Refrigerant blends with low global warming potential

Abstract

The present invention relates to a process for preparing a refrigerant blend containing one or more purified hydrofluorocarbon compounds. [Solution] One or more hydrofluorocarbon compounds are recovered and purified from one or more refrigeration, air conditioning, or heat pump systems.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 691,490, filed June 28, 2018, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of Invention) The present invention relates to a process for preparing a refrigerant blend comprising one or more purified hydrofluorocarbon compounds, wherein the one or more hydrofluorocarbon compounds are recovered and purified from one or more refrigeration systems. [Background technology]

[0003] Over the past several decades, many industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastic and thermosetting foams, heat transfer fluids, gaseous dielectrics, fire extinguishing and suppressing agents, power cycle working fluids, polymerization media, particulate control fluids, carrier fluids, buffing abrasives, and displacement drying agents. In the search for alternatives to these versatile compounds, many industries have turned their attention to the use of hydrofluorocarbons (HFCs) and / or hydrofluoroolefins (HFOs). With their low ozone depletion potential and low global warming potential, HFOs are considered candidates to replace saturated CFCs and can be used in a wide range of applications, including as refrigerants. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent Provisional Application No. 62 / 691,490 [Overview of the project] [Means for solving the problem]

[0005] This application relates, in particular, to a process for preparing a refrigerant blend containing one or more recovered hydrofluorocarbon compounds, (a) A process of recovering one or more hydrofluorocarbons from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 20 to form a refrigerant blend, The present invention provides a process in which one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

[0006] This application relates to a process for reducing the global warming potential of a refrigerant blend, (a) A step of selecting one or more hydrofluorocarbons recovered from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 20 to form a purified refrigerant blend, The purified refrigerant blend has a lower global warming potential compared to a refrigerant blend containing one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). The present invention further provides a process in which one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

[0007] This application further provides a refrigeration, air conditioning, or heat pump system comprising a refrigerant blend prepared according to the process described herein.

[0008] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. Methods and materials for use in the present invention are described herein, and other preferred methods and materials known in the art may also be used. Materials, methods, and examples are illustrative and not intended to limit the scope. All publications, patent applications, patents, sequences, database entries, and other references referenced herein are incorporated herein by reference in their entirety. In the event of any conflict, including definitions, this specification shall prevail. [Modes for carrying out the invention]

[0009] The Global Warming Potential (GWP) is an index used to estimate the relative contribution of one kilogram of atmospheric emissions of a particular greenhouse gas to global warming compared to one kilogram of carbon dioxide emissions. GWPs can be calculated for various time periods and reflect the atmospheric lifetime impact of a given gas. A GWP over a 100-year period is the commonly referenced value.

[0010] Since GWP is a measure of how much energy a one - ton emission of a gas absorbs over a given period, compounds (e.g., hydrofluorocarbons or hydrofluoroolefins) recovered from use in an apparatus or system and subsequently recycled and / or purified contribute a minimal or even zero “effective GWP” compared to newly manufactured compounds for use in making refrigerant mixtures or blends. For clarity, recovery means the process of removing the refrigerant from a refrigeration, air - conditioning, or heat - pump system after it has been used in that system for some period. Reuse is intended to mean the cleaning / purification of the recovered compound or blend, including removing impurities such as lubricants, solids, water, and air from the used refrigerant, and also potentially adjusting the composition of the refrigerant mixture. Reuse can be achieved on - site or at a “reuse facility” or entity specializing in the recovery, purification, and resale of used refrigerant. Recycling is intended to mean removing the refrigerant from the system on - site and then the cleaning and re - introduction into the same or a similar system is minimal to non - existent. Thus, as used herein, the term “effective GWP” refers to the GWP of a refrigerant mixture or blend containing compounds such as hydrofluorocarbons or hydrofluoroolefins that have been recovered from use in an apparatus or system and subsequently reused, recycled, and / or purified according to one or more of the processes provided herein. The effective GWP of such mixtures can be significantly reduced relative to the GWP of a refrigerant mixture or blend containing only “virgin” components newly manufactured for use in the refrigerant mixture or blend. The recovered, reused / recycled / purified portion of the refrigerant blend is not added to the net global supply of existing global - warming compounds, and thus the recovered portion of the refrigerant blend contributes zero to the GWP of the refrigerant mixture or blend. Refrigerant can be recovered and reused without recycling, reuse, or purification steps, but note that such reuse may not function as intended and the unpurified refrigerant may be harmful to the system in which it is later used.

