,1,2,4,4 - Pentafluoro - 2 - butene (CHF2CF=CHCHF2);

[0057] 1,1,2,3,3 - Pentafluoro - 1 - butene (CH3CF2CF=CF2);

[0058] 1,1,2,3,4 - Pentafluoro - 2 - butene (CH2FCF=CFCHF2);

[0059] 1,1,3,3,3 - Pentafluoro - 2 - methyl - 1 - propene (CF2=C(CF3)(CH3));

[0060] 2-(Difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3));

[0061] 2,3,4,4,4-Pentafluoro-1-butene (CH2=CFCHFCF3);

[0062] 1,2,4,4,4-Pentafluoro-1-butene (CHF=CFCH2CF3);

[0063] 1,3,4,4,4-Pentafluoro-1-butene (CHF=CHCHFCF3);

[0064] 1,3,3,4,4-Pentafluoro-1-butene (CHF=CHCF2CHF2);

[0065] 1,2,3,4,4-Pentafluoro-1-butene (CHF=CFCHFCHF2);

[0066] 3,3,4,4-Tetrafluoro-1-butene (CH2=CHCF2CHF2);

[0067] 1,1-Difluoro-2-(difluoromethyl)-1-propene (CF2=C(CHF2)(CH3));

[0068] 1,3,3,3-Tetrafluoro-2-methyl-1-propene (CHF=C(CF3)(CH3));

[0069] 3,3-Difluoro-2-(difluoromethyl)-1-propene (CH2=C(CHF2)2);

[0070] 1,1,1,2-Tetrafluoro-2-butene (CF3CF=CHCH3);

[0071] 1,1,1,3-Tetrafluoro-2-butene (CH3CF=CHCF3);

[0072] 1,1,1,2,3,4,4,5,5,5-Decafluoro-2-pentene (CF3CF=CFCF2CF3);

[0073] 1,1,2,3,3,4,4,5,5,5-Decafluoro-1-pentene (CF2=CFCF2CF2CF3);

[0074] 1,1,1,4,4,4-Hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCF3);

[0075] 1,1,1,2,4,4,5,5,5-Nonafluoro-2-pentene (CF3CF=CHCF2CF3);

[0076] 1,1,1,3,4,4,5,5,5 - Nonadecafluoro - 2 - pentene (CF3CH=CFCF2CF3);

[0077] 1,2,3,3,4,4,5,5,5 - Nonadecafluoro - 1 - pentene (CHF=CFCF2CF2CF3);

[0078] 1,1,3,3,4,4,5,5,5 - Nonadecafluoro - 1 - pentene (CF2=CHCF2CF2CF3);

[0079] 1,1,2,3,3,4,4,5,5 - Nonadecafluoro - 1 - pentene (CF2=CFCF2CF2CHF2);

[0080] 1,1,2,3,4,4,5,5,5 - Nonadecafluoro - 2 - pentene (CHF2CF=CFCF2CF3);

[0081] 1,1,1,2,3,4,4,5,5 - Nonadecafluoro - 2 - pentene (CF3CF=CFCF2CHF2);

[0082] 1,1,1,2,3,4,5,5,5 - Nonadecafluoro - 2 - pentene (CF3CF=CFCHFCF3);

[0083] 1,2,3,4,4,4 - Hexafluoro - 3 - (trifluoromethyl) - 1 - butene (CHF=CFCF(CF3)2);

[0084] 1,1,2,4,4,4 - Hexafluoro - 3 - (trifluoromethyl) - 1 - butene (CF2=CFCH(CF3)2);

[0085] 1,1,1,4,4,4 - Hexafluoro - 2 - (trifluoromethyl) - 2 - butene (CF3CH=C(CF3)2);

[0086] 1,1,3,4,4,4 - Hexafluoro - 3 - (trifluoromethyl) - 1 - butene (CF2=CHCF(CF3)2);

[0087] 2,3,3,4,4,5,5,5 - Octafluoro - 1 - pentene (CH2=CFCF2CF2CF3);

[0088] 1,2,3,3,4,4,5,5 - Octafluoro - 1 - pentene (CHF=CFCF2CF2CHF2);

[0089] 3,3,4,4,4 - Pentafluoro - 2 - (trifluoromethyl) - 1 - butene (CH2=C(CF3)CF2CF3);

[0090] 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCH(CF3)2);

[0091] 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF3)2);

[0092] 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3);

[0093] 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH²);

[0094] 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH²);

[0095] 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH²=CFCF2CF2CHF²);

[0096] 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3);

[0097] 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3));

[0098] 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH²=CFCH(CF3)²);

[0099] 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF3)²);

[0100] 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH²FCH=C(CF3)²);

[0101] 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)²);

[0102] 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF3)²C=CHCH3);

[0103] 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

[0104] 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3);

[0105] 3,3,4,5,5,5 - hexafluoro - 1 - pentene (CH2=CHCF2CHFCF3);

[0106] 4,4,4 - trifluoro - 2 - (trifluoromethyl) - 1 - butene (CH2=C(CF3)CH2CF3);

[0107] 1,1,2,3,3,4,4,5,5,6,6,6 - dodecafluoro - 1 - hexene (CF3(CF2)3CF=CF2);

[0108] 1,1,1,2,2,3,4,5,5,6,6,6 - dodecafluoro - 3 - hexene (CF3CF2CF=CFCF2CF3);

[0109] 1,1,1,4,4,4 - hexafluoro - 2,3 - bis(trifluoromethyl) - 2 - butene ((CF3)2C=C(CF3)2);

[0110] 1,1,1,2,3,4,5,5,5 - nonafluoro - 4 - (trifluoromethyl) - 2 - pentene ((CF3)2CFCF=CFCF3);

[0111] 1,1,1,4,4,5,5,5 - octafluoro - 2 - (trifluoromethyl) - 2 - pentene ((CF3)2C=CHC2F5);

[0112] 1,1,1,3,4,5,5,5 - octafluoro - 4 - (trifluoromethyl) - 2 - pentene ((CF3)2CFCF=CHCF3);

[0113] 3,3,4,4,5,5,6,6,6 - nonafluoro - 1 - hexene (CF3CF2CF2CF2CH=CH2);

[0114] 4,4,4 - trifluoro - 3,3 - bis(trifluoromethyl) - 1 - butene (CH2=CHC(CF3)3);

[0115] 1,1,1,4,4,4 - hexafluoro - 3 - methyl - 2 - (trifluoromethyl) - 2 - butene ((CF3)2C=C(CH3)(CF3));

[0116] 2,3,3,5,5,5 - hexafluoro - 4 - (trifluoromethyl) - 1 - pentene (CH2=CFCF2CH(CF3)2);

[0117] 1,1,1,2,4,4,5,5,5 - nonafluoro - 3 - methyl - 2 - pentene (CF3CF=C(CH3)CF2CF3);

[0118] 1,1,1,5,5,5 - hexafluoro - 4 - (trifluoromethyl) - 2 - pentene (CF3CH=CHCH(CF3)2);

[0119] 3,4,4,5,5,6,6,6 - octafluoro - 2 - hexene (CF3CF2CF2CF=CHCH3);

[0120] 3,3,4,4,5,5,6,6 - octafluoro - 1 - hexene (CH2=CHCF2CF2CF2CHF2);

[0121] 1,1,1,4,4 - pentafluoro - 2 - (trifluoromethyl) - 2 - pentene ((CF3)2C=CHCF2CH3);

[0122] 4,4,5,5,5 - pentafluoro - 2 - (trifluoromethyl) - 1 - pentene (CH2=C(CF3)CH2C2F5);

[0123] 3,3,4,4,5,5,5 - heptafluoro - 2 - methyl - 1 - pentene (CF3CF2CF2C(CH3)=CH2);

[0124] 4,4,5,5,6,6,6 - heptafluoro - 2 - hexene (CF3CF2CF2CH=CHCH3);

[0125] 4,4,5,5,6,6,6 - heptafluoro - 1 - hexene (CH2=CHCH2CF2C2F5);