[0011] As used herein, the term "ozone depletion potential (ODP)" is defined in Section 1.4.4, pages 1.28 - 1.31 (see the first paragraph of this section) of "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association’s Global Ozone Research and Monitoring Project". The ozone depletion potential (ODP) represents the degree of stratospheric ozone layer depletion expected from a compound based on the mass relative to the mass of trichlorofluoromethane (CFC - 11).

[0012] The coefficient of performance (COP) is the amount of heat removed in the evaporator divided by the energy required to operate the compressor. The higher the COP, the higher the energy efficiency. The COP is directly related to the energy efficiency ratio (EER), which is an efficiency rating for refrigeration or air - conditioning equipment at a specific set of internal and external temperatures.

[0013] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", or any other variations thereof are intended to cover non - exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements and may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or". For example, the condition A or B is satisfied by any one of the following: namely, A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0014] When used in the present invention, "consists essentially of" is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements do not substantially affect the basic and novel features(plural) of the claimed invention, in particular the mechanism of operation for achieving any of the desired results of the processes of the present invention. The terms "consists essentially of" or "consisting essentially of" take an intermediate position between "includes" and "consists of".

[0015] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0016] As used herein, the term "approximately" means to take into account variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein, unless otherwise specified, are understood to be modified by the term "approximately," whether or not the term is explicitly used.

[0017] Where a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and / or preferred lower values, these shall be understood to specifically disclose all ranges formed by any pair of any upper or preferred upper range values ​​and any lower or preferred lower range values, regardless of whether the ranges are disclosed separately. Where a numerical range is described herein, unless otherwise indicated, this range is intended to encompass its endpoints and all integers and fractions within that range.

[0018] The following abbreviations may be used herein and will be readily understood by those skilled in the art. CFC: Chlorofluorocarbon COP: Performance Factor GWP: Global Warming Potential HFC: Hydrofluorocarbon HCFC: Hydrochlorofluorocarbon HCFO: Hydrochlorofluoroolefin HFO: Hydrofluoroolefin ODP: Ozone Depletion Potential R-32 or HFC-32: Difluoromethane R-125 or HFC-125: Pentafluoroethane R-134a or HFC-134a: 1,1,1,2-tetrafluoroethane R-152a or HFC-152a: 1,1-difluoroethane R-134 or HFC-134: 1,1,2,2-tetrafluoroethane R-227ea or HFC-227ea: 1,1,1,2,3,3,3-heptafluoropropane HFO-1336mzz or 1336mzz:1,1,1,4,4,4-hexafluorobuta-2-ene (mixture of isomers) HFO-1336mzz-(Z) or 1336mzz(Z):(Z)-1,1,1,4,4,4-hexafluorobuta-2-ene HFO-1336mzz-(E) or 1336mzz(E):(E)-1,1,1,4,4,4-hexafluorobuta-2-ene HFO-1225ye-(E) or 1225ye(E):(E)-1,2,3,3,3-pentafluoropropene HFO-1234yf or 1234yf:2,3,3,3-tetrafluoropropene HFO-1234ze or 1234ze: 1,3,3,3-tetrafluoropropene (a mixture of isomers) HFO-1234ze-(Z) or 1234ze(Z):(Z)-1,3,3,3-tetrafluoropropene HFO-1234ze-(E) or 1234ze(E):(E)-1,3,3,3-tetrafluoropropene HFO-1123 or 1123: Trifluoroethylene HFO-1243zf or 1243zf:3,3,3-trifluoropropene R-407A: A refrigerant blend designated by ASHRAE to contain R-32, R-125, and R-134a (in 20 / 20 / 40 weight percent, respectively). R-407C: A refrigerant blend designated by ASHRAE to contain R-32, R-125, and R-134a (in 23 / 25 / 52 weight percent, respectively). R-410A: A refrigerant blend designated by ASHRAE to contain R-32 and R-125 (in 50 / 50 weight percent, respectively). R-454A: A refrigerant blend designated by ASHRAE as containing R-32 and HFO-1234yf (each in 35 / 65 weight percent). R-454B: A refrigerant blend designated by ASHRAE as containing R-32 and HFO-1234yf (68.9 / 31.1 weight percent, respectively). R-454C: A refrigerant blend designated by ASHRAE to contain R-32 and R-HFO-1234yf (21.5 / 78.5 weight percent, respectively). R-449A: A refrigerant blend designated by ASHRAE to contain R-32, R-125, R-134a, and HFO-1234yf (24.3 / 24.7 / 25.7 / 25.3 weight percent, respectively). R-513A: A refrigerant blend designated by ASHRAE as containing R-134a and HFO-1234yf (each in 44 / 56 weight percent).

[0019] Process for preparing the composition of the present invention This application relates to a process for preparing a refrigerant blend containing one or more recovered hydrofluorocarbon compounds, (a) A process of recovering one or more hydrofluorocarbons from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A process comprising the step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 50 to form a refrigerant blend.

[0020] In some embodiments, one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

[0021] In some embodiments, the hydrofluorocarbon compound is difluoromethane (R-32).

[0022] In some embodiments, the hydrofluorocarbon compound is pentafluoroethane (R-125).

[0023] In some embodiments, the hydrofluorocarbon compound is 1,1,1,2-tetrafluoroethane (R-134a).

[0024] In some embodiments, the hydrofluorocarbon compound is 1,1-difluoroethane (HFC-152a).

[0025] In some embodiments, the hydrofluorocarbon compound is 1,1,2,2-tetrafluoroethane (HFC-134).

[0026] In some embodiments, the hydrofluorocarbon compound is 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

[0027] In some embodiments, the hydrofluorocarbon is a mixture of two or more hydrofluorocarbons selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

[0028] In some embodiments, the hydrofluorocarbon is a mixture of two, three, four, or five hydrofluorocarbons selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

[0029] In some embodiments, one or more hydrofluoroolefins have a global warming potential of less than about 40, less than about 30, less than about 20, less than about 10, less than about 5, less than about 2.5, or less than about 1.

[0030] In some embodiments, each of the one or more hydrofluoroolefins has an effective global warming potential of less than about 10. In some embodiments, each of the one or more hydrofluoroolefins has an effective global warming potential of less than about 2. In some embodiments, each of the one or more hydrofluoroolefins has an effective global warming potential of less than about 1.

[0031] In some embodiments, one or more hydrofluoroolefins have an effective global warming potential of about 1 to about 50, for example, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 1 to about 5, about 1 to about 2.5, about 2.5 to about 40, about 2.5 to about 30, about 2.5 to about 20, about 2.5 to about 10, about 2.5 to about 5, about 5 to about 40, about 5 to about 30, about 5 to about 20, about 5 to about 10, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 40, about 20 to about 30, or about 30 to about 40.

[0032] In some embodiments, one or more hydrofluoroolefins have a global warming potential of about 1 to about 10.

[0033] In some embodiments, one or more hydrofluoroolefins have a global warming potential of about 1 to about 5.

[0034] In some embodiments, one or more hydrofluoroolefins have a global warming potential of about 0.1 to about 1.

[0035] In some embodiments, each of the one or more purified refrigerant (either hydrofluorocarbon or hydrofluoroolefin) compounds has an effective global warming potential of less than 5, for example, less than 4, less than 3, less than 2, less than 1, or less than 0.1.

[0036] In some embodiments, each of the one or more purified refrigerant compounds has an effective global warming potential of about 0 to about 5, for example, about 0 to about 4, about 0 to about 3, about 0 to about 2, and about 0 to about 1.

[0037] In some embodiments, each of the one or more purified refrigerant compounds has an effective global warming potential of about 0.

[0038] In some embodiments of the processes described herein, step (b) is performed one or more times before the mixing in step (c).

[0039] In some embodiments, step (b) is performed one or more times using one or more purification techniques, which may be the same or different.