[0126] 1,1,1,2,2,3,4 - heptafluoro - 3 - hexene (CF3CF2CF=CFC2H5);

[0127] 4,5,5,5 - tetrafluoro - 4 - (trifluoromethyl) - 1 - pentene (CH2=CHCH2CF(CF3)2);

[0128] 1,1,1,2,5,5,5 - heptafluoro - 4 - methyl - 2 - pentene (CF3CF=CHCH(CF3)(CH3));

[0129] 1,1,1,3 - tetrafluoro - 2 - (trifluoromethyl) - 2 - pentene ((CF3)2C=CFC2H5);

[0130] 1,1,1,2,3,4,4,5,5,6,6,7,7,7 - tetradecafluoro - 2 - heptene (CF3CF=CFCF2CF2C2F5);

[0131] 1,1,1,2,2,3,4,5,5,6,6,7,7,7 - tetradecafluoro - 3 - heptene (CF3CF2CF=CFCF2C2F5);

[0132] 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5);

[0133] 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5);

[0134] 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5);

[0135] 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5);

[0136] pentafluoroethyl trifluorovinyl ether (CF2=CFOCF2CF3);

[0137] trifluoromethyl trifluorovinyl ether (CF2=CFOCF3); and combinations thereof.

[0138] One embodiment of the present invention relates to a method for regenerating a refrigerant comprising any combination of the foregoing hydrofluoroolefins, the method comprising:

[0139] transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source container (or

[0140] equipment) to a processing container;

[0141] transporting the receiving container to a processing center;

[0142] performing an analysis selected from gas chromatography, mass spectrometry, atomic absorption spectroscopy, flame emission spectroscopy, infrared spectroscopy, and combinations thereof on the unregenerated refrigerant composition to

[0143] determine the composition of a sample of the unregenerated refrigerant composition;

[0144] determining a target composition based on the analyzed unregenerated refrigerant composition;

[0145] determining one or more treatments based on the target composition;

[0146] performing at least one treatment selected from transfer, blending, distillation, nitrogen purging, filtration, dehydration, caustic washing, decantation, and combinations thereof to form a partially regenerated refrigerant composition or a regenerated refrigerant composition.

[0147] One embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the composition is a regenerated refrigerant composition; and

[0148] wherein the regenerated refrigerant composition is equal to the target composition.

[0149] Another embodiment of the present invention relates to any combination of the foregoing embodiments and further includes:

[0150] adding an additive to the regenerated refrigerant composition;

[0151] wherein the additive is present in a concentration of less than 0.4% by weight based on the regenerated refrigerant composition.

[0152] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the target composition comprises at least one major component and at least one minor component.

[0153] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the minor component comprises a non-condensable material having a concentration greater than 1.5% by volume at 25 degrees Celsius according to AHRI 700.

[0154] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the non-condensable material comprises fluorinated oligomers.

[0155] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the non-condensable material comprises oxidized polyol esters.

[0156] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein based on the total weight of the unregenerated refrigerant composition, at least one treatment increases the concentration ratio of at least one major component to at least one minor component.

[0157] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the treatment includes transferring the unregenerated refrigerant from a receiving container to a treatment container.

[0158] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the treatment includes blending the unregenerated refrigerant and transferring it from a receiving container to a treatment container.

[0159] Another embodiment of the present invention relates to any combination of the foregoing 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.

[0160] Another embodiment of the present invention relates to any combination of the foregoing 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.

[0161] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the unregenerated refrigerant composition comprises oil.

[0162] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the oil comprises a polyol ester, a polyalkylene glycol, or a polyethylene ether.

[0163] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein one or more treatments include transfer, blending, filtration, and combinations thereof.

[0164] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the unregenerated refrigerant composition comprises at least two immiscible compounds.

[0165] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the treatment includes decantation.

[0166] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition is greater than 99.5% by weight.

[0167] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein one or more treatments include at least two treatments.

[0168] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein, based on the total weight of the unregenerated refrigerant composition, the first treatment increases the concentration ratio of at least one major component to at least one minor component.

[0169] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the partially regenerated refrigerant composition is treated by at least one second treatment to form a regenerated refrigerant composition.

[0170] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein, based on the total weight of the partially regenerated refrigerant composition, at least one second treatment increases the concentration ratio of at least one major component to at least one minor component.

[0171] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the second treatment includes filtration through a screen of 0.1 micron or less.

[0172] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein based on the total weight of the unregenerated refrigerant composition, the oil concentration of the unregenerated refrigerant composition is reduced by at least 0.5% by weight; and

[0173] wherein based on the total weight of the partially regenerated refrigerant composition, the oil concentration is reduced to less than 0.5% by weight.

[0174] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the second treatment includes dehydration.

[0175] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the unregenerated refrigerant composition is contacted with a desiccant;

[0176] wherein based on the total weight of the unregenerated refrigerant composition, the water concentration of the unregenerated refrigerant composition is reduced by at least 0.5% by weight; and

[0177] wherein based on the total weight of the partially regenerated refrigerant composition, the water concentration is reduced to less than 0.5% by weight.

[0178] One embodiment of the present invention relates to a partially regenerated refrigerant composition formed by any combination of the foregoing methods.

[0179] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the first treatment includes transfer or blending.

[0180] One embodiment of the present invention relates to an apparatus for treating a combustible refrigerant composition, the apparatus comprising:

[0181] A treatment unit having one or more treatment modules configured to treat a combustible refrigerant composition;

[0182] wherein the combustible refrigerant composition contains hydrofluoroolefins; and

[0183] wherein the treatment unit includes one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, an alkali washing module, or a decantation module.

[0184] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the hydrofluoroolefin includes 2,3,3,3-tetrafluoropropene.

[0185] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein one or more of the treatment modules are electrically grounded.

[0186] One embodiment of the present invention relates to a method for regenerating a refrigerant, the method comprising:

[0187] Receiving an analysis of an unregenerated refrigerant composition from a customer;

[0188] Determining a target composition based on the analysis;

[0189] Determining one or more treatments based on the target composition;

[0190] Scheduling a mobile processing unit that includes one or more processing modules configured to perform the one or more treatments;

[0191] Processing the unregenerated refrigerant composition by the mobile processing unit to form a regenerated refrigerant composition that includes the target composition;

[0192] Wherein 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.

[0193] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein one or more of the processing modules include one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, an alkali wash module, or a decantation module.

[0194] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein one or more of the processing modules are electrically grounded.

[0195] Another embodiment of the present invention relates to any combination of the foregoing embodiments, wherein the target composition is at least 99.5% pure.

[0196] The embodiments of the present invention can be used alone or in combination with each other. In conjunction with the drawings that illustrate the principles of the invention by way of example, other features and advantages of the invention will become apparent from the following more detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0197] Figure 1 is a schematic diagram of a refrigerant regeneration system according to one embodiment.

[0198] Figure 2 is a block diagram of a method for regenerating a refrigerant according to one embodiment.

[0199] Figure 3 is a block diagram of a method for regenerating a refrigerant according to one embodiment.

[0200] Figure 4 is a front view of a vertical ton tank according to an embodiment.

[0201] Figure 5 is a side view of a vertical ton tank according to an embodiment.

[0202] Figure 6 is an unfolded side view of the internal piping of a vertical ton tank according to an embodiment.

[0203] Figure 7 shows a piping connector of a vertical ton tank according to an embodiment.

[0204] Figure 8 is a view of the bottom portion of a vertical ton tank according to an embodiment.

[0205] Figure 9 is an unfolded top view of the valve configuration of a vertical ton tank according to an embodiment.

[0206] Figure 10 is an unfolded side view of the valve configuration of a vertical ton tank according to an embodiment.

[0207] Figure 11 is a view of a vertical ton tank with a bottom protection gasket according to an embodiment.

[0208] Figure 12 shows a door that is part of the bottom protection gasket of a vertical ton tank according to an embodiment.