[0040] In some embodiments, one or more purified hydrofluorocarbon compounds exhibit a purity improvement of about 1 to about 99.9% compared to one or more hydrofluorocarbons before performing step (b), for example, about 1 to about 95%, about 1 to about 90%, about 1 to about 75%, about 1 to about 50%, about 1 to about 25%, about 1 to about 10%, about 10 to about 95%, about 10 to about 90%, about 10 to about 75%, about 10 to about 50%, about 10 to about 25%, about 25 to about 95%, about 25 to about 90%, about 25 to about 75%, about 25 to about 50%, about 50 to about 95%, about 50 to about 90%, about 50 to about 75%, about 75 to about 95%, and about 75 to about 90% compared to one or more hydrofluorocarbons before performing step (b).

[0041] For example, one or more purified hydrofluorocarbon compounds contain impurities (i.e., contaminants) in amounts below the maximum permissible level of contaminants as described in AHRI Standard 700-2017 Specification for Refrigerants, the entire disclosure of which is incorporated herein by reference.

[0042] For example, one or more purified hydrofluorocarbon compounds contain one or more impurities (i.e., contaminants) below the maximum permissible level, including air and other noncondensables, water, volatile impurities, particulate matter / solids, and chlorides. Noncondensables may include, but are not limited to, oxygen, nitrogen, carbon dioxide, helium, argon, or any combination thereof.

[0043] For example, one or more purified hydrofluorocarbon compounds contain a total amount of impurities (i.e., contaminants) below the maximum permissible level of any of the contaminants listed in any one of Tables 1 to 8 provided herein and in the AHRI Standard 700-2017 Specification for Refrigerants, the entire disclosure of which is incorporated herein by reference.

[0044] [Table 1]

[0045] [Table 2]

[0046] [Table 3]

[0047] [Table 4]

[0048] [Table 5]

[0049] [Table 6]

[0050] [Table 7]

[0051] [Table 8]

[0052] [Table 9]

[0053] [Table 10]

[0054] [Table 11]

[0055] [Table 12] In some embodiments, the processes provided herein are (d) Further comprising the step of recovering one or more hydrofluoroolefins from one or more refrigeration, air conditioning, or heat pump systems.

[0056] In some embodiments, step (d) is performed before the blending in step (c).

[0057] In some embodiments, the processes provided herein are (e) Further comprising the step of purifying one or more hydrofluoroolefins to form one or more purified hydrofluoroolefins.

[0058] In some embodiments, step (e) is performed before the blending in step (c).

[0059] In some embodiments, the processes provided herein are (d) A step of recovering one or more hydrofluoroolefins from one or more refrigeration, air conditioning, or heat pump systems, (e) A step of purifying one or more hydrofluoroolefins to form one or more purified hydrofluoroolefins, further comprising this step.

[0060] In some embodiments, steps (d) and (e) are performed before the blending in step (c), respectively.

[0061] In some embodiments, one or more purified hydrofluoroolefin compounds exhibit a purity improvement of about 1 to about 99.9% compared to one or more hydrofluoroolefins before performing step (b), for example, about 1 to about 95%, about 1 to about 90%, about 1 to about 75%, about 1 to about 50%, about 1 to about 25%, about 1 to about 10%, about 10 to about 95%, about 10 to about 90%, about 10 to about 75%, about 10 to about 50%, about 10 to about 25%, about 25 to about 95%, about 25 to about 90%, about 25 to about 75%, about 25 to about 50%, about 50 to about 95%, about 50 to about 90%, about 50 to about 75%, about 75 to about 95%, and about 75 to about 90% compared to one or more hydrofluoroolefins before performing step (b).

[0062] For example, one or more purified hydrofluoroolefin compounds contain impurities (i.e., contaminants) in amounts below the maximum permissible level of contaminants as described in AHRI Standard 700-2017 Specification for Refrigerants, the entire disclosure of which is incorporated herein by reference.

[0063] For example, one or more purified hydrofluoroolefin compounds contain one or more impurities (i.e., contaminants) below the maximum permissible level, including air and other noncondensables, water, volatile impurities, particulate matter / solids, and chlorides.

[0064] For example, one or more purified hydrofluoroolefin compounds contain a total amount of impurities (i.e., contaminants) below the maximum permissible level of any of the contaminants listed in any one of Tables 1 to 8 provided herein and in the AHRI Standard 700-2017 Specification for Refrigerants, the entire disclosure of which is incorporated herein by reference.

[0065] One or more hydrofluoroolefins are selected from the group consisting of (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)), (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)), trifluoroethylene (HFO-1123), (E)1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)), and 3,3,3-trifluoropropene (HFO-1243zf), or any mixture thereof.

[0066] In some embodiments, the hydrofluorocarbon compound is difluoromethane (R-32).

[0067] In some embodiments, the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0068] In some embodiments, the hydrofluoroolefin is (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)).

[0069] In some embodiments, the hydrofluoroolefin is (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)).

[0070] In some embodiments, the hydrofluoroolefin is (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)).

[0071] In some embodiments, the hydrofluoroolefin is trifluoroethylene (HFO-1123).

[0072] In some embodiments, the hydrofluoroolefin is (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)).

[0073] In some embodiments, the hydrofluoroolefin is 3,3,3-trifluoropropene (HFO-1243zf).

[0074] In some embodiments, the hydrofluoroolefin is a mixture of any two or more hydrofluoroolefins selected from (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)), (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)), trifluoroethylene (HFO-1123), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)), and 3,3,3-trifluoropropene (HFO-1243zf).

[0075] In some embodiments, the mixture is any two, three, four, or five hydrofluoroolefins selected from (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)), (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)), trifluoroethylene (HFO-1123), (E)1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)), and 3,3,3-trifluoropropene (HFO-1243zf).

[0076] In some embodiments, the hydrofluorocarbon is a mixture of difluoromethane (R-32) and pentafluoroethane (R-125).

[0077] In some embodiments, the hydrofluorocarbon is a mixture of difluoromethane (R-32), pentafluoroethane (R-125), and 1,1,1,2-tetrafluoroethane (R-134a).

[0078] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 21-22 weight percent purified difluoromethane (R-32), and It contains approximately 78-79% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0079] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 21-22 weight percent purified difluoromethane (R-32), and It essentially consists of approximately 78-79 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0080] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 21-22 weight percent purified difluoromethane (R-32), and It consists of approximately 78-79% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0081] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 68-69 weight percent purified difluoromethane (R-32), It contains approximately 30 to 31 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0082] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 68-69 weight percent purified difluoromethane (R-32), It essentially consists of approximately 30 to 31 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0083] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 68-69 weight percent purified difluoromethane (R-32), It consists of approximately 30 to 31 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0084] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 34 to 36 weight percent of purified difluoromethane (R-32), It contains approximately 64 to 66 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0085] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 34 to 36 weight percent of purified difluoromethane (R-32), It essentially consists of approximately 64 to 66 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0086] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 34 to 36 weight percent of purified difluoromethane (R-32), It consists of approximately 64 to 66 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0087] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 66-68 weight percent purified difluoromethane (R-32), Approximately 6 to 8 weight percent of purified pentafluoroethane (R-125), It contains approximately 25 to 27 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0088] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 66-68 weight percent purified difluoromethane (R-32), Approximately 6 to 8 weight percent of purified pentafluoroethane (R-125), It essentially consists of approximately 25 to 27 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0089] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 66-68 weight percent purified difluoromethane (R-32), Approximately 6 to 8 weight percent of purified pentafluoroethane (R-125), It consists of approximately 25 to 27 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0090] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 24-25 weight percent purified difluoromethane (R-32), Approximately 24-25 weight percent of purified pentafluoroethane (R-125), Approximately 25-26 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It contains approximately 25 to 26 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0091] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 24-25 weight percent purified difluoromethane (R-32), Approximately 24-25 weight percent of purified pentafluoroethane (R-125), Approximately 25-26 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It essentially consists of approximately 25-26 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0092] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 24-25 weight percent purified difluoromethane (R-32), Approximately 24-25 weight percent of purified pentafluoroethane (R-125), Approximately 25-26 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It consists of approximately 25 to 26 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0093] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 43 to 45 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It contains approximately 55 to 57 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0094] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 43 to 45 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It essentially consists of approximately 55 to 57 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0095] In some embodiments, the refrigerant blend prepared according to the process described herein is Approximately 43 to 45 weight percent of purified 1,1,1,2-tetrafluoroethane (R-134a), It consists of approximately 55 to 57 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0096] In some embodiments of the processes described herein, the purification of step (b) includes removing solid impurities from one or more hydrofluorocarbon compounds.