[0209] Wherever possible, the same reference numerals will be used throughout the drawings to refer to the same components. DETAILED DESCRIPTION

[0210] The present invention provides methods for recovering, recycling, and regenerating degraded or used refrigerants. Embodiments of the present disclosure include, for example, recovering a refrigerant composition from a use site, testing the refrigerant composition to determine impurities, modifying the characteristics of the refrigerant composition to be above a predetermined threshold, and transferring the refrigerant composition to a use site.

[0211] The refrigerant regeneration system 100 is described in Figure 1 in. In Figure 1In the example, the source tank 110 containing the unregenerated refrigerant composition 115 is communicatively connected to the receiving tank 120 and is 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 can be collected from the source tank 110 or the receiving tank 120 or a combination thereof. The samples can be analyzed to determine the content of one or more components in the unregenerated refrigerant composition 115. The content of one or more components can result in the unregenerated refrigerant composition 115 being outside the desired compositional specifications. In some embodiments, the unregenerated refrigerant composition 115 can be azeotropic composition. In other embodiments, the unregenerated refrigerant composition 115 can be a non-azeotropic composition.

[0212] In some embodiments, the unregenerated refrigerant composition 115 can include components obtained by polymerization or decomposition of one or more hydrofluoroolefin refrigerants. In some embodiments, the components can include polymers, oligomers, phthalates, adipates, fluorinated hydrocarbons, or other reaction products. In one embodiment, the unregenerated refrigerant composition can include a homopolymer obtained by polymerization of one or more refrigerant components of the unregenerated refrigerant composition 115. In some embodiments, the unregenerated refrigerant composition 115 can include an acid component that can reduce the cycle performance of the unregenerated refrigerant composition 115. In some embodiments, the unregenerated refrigerant composition 115 can include chlorine-containing substances or oxidizing substances that may be harmful to refrigeration system components such as hoses, gaskets, or fittings. In some embodiments, the unregenerated refrigerant composition 115 can include other components such as water, oil (e.g., mineral oil or polyol ester), or dyes.

[0213] The presence and concentration of the various components of the unregenerated refrigerant composition 115 can be analyzed using various analytical techniques, including gas chromatography, mass spectrometry, infrared spectroscopy, moisture content, acid content, non-condensable content, high-boiling residues, and / or color measurement. If the content of one or more components is outside one or more predetermined thresholds of the components, a treatment plan (or procedure) for the unregenerated refrigerant composition 115 is determined.

[0214] The treatment plan includes the step of changing the composition of the unregenerated refrigerant composition 115 to conform to 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 suitable for use in a refrigeration system that conforms to the composition specifications. In some embodiments, the target composition comprises 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 comprises 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 equal to or greater than 99.5% of the refrigerant composition.

[0215] In some embodiments, one or more of the refrigerants in the unregenerated refrigerant composition 115 may be a flammable refrigerant. By flammable is meant a gas having a flammable concentration range in air at 60 degrees Celsius and 101.3 kPa pressure according to ASTM E-681-09–Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases).

[0216] Vertical ton tank (VTT)

[0217] In one embodiment, one aspect of the process is the use of a convenient container that is capable of facilitating the recycling, reclamation, and regeneration of used refrigerant. In the exemplary embodiments described herein, the container is a vertical cylinder of 500L to 1000L, or more specifically 750L to 950L, or more specifically 850L to 950L, which is designed to hold, transfer, or convey the flammable composition during recycling, reclamation, and regeneration, and which, due to its vertical orientation, is adapted to facilitate the handling of the used refrigerant. It should be noted that any vertical cylinder designed for flammable refrigerants can also be conveniently used for non-flammable refrigerants. The vertical ton tank (VTT) of the present invention has specific design parameters that, in the combinations described below, enable it to be uniquely used in combination with the other regeneration processes mentioned above. One or more vertical ton tanks can be used for different functions in the refrigeration distribution system 100, including as a source tank 110 and / or a receiving tank 120.

[0218] Orientation

[0219] The VTT cylinder is designed such that the pressure vessel is vertically oriented, meaning the cylinder is upright (vertical) during use, transportation, and storage. Since the footprint (m2) may be restricted when approaching the recovery / recycle / refill (R / R / R) operation, the specific orientation is suitable for a smaller physical footprint at the potential recovery location. Additionally, the vertical orientation design is advantageously suitable for the actual conveyance of vertical tote tanks. The vertical tote tank can be conveniently loaded onto a forklift without any loss of gravity or unusual positioning as in the case of horizontal tote tanks. The design of the base of the vertical tote tank is also designed to improve product conveyance. In one design option, the bottom of the vertical tote tank has an integrated pallet with openings for forklift tines. Thus, the VTT can be used safely and conveniently to physically move combustible refrigerants to a remote recovery processing location.

[0220] Depending on the refrigerant used in the R / R / R process, the pressure, flammability, and volume will follow the appropriate design codes. For example, in the United States, vertical tote tanks will follow ASME design construction and rating pressures, while in the EU, vertical tote tanks will follow ADR, and in Japan, vertical tote tanks will follow HPGL.

[0221] Orientation of the dip tube

[0222] Another embodiment of the improved VTT is the position and orientation of the dip tubes. While dip tubes are fundamental to the cylinder design, the combination of the position of the dip tubes relative to the flanges and the orientation at which the dip tubes meet the upper and lower flanges provides unique product conveyance for the R / R / R of the refrigerant used, as described in the following section. Figure 4 and Figure 5 Front and side views of an embodiment of a vertical tote tank (VTT) with dip tubes are shown. The dip tubes 62 and 65 are shown with 1 / 2 inch and 1 inch connections at the top and bottom of the tank. The attachment of the dip tubes 62 and 65 to the top flange 60 and bottom flange 61 is also depicted. Note the orientation of the dip tubes #62 and #65 and how they mate with the top and bottom flanges.

[0223] Bottom flange and top flange

[0224] Another implementation of the utility of the redesigned VTT is the addition and positioning of flanges, which also aids in the R / R / R process. While process refrigerant can be transferred from one VTT to another or to a separate storage container, it is desirable to be able to access the VTT to see what residues have been left in the VTT. Accordingly, the VTT is designed to include two larger flanges labeled (top flange 60) and (bottom flange 61). The bottom flange and the top flange assist in opening the VTT can and allow for visual inspection or easy inspection via a peeking process such as an endoscope. The flanges also aid in the easy removal of any debris that may have been collected from used refrigerant impurities. The flanges are shown in Figure 4 and Figure 5 in.

[0225] Pipe from flange to valve

[0226] Another implementation in the redesigned VTT is the positioning and design of the piping / connections from the flanges to the valve. As can be seen from the figures, the bottom flange has larger and smaller discharge pipes from the flange. Figure 6 shows the position and orientation of the discharge pipes.

[0227] Figure 7 and Figure 8 are the developed top view and side view of the bottom portion of the (VTT). These figures show the components in more detail and how they are configured into the main bottom flange. The smaller piping details are given in components 83, 84, 85 (smaller flanges), which are connected to a 1 / 2' pipe 64, which then leads to a connector. The larger piping details are given in components 87, 88, and 89, which are connected to a 1' pipe 63.

[0228] Parts list

[0229]

[0230] Gasket

[0231] Another design element is the addition of a PTFE gasket as shown, which ensures no additional contamination from the gasket. The PTFE gasket has been found to be harmless to HFO-type products and is therefore required to be used in combination with this design.

[0232] Valve

[0233] Another unique design element is the addition of a dry bulk coupler (DBC), which limits the amount of refrigerant that can be released during refrigerant transfer. The DBC has a specific locking mechanism that stops product transfer until the unlocking mechanism engages. After the unlocking mechanism engages, the product is transferred. 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 delivery of refrigerant, as typically less than one gram of refrigerant is released during the coupling and decoupling of the DBC. The combination of the DBC with this process contributes to the ease of product transfer, increased safety and containment, and limits any unintentional exposure to refrigerant and / or contaminants. These are elements 122, 124, and 125 in the figures. The adapter from the metal pipe to the DBC is element 123. DBC brands are commonly known as Denver Gardner TODO, Econosto valves, and Dixon valves.