[0097] In some embodiments, solid impurities are removed by one or more purification techniques selected independently of filtration. Types or methods of filtration include pressure, vacuum, membrane centrifugation, gravity, deep filtration, granular bed, cartridge filtration using carbon, fiber, or metal, and pre-coat filtration. Filtration is particularly useful for removing metal particles and solid particles such as insoluble polymers, plastics, and elastomers.

[0098] In some embodiments, the purification in step (b) includes removing liquid impurities, gaseous impurities, or a combination thereof from one or more hydrofluorocarbon compounds.

[0099] In some embodiments, liquid impurities, gaseous impurities, or combinations thereof are removed by one or more purification techniques independently selected from distillation, decantation, contact with molecular sieves, and vapor space purging. Molecular sieves are particularly useful for water removal for air removal and vapor space purging. Distillation and decantation are effective for removing organic, oligomeric, and soluble polymer impurities.

[0100] In some embodiments, the purification in step (e) includes removing solid impurities from one or more hydrofluoroolefins.

[0101] In some embodiments, solid impurities are removed by one or more purification techniques independently selected from pressure filtration, vacuum filtration, membrane centrifugation filtration, gravity filtration, deep filter filtration, granular bed filtration, cartridge filtration using carbon, fiber, or metal filtration, and pre-coat filtration.

[0102] In some embodiments, the purification in step (e) includes removing liquid impurities, gaseous impurities, or a combination thereof from one or more hydrofluoroolefins.

[0103] In some embodiments, liquid impurities, gaseous impurities, or combinations thereof are removed by one or more purification techniques, independently selected from distillation, contact with molecular sieves, and vapor space purging.

[0104] In some embodiments, the present application relates to a process for reducing the global warming potential of a refrigerant blend, (a) A step of selecting one or more hydrofluorocarbons recovered from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 50 to form a purified refrigerant blend, The purified refrigerant blend has a lower global warming potential compared to a refrigerant blend containing one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). The present invention further provides a process in which one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

[0105] In some embodiments, the refrigerant blend has an effective global warming potential of about 5% or less, for example, about 10% or less, about 20% or less, about 30% or less, about 40% or less, about 50% or less, about 60% or less, about 70% or less, about 80% or less, about 90% or less, or about 99% or less, compared to the GWP of a refrigerant blend comprising one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c).

[0106] In some embodiments, the purified refrigerant blend has an effective global warming potential of about 5% or less compared to a refrigerant blend containing one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c).

[0107] In some embodiments, the refrigerant blend has a global warming potential of about 1% or less compared to a refrigerant blend comprising one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c).

[0108] In some embodiments, the refrigerant blend has an effective global warming potential of about 5% to about 99% of the GWP of the refrigerant blend, which comprises one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c), for example, about 5% to about 90%, about 5% to about 80%, about 5% to about 70%, about 5% to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, or about 5% to about 10%.

[0109] How to use Compositions prepared according to the processes described herein can act as working fluids used to transfer heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles in which a fluid undergoes a phase transition, i.e., a cycle in which a fluid changes from liquid to gas and then back to liquid, or vice versa. Exemplary heat transfer systems include, but are not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, coolers (e.g., water chillers, full-liquid evaporator coolers, direct expansion coolers, centrifugal coolers), walk-in coolers, high-temperature heat pumps, mobile refrigerators, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof.

[0110] Mechanical vapor-compression refrigeration, air conditioning, and heat pump systems include evaporators, compressors, condensers, and expansion devices. A refrigeration cycle reuses a refrigerant in multiple processes, producing a cooling effect in one process and a heating effect in a different process. The cycle can be described as follows: Liquid refrigerant enters the evaporator through an expansion device, where it boils in the evaporator at a low temperature, absorbing heat from the environment to form a gas and produce cooling. Often, air or a heat transfer fluid flows over or around the evaporator, transferring the cooling effect produced by the evaporation of the refrigerant in the evaporator to the object being cooled. The low-pressure gas enters the compressor, where it is compressed and its pressure and temperature increase. The high-pressure (compressed) gaseous refrigerant then enters the condenser, where it condenses and releases its heat into the environment. The refrigerant returns to the expansion device, through which the liquid expands from the higher pressure level in the condenser to the lower pressure level in the evaporator, thus repeating the cycle.