[0234] Bottom gasket

[0235] The specially designed VTT has a bottom gasket that latches in place to protect the bottom valve associated with the VTT. The gasket prevents potential forklift tine collisions with the lower valve and / or flange, thus protecting the product. Additionally, the bottom gasket can be zipper-tied to aid in anti-counterfeiting detection. Any breakage of the certified zipper lock can indicate that the product has potentially been tampered with.

[0236] See Figure 9 , which shows how the gasket fits onto the valve. Figure 10 A protective door is shown that can further protect the valve when the tank is not externally connected.

[0237] In Figure 1 example, the unregenerated refrigerant composition 115 can be transferred from the receiving tank 120 to the processing unit 130. The processing unit 130 includes one or more processing modules that act on the unregenerated refrigerant composition 115 to reduce the concentration of one or more components of the unregenerated refrigerant composition 115 to below one or more predetermined thresholds of the unregenerated refrigerant composition 115. In some embodiments, the unregenerated refrigerant composition 115 can be processed by a first treatment to form a partially regenerated refrigerant composition.

[0238] In one embodiment, the processing unit 130 includes a blending module 131. The blending module 131 adds a composition to the unregenerated refrigerant composition 115 or the partially regenerated refrigerant composition to change the concentration of one or more components. This change can cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.5 wt%.

[0239] 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 causes a change in the concentration of one or more components of the unregenerated refrigerant composition 115. In some embodiments, the transfer partially fills the regeneration tank.

[0240] In some embodiments, a method for filling a regeneration tank with a refrigerant mixture containing azeotropic (or zeotropic) refrigerants includes adjusting the proportion of at least one component of the refrigerant composition in the liquid phase of the refrigerant mixture to a specific range before transfer. In some embodiments, the refrigerant composition can be processed by the blending module 131 before being processed by the transfer module 132.

[0241] The mixture ratios are described below based on a partially regenerated refrigerant composition or an unregenerated refrigerant composition 115 before transfer from a refrigerant composition source that is filled with a refrigerant composition in an amount less than 100 wt% of the maximum fill of the refrigerant mixture.

[0242] As used herein, the term "maximum fill" (100 wt% of the maximum fill) refers to the maximum amount that can be filled into a container, as defined by regulatory authorities such as the United States Department of Transportation (USDOT), the EU ADR, the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR), and the Japanese High Pressure Gas Safety Law. According to these transportation regulations, the maximum fill is calculated as follows:

[0243] G = V / C

[0244] G: mass of fluorocarbon (kg)

[0245] V: capacity of the container (L)

[0246] C: constant according to the type of fluorocarbon filled into the container and the temperature or pressure limits defined in the regulations.

[0247] When the unregenerated refrigerant composition 115 is partially filled in the regeneration container, a part of each component vaporizes to fill the remaining space in the regeneration container. For azeotropic compositions, the relative proportion of the lower-boiling component in the vapor is greater than the proportion of the lower-boiling component in the unregenerated refrigerant composition 115 in the liquid state. Therefore, the proportion of the lower-boiling component relative to the higher-boiling component of the unregenerated refrigerant composition in the liquid state is changed by the transfer.

[0248] In some embodiments, the target composition comprises an azeotropic composition. In some embodiments, the target composition comprises at least one main component. In addition to the at least one main component, the unregenerated refrigerant composition 115 may further comprise at least one minor component. In some embodiments, the at least one main component is the desired material of the target composition. In some embodiments, the at least one minor component is an undesired component of the target composition. In some embodiments, the at least one minor component may exhibit a lower boiling point than the at least one main component. During processing by the transfer module 132, the ratio of the at least one main component to the at least one minor component may be increased based on the unregenerated refrigerant composition 115 in the liquid state.

[0249] In one embodiment, the processing unit 130 includes a decantation module 133. The decantation module 133 can separate one or more immiscible materials from the partially regenerated refrigerant composition or the unregenerated refrigerant composition 115. For example, the decantation module 133 can separate a plurality of immiscible liquids by pumping and / or discharging one or more liquids out of the decantation module 132. In one embodiment, the separated liquid is an impurity, so it is separated from the unregenerated refrigerant composition 115 remaining in the decantation module 133. In one embodiment, the separated liquid may contain the desired refrigerant composition, so the desired material is separated from one or more impurities remaining in the decantation module 132. Decantation may cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, the ratio of the at least one main component to the at least one minor component may be increased based on the unregenerated refrigerant composition 115 in the liquid state. In some embodiments, the concentration of the non-condensable material may be changed to obtain a concentration of less than 1.5 vol% at 25 degrees Celsius in accordance with AHRI 700 (Air-Conditioning, Heating, and Refrigeration Institute Standard, "Specifications for Fluorocarbon Refrigerants", AHRI 700, September 2016). In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.5 wt%.

[0250] 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 refrigerant composition or the 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 out of the distillation module 134. In one embodiment, the separated material is an impurity, and thus it is separated from the unregenerated refrigerant composition 115 remaining in the distillation module 134. In one embodiment, the separated material can include the desired refrigerant composition, and thus the desired material is separated from one or more impurities remaining in the distillation module 134. Distillation can cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, based on the unregenerated refrigerant composition 115 in a liquid state, the ratio of at least one major component to at least one minor component can be increased. In some embodiments, the concentration of non-condensable materials can be changed to obtain a concentration of less than 1.5% by volume at 25 degrees Celsius according to AHRI 700. In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.5% by weight.

[0251] In one embodiment, the processing unit 130 includes a filtration module 135. The filtration module 135 can separate one or more insoluble particles from the partially regenerated refrigerant composition or the 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 a screen of at least 0.01 microns, at least 0.03 microns, at least 0.05 microns, at least 0.08 microns, at least 0.1 microns, or at least 0.15 microns. In one embodiment, the unregenerated refrigerant composition 115 is filtered through a 0.1 micron screen. Filtration can cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, based on the unregenerated refrigerant composition 115 in a liquid state, the ratio of at least one major component to at least one minor component can be increased. In one embodiment, the concentration of one or more components can be changed to obtain an oil concentration of less than 0.5% by weight, but preferably less than 0.05% by weight, and even more preferably less than 0.0025% by weight, less than 22 parts per million by weight (ppm). In one embodiment, the concentration of one or more components can be changed, resulting in a decrease in the dye concentration. In one embodiment, the color of the unregenerated refrigerant composition 115 is changed to a Gardner color value of less than 3.

[0252] In one embodiment, the processing unit 130 includes a washing module 136. The washing module 136 can process the unregenerated refrigerant composition 115 by contacting the unregenerated refrigerant composition 115 with a processing composition. In some embodiments, the processing composition can be a caustic (alkaline) detergent. For example, the washing module 136 can contact the unregenerated refrigerant composition 115 with a caustic solution to remove components containing an acid moiety. In one embodiment, a venturi scrubber is used to contact the unregenerated refrigerant composition 115 with an aqueous sodium hydroxide solution. The washing can cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, the concentration of one or more components can be changed to obtain a total acid number (TAN) of less than 2 milligrams of KOH per 2 grams of the unregenerated refrigerant composition 115. In one embodiment, the concentration of one or more components can be changed to obtain an acidity level of less than 1 ppm by weight according to AHRI 700. In some embodiments, the resulting washed unregenerated refrigerant composition 115 can be further collected and dried to remove any residual water.

[0253] In one embodiment, the processing unit 130 includes a dehydration module 137. The dehydration module 137 can be used to remove water from the unregenerated refrigerant composition 115. For example, the dehydration module 137 can contact the unregenerated refrigerant composition 115 with a desiccant such as molecular sieve. The dehydration can cause the concentration of one or more impurities to be reduced to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, the washed unregenerated refrigerant composition 115 can be dehydrated by passing the washed unregenerated refrigerant composition 115 through the dehydration module 137. In some embodiments, the water concentration can be changed to obtain a water content of less than 20 ppm by weight according to AHRI 700. In one embodiment, the water concentration can be changed to obtain a water content of less than 10 ppm by weight according to AHRI 700 or a water content of less than 5 ppm by weight according to AHRI 700.

[0254] In one embodiment, the processing unit 130 includes an inert gas purge module 138. The inert gas purge module 138 can bring the unregenerated refrigerant composition 115 into contact with an inert gas such as nitrogen, argon, or xenon to displace the dissolved reactive gases in the unregenerated refrigerant composition 115. In one embodiment, the inert gas may include dry nitrogen. The inert gas purge can cause the concentration of one or more components to be changed to less than one or more predetermined thresholds of the unregenerated refrigerant composition 115. In one embodiment, the concentration of non-condensable gas (NCG) or non-absorbable gas (NAG) can be changed to obtain a concentration of less than 1.5 vol% at 25 degrees Celsius according to AHRI 700, preferably less than 0.9 vol% at 25 degrees Celsius according to AHRI 700. NAG typically contains air (which generally consists of 78% nitrogen, 21% oxygen, and about 1% argon) that accumulates in the refrigerant gas phase, where the solubility of air in the refrigerant liquid phase is extremely low. While reducing the total amount of NAG contained in the refrigerant may be important, it is generally more desirable to preferentially reduce the oxygen-containing portion of NAG over the nitrogen portion. In some cases, the oxygen-containing portion can increase the tendency of the refrigerant to decompose or form undesired polymeric materials.

[0255] In one embodiment, the processing unit 130 includes a non-absorbable gas (NAG) reduction unit 139.

[0256] The NAG reduction unit 139 can bring the unregenerated refrigerant composition into contact with a reducing agent such as metal powder, which can react with the oxygen or other oxidizable components of the unregenerated refrigerant composition. In one embodiment, the reducing agent may include iron powder. The treatment by the NAG reduction unit 139 can cause the concentration of one or more components of the unregenerated refrigerant composition to be reduced to less than one or more predetermined thresholds of the unregenerated refrigerant composition. In one embodiment, the concentration of non-condensable materials can be changed to obtain a concentration of less than 1.5 vol% at 25 degrees Celsius according to AHRI 700, preferably less than 0.9 vol% at 25 degrees Celsius according to AHRI 700.

[0257] In another embodiment, a condenser is used in combination with a cooling medium that is cold enough to condense the refrigerant and allows the NAG to pass through with minimal refrigerant loss. A compressor can be used in combination with the condenser to increase the pressure and make it easier to condense the refrigerant at a higher temperature.

[0258] And in yet another embodiment, a membrane is placed such that the NAG can pass through the membrane and be removed while the refrigerant does not pass through, thus separating the NAG from the refrigerant.

[0259] The modules of the processing unit 130 can be used alone or in combination. The unregenerated refrigerant composition 115 can be processed one or more times by any module of the processing unit 130. One or more processes performed by one or more modules of the processing unit 130 can cause the unregenerated refrigerant composition 115 to become a regenerated refrigerant composition, in which all concentrations of one or more impurities are reduced to less than one or more predetermined thresholds. In some embodiments, the regenerated refrigerant composition will exhibit impurity levels equivalent to those of unused material. In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.5 wt%. In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.7 wt%. In some embodiments, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition will be greater than 99.9 wt%.

[0260] As Figure 1 shown, the regenerated refrigerant composition can be transferred from the processing unit 130 to the use tank 140. The use tank 140 can contain both regenerated material and unused material. The use tank 140 can be directly connected to the refrigeration system and is configured to supply refrigerant to the refrigeration system. Alternatively, the use tank 140 can be connected to the distribution tank 150. The use tank 140 can supply refrigerant to the generally smaller distribution tank 150. Thereafter, the distribution tank 150 can be transported to the use site and used to supply refrigerant to the refrigeration system or the customer's storage tank. In some embodiments, based on the total weight of the refrigerant composition, the purity of the refrigerant composition in the use tank 140 or the distribution tank 150 will be greater than 99.5 wt%. In some embodiments, based on the total weight of the refrigerant composition, the purity of the refrigerant composition in the use tank 140 or the distribution tank 150 will be greater than 99.7 wt%. In some embodiments, based on the total weight of the refrigerant composition, the purity of the refrigerant composition in the use tank 140 or the distribution tank 150 will be greater than 99.9 wt%.

[0261] In some embodiments, additives can be added to the regenerated refrigerant composition. In one embodiment, based on the regenerated refrigerant composition, the additive is present at a concentration of less than 0.4 wt%. In one embodiment, the additive can include an inhibitor. In one embodiment, the inhibitor can include at least one of limonene, a-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, or benzene-1,4-diol. In one embodiment, the inhibitor comprises a material having a melting point at a temperature of -70 degrees Celsius to 180 degrees Celsius.

[0262] In some embodiments, the regenerated refrigerant composition can include one or more optional non-refrigerant components selected from lubricants, dyes (including UV dyes), solubilizers, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion inhibitors 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 components can be referred to as additives. In fact, many of these optional non-refrigerant components fit into one or more of these categories and can have qualities that enable them to achieve one or more performance characteristics on their own.

[0263] In some embodiments, one or more non-refrigerant components are present in a minor amount relative to the overall composition. In some embodiments, the amount of the additive concentration in the disclosed composition is from less than about 0.1 wt% to up to about 5 wt% of the total composition. In some embodiments of the present invention, the additive is present in the disclosed composition in an amount of from about 0.1 wt% to about 5 wt% of the total composition or in an amount of from about 0.1 wt% to about 3.5 wt%. In one embodiment, based on the regenerated refrigerant composition, the additive is present at a concentration of less than 0.4 wt%. The additive components selected for the disclosed composition are selected based on utility and / or the requirements of individual equipment components or systems.

[0264] In one embodiment, the lubricant is selected from mineral oils, alkylbenzenes, polyol esters, polyalkylene glycols, polyethylene ethers, polycarbonates, perfluoropolyethers, silicones, silicate esters, phosphate esters, alkanes, cycloalkanes, polyalpha-olefins, and combinations thereof.

[0265] The lubricants disclosed herein can be commercially available lubricants. For example, the lubricant can be a paraffin mineral oil sold by BVA Oils as BVM 100N; a naphthenic mineral oil sold by Crompton Co. under the trade names 1GS, 3GS, and 5GS; a naphthenic mineral oil sold by Pennzoil under the trade name 372LT; a naphthenic mineral oil sold by Calumet Lubricants under the trade name RO-30; a linear alkylbenzene sold by Shrieve Chemicals under the trade names 75, 150, and 500; and a branched alkylbenzene sold by Nippon Oil as HAB 22; a polyol ester (POE), under the trade name 100 is sold by Castrol, United Kingdom; polyalkylene glycol (PAG), such as RL-488A, is obtained from Dow (Dow Chemical, Midland, Michigan); and mixtures thereof (meaning mixtures of any of the lubricants disclosed in this paragraph).

[0266] In the compositions of the present invention containing a lubricant, the lubricant is present in an amount less than 40.0% by weight relative to the total composition. In other embodiments, the amount of the lubricant is less than 20% by weight of the total composition. In other embodiments, the amount of the lubricant is less than 10% by weight of the total composition. In other embodiments, the amount of the lubricant ranges between about 0.1% by weight and 5.0% by weight of the total composition.

[0267] Despite the above weight ratios of the compositions disclosed herein, it should be understood that in some heat transfer systems, when the compositions are used, additional lubricants may be obtained from one or more equipment components of such heat transfer systems. For example, in some refrigeration systems, air conditioning systems, and heat pump systems, lubricants may be loaded into the compressor and / or the compressor lubricant reservoir. In addition to any lubricant additives, such lubricants will be present in the refrigerant of such systems. In use, when in the compressor, the refrigerant composition may acquire an amount of equipment lubricant to change the refrigerant-lubricant composition from the starting ratio.

[0268] 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 ultraviolet (UV) dye. The UV dye may be a fluorescent dye. The fluorescent dye may be selected from naphthalimides, perylenes, coumarins, anthracenes, phenanthrenes, xanthenes, thioxanthenes, benzoxanthenes, fluoresceins, and derivatives of said dyes, and combinations thereof (meaning mixtures of any of the foregoing dyes or their derivatives disclosed in this paragraph).

[0269] In some embodiments, the disclosed compositions contain from about 0.001% by weight 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% by weight to about 0.5% by weight; and in other embodiments, the UV dye is present in an amount of from 0.01% by weight to about 0.25% by weight of the total composition.

[0270] The UV dye is a useful component for detecting leaks of the composition by allowing the fluorescence of the dye at or near the leak point of the equipment (such as a refrigeration unit, air conditioner, or heat pump) to be observed. UV emission, such as the fluorescence of the dye, can be observed under ultraviolet light. Thus, if the composition containing such a UV dye leaks from a given point in the equipment, the fluorescence can be detected at or near the leak point.

[0271] Another non-refrigerant component that can be used with the compositions of the present invention can include at least one solubilizer, which is selected to improve the solubility of one or more dyes in the disclosed compositions. In some embodiments, the weight ratio of the dye to the solubilizer ranges from about 99:1 to about 1:1. The solubilizer includes at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorinated hydrocarbons (such as dichloromethane, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes, and mixtures thereof (meaning mixtures of any of the solubilizers disclosed in this paragraph).

[0272] In some embodiments, the non-refrigerant component comprises at least one compatibilizer to improve the compatibility of one or more lubricants with the disclosed compositions. The compatibilizer can be selected from hydrocarbons, hydrocarbon ethers, polyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorinated hydrocarbons (such as dichloromethane, 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 paragraph).

[0273] The solubilizer and / or compatibilizer can be selected from hydrocarbon ethers, which consist of ethers containing only carbon, hydrogen, and oxygen, such as dimethyl ether (DME) and mixtures thereof (meaning mixtures of any of the hydrocarbon ethers disclosed in this paragraph).

[0274] The compatibilizer can be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing 3 to 15 carbon atoms. The compatibilizer can be at least one hydrocarbon, which can be selected from at least one propane (including propylene and propane), butane (including n-butane and isobutene), pentane (including n-pentane, isopentane, neopentane, and cyclopentane), hexane, octane, nonane, and decane, etc. Commercially available hydrocarbon compatibilizers include, but are not limited to, those sold under the trade name H by Exxon Chemical (USA), the mixture of undecane (C 11 ) and dodecane (C 12 ) (high purity C 11 to C 12 isoparaffin), Aromatic 150 (C9 to C 11 aromatic), Aromatic 200 (C9 to C 15 aromatic), and Naptha 140 (a mixture of C5 to C 11 paraffins, naphthenes, and aromatics), and mixtures thereof (meaning mixtures of any of the hydrocarbons disclosed in this paragraph).

[0275] The compatibilizer may alternatively be at least one polymeric compatibilizer. The polymeric compatibilizer may be a random copolymer of fluorinated and non-fluorinated acrylates, where the polymer comprises repeating units of at least one monomer represented by the formula CH2═C(R 1 )CO2R 2 , CH2═C(R 3 )C6H4R 4 and CH2═C(R 5 )C6H4XR 6 , where X is oxygen or sulfur; R 1 , R 3 and R 5 are independently selected from H and C1-C4 alkyl groups; and R 2 , R 4 and R 6 are independently selected from carbon chain-based groups containing C and F, and may also contain H, Cl, ether oxygen, or sulfur in the form of sulfide, sulfoxide, or sulfone groups, and mixtures thereof. Examples of such polymeric compatibilizers include those commercially available under the trade name PHS from E.I. du Pont de Nemours and Company, (Wilmington, DE, 19898, USA). PHS is a random copolymer prepared by polymerizing: 40 wt% of CH2═C(CH3)CO2CH2CH2(CF2CF2)mF (also known as fluoromethyl acrylate or ZFM), where m is from 1 to 12, predominantly from 2 to 8, and 60 wt% of lauryl methacrylate (CH2═C(CH3)CO2(CH2) 11 CH3, also known as LMA).

[0276] In some embodiments, the compatibilizer component comprises from about 0.01 wt% to 30 wt% (based on the total amount of the compatibilizer) of an additive that reduces the surface energy of the metals copper, aluminum, steel, or other metals and their metal alloys present in the heat exchanger in a manner that reduces the adhesion of the lubricant to the metal. Examples of additives that reduce the metal surface energy include those commercially available under the trade names FSA, FSP, and FSJ from DuPont.

[0277] Another optional non-refrigerant component that can be used with the compositions of the present invention can be a metal surface deactivator. The metal surface deactivator is selected from oxalyl bis(benzylidene)hydrazide (CAS registration number 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide (CAS registration number 32687-78-8), 2,2'-oxalamido bis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (CAS registration number 70331-94-1), N,N'-(disalicylidene)-1,2-diaminopropane (CAS registration number 94-91-7), and ethylenediaminetetraacetic acid (CAS registration number 60-00-4) and its salts, and mixtures thereof (meaning mixtures of any of the metal surface deactivators disclosed in this paragraph).

[0278] The optional non-refrigerant component used with the compositions of the present invention can alternatively be a stabilizer selected from: hindered phenols, thiophosphates, tributyl thiophosphate, organic phosphates, or phosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenone derivatives, aryl thioethers, divinyl terephthalate, diphenyl terephthalate, ionic liquids, and mixtures thereof (meaning mixtures of any of the stabilizers disclosed in this paragraph).

[0279] The stabilizer can be selected from: tocopherol; hydroquinone; tert-butylhydroquinone; monothiophosphates; and dithiophosphates, commercially available under the trade name 63 from Ciba Specialty Chemicals (Basel, Switzerland) (hereinafter referred to as "Ciba"); dialkyl thiophosphates, commercially available under the trade names 353 and 350 from Ciba; tributyl thiophosphate, commercially available under the trade name 232 from Ciba; phosphoric acid amines, commercially available under the trade name 349 (Ciba) from Ciba; hindered phosphites, available as 168 from Ciba, and tris-(di-tert-butylphenyl) phosphite, commercially available under the trade name OPH from Ciba; (di-n-octyl phosphite); and isodecyl diphenyl phosphite, commercially available under the trade name The DDPP was commercially obtained from Ciba; trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, and tris(2-ethylhexyl) phosphate; triaryl phosphates including triphenyl phosphate, tricresyl phosphate, and xylenyl phosphate; and mixed alkyl-aryl phosphates including isopropylphenyl phosphate (IPPP) and bis(tert-butylphenyl)phenyl phosphate (TBPP); butylated triphenyl phosphate such as those commercially obtained under the trade name those commercially obtained, including 8784; tert-butylated triphenyl phosphate such as those commercially obtained under the trade name those; isopropylphenylated triphenyl phosphate such as those commercially obtained under the trade name 220 and those commercially obtained; anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; myrcene, allo-ocimene, limonene (especially d-limonene); retinal; pinene; menthol; geraniol; farnesol; phytol; vitamin A; terpinene; δ-3-carene; terpinolene; phellandrene; fenchene; dipentene; carotenoids such as lycopene, β-carotene, and xanthophylls such as zeaxanthin; retinoids such as hepatoxanthin and isotretinoin; camphane; 1,2-epoxypropane; 1,2-epoxybutane; n-butyl glycidyl ether; trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane; 3-ethyl-3-hydroxymethyloxetane such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3-((phenoxy)methyl)oxetane such as OXT-211 (Toagosei Co., Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)oxetane such as OXT-212 (Toagosei Co., Ltd); ascorbic acid; methanethiol (methyl mercaptan); ethanethiol (ethyl mercaptan); coenzyme A; dimercaptosuccinic acid (DMSA); naringinethiol ((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-

[0280] [2,3(or 3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially obtained from Ciba under the trade name HP-136; benzyl phenyl sulfide; diphenyl sulfide; diisopropylamine; dioctadecyl 3,3'-thiodipropionate, commercially obtained from Ciba under the trade name PS 802 (Ciba) from Ciba; dilauryl 3,3'-thiodipropionate, under the trademark PS 800 was commercially obtained from Ciba; bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, under the trade name 770 was commercially obtained from Ciba; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl) succinate, under the trade name 622LD (Ciba) was commercially obtained from Ciba; methyl bis-tallow amine; bis-tallow amine; 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.

[0281] Optional non-refrigerant components used with the compositions of the present invention may alternatively be ionic liquid stabilizers. Ionic liquid stabilizers may be selected from organic salts that are liquid at room temperature (about 25 °C), those salts comprising cations selected from pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, and triazolium, and mixtures thereof; and salts having anions selected from [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 stabilizers are selected from 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 purchased from Fluka (Sigma-Aldrich).

[0282] In some embodiments, the stabilizer can be a hindered phenol, which is any substituted phenol compound, including phenols containing one or more substituted or cyclic, straight-chain, or branched aliphatic substituents, such as alkylated monophenols, including 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; tocopherol; and the like; hydroquinones and alkylated hydroquinones, including tert-butyl hydroquinone, 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); and the like; alkylidene-bisphenols, including: 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); derivatives of 2,2'- or 4,4-biphenol diol; 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 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-biphenyl diol, including 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); butylated hydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol), bisphenols containing heteroatoms, including 2,6-di-tert-α-dimethylaminocresol, 4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); including thioethers; bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and mixtures thereof (meaning any mixture of the phenols disclosed in this paragraph).

[0283] In some embodiments, the stabilizer can be a single stabilizing compound as described in detail above. In other embodiments, the stabilizer can be a mixture of two or more of the stabilizing compounds, which can be from the same class of compounds or from different classes of compounds, the classes of which will be described in detail above.

[0284] Optional non-refrigerant components used with the compositions of the present invention may alternatively be tracers. The tracer may be a single compound from the same class of compounds or from different classes of compounds or two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of from about 1 part per million by weight (ppm) to about 5000 ppm, based on the weight of the overall composition. In other embodiments, the tracer is present at a total concentration of from about 10 ppm to about 1000 ppm. In other embodiments, the tracer is present at a total concentration of from about 20 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of from about 25 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of from about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of from about 100 ppm to about 300 ppm.

[0285] The tracer can be selected from hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), chlorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, and ketones, nitrous oxide, and combinations thereof. Alternatively, the tracer can be selected from trifluoromethane (HFC-23), dichlorodifluoromethane (CFC-12), chlorodifluoromethane (HCFC-22), chloromethane (R-40), chlorofluoromethane (HCFC-31), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), pentafluorochloroethane (CFC-115), 1,2-dichloro-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-hexafluoropropane (HFC-236fa), 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), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee), 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetrafluorooctane, hexafluorobutadiene, 3,3,3-trifluoropropyne, trifluoroiodomethane, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O), and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or a combination of one hydrofluorocarbon and 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.

[0286] A tracer can be added to the compositions of the present invention in a predetermined amount to allow detection of any diluted, contaminated, or otherwise altered composition. Additionally, the tracer can allow detection of products that infringe existing patents by identifying the patent owner's product relative to competing infringing products. Further, in one embodiment, the tracer compound can allow detection of the manufacturing process for preparing the product, thus allowing detection of infringement of the patent on the chemistry of a particular manufacturing process.

[0287] Additives that can be used with the compositions of the present invention can alternatively be perfluoropolyethers, as detailed in US2007 - 0284555, which is incorporated herein by reference.

[0288] It will be recognized that some of the above - mentioned additives, as applicable to non - refrigerant components, have been identified as potential refrigerants. However, according to the present invention, when these additives are used, they are not present in an amount that would affect the novel and essential characteristics of the refrigerant mixtures of the present invention. Preferably, the refrigerant mixtures and the compositions of the present invention containing them contain no more than about 0.5 wt% of refrigerants other than HFC - 32, HFO - 1234yf, and CO2.

[0289] In some embodiments, the transfer, handling, and storage of the refrigerant composition can be carried out using equipment and processes that comply with ATEX guidelines. In some embodiments, the equipment and processes comply with 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 in the processing unit 130 comply with 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 in the processing area 130 comply with one or more of Directive 99 / 92 / EC (ATEX 137) and / or Directive 94 / 9 / EC (ATEX 95). In some embodiments, ignition sources can be reduced by reducing electrostatic charging / discharging. In one embodiment, the equipment can be electrically grounded. In some embodiments, the transfer, handling, and storage of the refrigerant composition can be carried out using equipment and processes that comply with NFPA guidelines. In some embodiments, the equipment and processes comply with one or more of NFPA 497 / NFPA 90 and / or NFPA 69 requirements. In one embodiment, some or all of the modules in the processing unit 130 comply with one or more of NFPA 497 / NFPA 90 and / or NFPA 69 requirements.

[0290] A method 200 for regenerating a refrigerant is described in Figure 2In the middle. At block 210, transfer the unregenerated refrigerant composition from the source container to the receiving container. At block 220, transport the receiving container to the recycling center. At block 230, analyze the unregenerated refrigerant composition to determine that one or more impurity levels of the impurities in the unregenerated refrigerant composition sample are higher than one or more predetermined thresholds. At block 240, determine the target composition based on the analyzed unregenerated refrigerant composition. At block 250, determine one or more treatments based on the target composition and one or more impurity levels. At block 260, treat the unregenerated refrigerant composition through one or more treatments to form a regenerated refrigerant composition. During the treatment, one or more impurity levels of the regenerated refrigerant composition are reduced to below one or more predetermined thresholds.

[0291] The method 300 for regenerating refrigerant is described in Figure 3 In the middle. At block 310, receive an analysis of the unregenerated refrigerant composition from a customer. At block 320, determine the target composition based on the analysis. At block 330, determine one or more treatments based on the target composition. At block 340, schedule a mobile treatment unit that includes one or more treatment modules configured to perform one or more treatments. At block 350, treat the unregenerated refrigerant composition by the mobile treatment unit to form a regenerated refrigerant composition that includes the target composition. In some embodiments, the target composition includes 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 includes 2,3,3,3-tetrafluoropropene.

[0292] The following examples are provided to illustrate certain embodiments of the present invention and should not limit the scope of the appended claims.

[0293] Example #1

[0294] The non-volatile residues of the HFO-1234yf refrigerant sample were tested and found to have a residue content (residue by weight > 100 ppm). For this HFO-1234yf sample, the residue only appears when all the refrigerant has vaporized. Therefore, the residue is not a hard particulate matter, but a dissolved substance and cannot be removed via a sieve. However, based on the limited solubility of the residue in the refrigerant gas phase, the residue can be separated from the refrigerant. By using a gas compressor to transfer the gas phase of the HFO-1234yf refrigerant, the residue can be separated from the refrigerant. The refrigerant gas is transported to a new container while the residue remains in the original container. The bottom liquid or refrigerant remaining in the original container can be destroyed by incineration. Generally, depending on the refrigerant composition, the vapor recovery process yields about 80%-90% "reclaimed refrigerant". The gas compressor used to move or transfer the refrigerant vapor can be any type of oil-free industrial gas compressor (vertical or horizontal), which can appropriately transport the fluorinated refrigerant based on the flammability and pressure of the refrigerant being reclaimed. If necessary, a single-stage or two-stage compressor or a combination of multiple gas compressors can be used.

[0295] A Corken brand single-stage oil-free industrial gas compressor with the following specifications was used to transfer the refrigerant from one ISO container to a cleaned and purged ISO container.

[0296]

[0297] The compressor was set to have a temperature cut-off setting of up to 100 °C.

[0298] Data from the vapor recovery process are shown below: Example #1

[0299] Initial container Initial NVR Transfer container Final NVR Ton tank 56 ppm Ton tank Approximately 0 ppm

[0300] It was found that the reclaimed refrigerant product had an NVR of < 50 ppm by weight and was determined to be acceptable for use as a refrigerant. The reclaimed refrigerant should have an NVR of < 20 ppm by weight to account for different contaminant densities. The reclaimed refrigerant was then analyzed according to AHRI 700 and determined to meet the required specifications for HFO-1234yf, thus confirming that the reclaiming process does not affect the product purity, moisture, acid, color, or other release characteristics.

[0301] Example #2

[0302] The refrigerant can be processed by re-blending the pure or existing blend with other materials to form a new blend or (in some cases) an improved performance blend. This can be done together with other processes mentioned herein or separately if the composition of the refrigerant blend does not meet the target composition.

[0303] Blending to achieve a change in product composition requires transferring the recycled refrigerant such that any undesired materials (high MW lubricants or dissolved polymers such as greases) remain in the original container as a "bottom liquid". The recycled refrigerant, designated as component "A", can be transferred as a liquid such that the undesired bottom liquid (which contains lubricants or dissolved polymers) remains in the vapor bottom liquid portion of the original ISO. Then the new, unused component "B" can be added to the new ISO container such that the resulting blend is some composition of "A" and "B" with properties meeting the new specifications.

[0304] Example #3 :

[0305] In addition, it is desirable to remove moisture from the recycled refrigerant. The recycled refrigerant is passed through a molecular sieve (dryer) such that the moisture is trapped within the sieve.

[0306] Although the invention has been described with reference to one or more embodiments, those skilled in the art will understand that various changes can be made and elements can be replaced with equivalents without departing from the scope of the invention. In addition, numerous modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the invention is not intended to be limited to the specific embodiments disclosed as the best mode contemplated for carrying out the invention, but the invention will include all embodiments falling within the scope of the appended claims. In addition, all numerical values identified in the detailed description will be interpreted as if both the exact value and the approximation were explicitly identified.

Claims

1. A method for regenerating a refrigerant, the method comprising: transferring an unregenerated refrigerant composition comprising one or more hydrofluoroolefins from a source container to a receiving container, at least one of the source container and the receiving container being a vertical ton tank, wherein the bottom of the vertical ton tank has an integrated pallet and / or wherein the vertical ton tank has a bottom valve, the bottom valve optionally being protected by a gasket; transporting the receiving container to a processing center, performing an analysis selected from gas chromatography, mass spectrometry, atomic absorption spectroscopy, flame emission spectroscopy, infrared spectroscopy, and combinations thereof on the unregenerated refrigerant composition to determine the composition of a sample of the unregenerated refrigerant composition; determining a target composition based on the analyzed unregenerated refrigerant composition, the target composition comprising at least one major component and at least one minor component; determining at least two treatments based on the target composition; performing at least one treatment selected from transfer, blending, distillation, nitrogen purging, filtration, dehydration, caustic washing, decantation, and combinations thereof to form a partially regenerated refrigerant composition or a regenerated refrigerant composition, wherein based on the total weight of the unregenerated refrigerant composition, a first treatment increases the concentration ratio of at least one major component to at least one minor component, and based on the total weight of the partially regenerated refrigerant composition, a second treatment increases the concentration ratio of at least one major component to at least one minor component, wherein the partially regenerated refrigerant composition is treated with the second treatment to form a regenerated refrigerant composition, and wherein one or more refrigerants in the unregenerated refrigerant composition comprise a flammable refrigerant.

2. The method according to claim 1, the method further comprising: adding an additive to the regenerated refrigerant composition; wherein the additive is present at a concentration of less than 0.4 wt% based on the regenerated refrigerant composition, preferably, the minor component comprises a non-condensable material having a concentration greater than 1.5 vol% at 25 degrees Celsius according to AHRI 700, more preferably, the non-condensable material comprises a fluorinated oligomer and / or an oxidized polyol ester.

3. The method according to claim 1, wherein the treatment comprises blending the unregenerated refrigerant and transferring it from the receiving container to a processing container, and / or wherein the unregenerated refrigerant 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, and / or wherein the unregenerated refrigerant composition comprises 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, and / or wherein the unregenerated refrigerant composition comprises oil, preferably, the oil comprises a polyol ester, a polyalkylene glycol, or a polyethylene ether, and / or Wherein the at least two treatments include transfer, blending, filtration, and combinations thereof.

4. The method according to claim 1, wherein the unregenerated refrigerant composition comprises at least two immiscible compounds, preferably, the treatment includes decantation, and / or wherein, based on the total weight of the refrigerant composition, the purity of the regenerated refrigerant composition is greater than 99.5% by weight, and / or wherein, based on the total weight of the partially regenerated refrigerant composition, the at least one second treatment increases the concentration ratio of the at least one major component to the at least one minor component, preferably, based on the total weight of the unregenerated refrigerant composition, the oil concentration of the unregenerated refrigerant composition is reduced by at least 0.5% by weight, and / or based on the total weight of the partially regenerated refrigerant composition, the oil concentration is reduced to less than 0.5% by weight, and / or wherein the second treatment includes dehydration, preferably, contacting the unregenerated refrigerant composition with a desiccant, and / or wherein, based on the total weight of the unregenerated refrigerant composition, the water concentration of the unregenerated refrigerant composition is reduced by at least 0.5% by weight; and wherein, based on the total weight of the partially regenerated refrigerant composition, the water concentration is reduced to less than 0.5% by weight, and / or wherein the second treatment includes filtration through a sieve of 0.1 micron or less, and / or wherein the first treatment includes transfer or blending, and / or wherein the method further includes analyzing the unregenerated refrigerant composition to determine the composition of the unregenerated refrigerant composition and whether one or more impurity levels of impurities in the unregenerated refrigerant composition are higher than one or more predetermined thresholds, wherein performing at least one treatment can reduce the one or more impurity levels to below the one or more predetermined thresholds.

5. A partially regenerated refrigerant composition formed by the method according to claim 1.

6. A partially regenerated refrigerant composition formed by the method according to claim 4.

7. A device for treating a combustible refrigerant composition, the device comprising: a treatment unit having one or more treatment modules configured to treat the combustible refrigerant composition stored in a vertical ton tank, wherein the bottom of the vertical ton tank has an integrated pallet and / or wherein the vertical ton tank has a bottom valve, and the bottom valve is optionally protected by a gasket; wherein the combustible refrigerant composition contains hydrofluoroolefins; and wherein the treatment unit includes one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, an alkali washing module, or a decantation module.

8. The device according to claim 7, wherein the hydrofluoroolefin includes 2,3,3,3-tetrafluoropropene, and / or wherein the one or more treatment modules are electrically grounded.

9. A method for regenerating a refrigerant, the method comprising: Receiving an analysis of an unregenerated refrigerant composition from a customer; Determine a target composition based on the analysis, the target composition comprising at least one major component and at least one minor component; Determine at least two treatments based on the target composition; Dispatch a mobile processing unit, the mobile processing unit including one or more processing modules configured to perform the one or more treatments; Process the unregenerated refrigerant composition stored in a vertical ton tank by the mobile processing unit to form a regenerated refrigerant composition comprising the target composition, wherein the bottom of the vertical ton tank has an integrated pallet and / or wherein the vertical ton tank has a bottom valve, the bottom valve optionally protected by a gasket; wherein 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, and wherein the minor component comprises a non-condensable material having a concentration greater than 1.5 vol% at 25 degrees Celsius according to AHRI 700, wherein based on the total weight of the unregenerated refrigerant composition, a first treatment increases the concentration ratio of at least one major component to at least one minor component, and based on the total weight of the partially regenerated refrigerant composition, a second treatment increases the concentration ratio of at least one major component to at least one minor component, wherein the partially regenerated refrigerant composition is treated with a second treatment to form a regenerated refrigerant composition.

10. The method according to claim 9, wherein the one or more processing modules comprise one or more of a blending module, a distillation module, a nitrogen purge module, a filtration module, a dehydration module, an alkali wash module or a decantation module. Preferably, the one or more processing modules are electrically grounded, and / or the target composition is at least 99.5% pure, and / or the method further comprises determining based on an analysis the composition of the unregenerated refrigerant composition and whether one or more impurity levels of impurities in the unregenerated refrigerant composition are higher than one or more predetermined thresholds, wherein processing the unregenerated refrigerant composition can reduce the one or more impurity levels to below one or more predetermined thresholds to form a regenerated refrigerant composition.

Images