[0111] An object to be cooled or heated can be defined as any space, place, thing, or object for which cooling or heating is desirable. Examples include rooms, apartments, or buildings (open or enclosed) that require air conditioning, cooling, or heating, such as apartment buildings, university dormitories, single-family homes or other annexed houses or single-person residences, hospitals, office buildings, supermarkets, classrooms or administrative buildings of colleges or universities, and passenger compartments of automobiles or trucks. Furthermore, electronic devices such as computer equipment, central processing units (CPUs), data centers, server banks, and personal computers can be cited as examples of objects to be cooled.

[0112] "Nearby" means that the evaporator of a system containing a refrigerant composition is located either inside or in close proximity to the object being cooled, so that the air moved through the evaporator moves inside or around the object being cooled. In processes that produce heating, "nearby" means that the condenser of a system containing a refrigerant composition is located either inside or in close proximity to the object being heated, so that the air moved through the evaporator moves inside or around the object being heated. In some embodiments, for heat transfer, "nearby" may mean, for example, that the object being cooled is directly immersed in the heat transfer composition, or that a tube containing the heat transfer composition flows inside or around it, for example, out of an electronic device.

[0113] Examples of refrigeration systems in which the compositions provided herein may be useful include commercial, industrial, or residential refrigerators and freezers, ice makers, built-in coolers and freezers, full-liquid evaporator coolers, direct expansion coolers, screw coolers, scroll coolers, centrifugal coolers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the compositions provided herein may be used in supermarket refrigeration systems. Furthermore, stationary applications may utilize a secondary loop system in which a primary refrigerant is used to generate cooling at one location, and this cooling is then transferred to a remote location via a secondary heat transfer fluid.

[0114] In some embodiments, the compositions provided herein are useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices. In some embodiments, the compositions provided herein are useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices.

[0115] As used herein, a mobile refrigerator, air conditioning, or heat pump system refers to any refrigeration, air conditioning, or heat pump device incorporated into a road, rail, sea, or air transport unit. Mobile air conditioning or heat pump systems may be used in automobiles, trucks, trains, or other transport systems. In particular, mobile heat pumps may be useful in hybrid or electric vehicles that do not have a combustion engine to generate heat. Mobile refrigerators may include transport refrigerators for trucks, airplanes, or trains. Furthermore, devices intended to provide refrigeration to any mobile carrier-independent system, known as a “multimodal transport” system, are included in the present invention. Such multimodal transport systems include “containers” (e.g., sea / land multimodal transport) and “swap bodies” (e.g., road and rail multimodal transport).

[0116] As used herein, a fixed air conditioning or heat pump system is a system that is fixed in place during operation. Fixed air conditioning or heat pump systems may be associated with or installed in any of various buildings. These fixed applications may include, but are not limited to, fixed air conditioning and heat pumps, including coolers, heat pumps including residential and high-temperature heat pumps, residential, commercial, or industrial air conditioning systems, and windowed package terminals connected to buildings such as rooftop systems, with or without ducts, and their exteriors.

[0117] Fixed heat transfer can refer to systems for cooling electronic equipment, such as immersion cooling systems, water immersion cooling systems, phase transition cooling systems, data center cooling systems, or simply liquid cooling systems.

[0118] In some embodiments, a method is provided for using the compound or composition of the present invention as a heat transfer fluid. The method includes the step of transporting the composition from a heat source to a heat sink.

[0119] In some embodiments, a method is provided for generating cooling, comprising the steps of evaporating one of the compositions disclosed herein in the vicinity of an object to be cooled, and then condensing the composition.

[0120] In some embodiments, a method is provided for generating heating, comprising the steps of condensing one of the compositions disclosed herein in the vicinity of an object to be heated, and then evaporating the composition.

[0121] In some embodiments, the compositions provided herein are useful in heat transfer applications, and the working fluid is the heat transfer component. Preferably, the composition for use as the heat transfer component has a boiling point range of -60°C to 300°C.

[0122] In some embodiments, the compositions provided herein are for use in refrigeration or air conditioning. Preferably, compositions for use as refrigerants or air conditioning components have a boiling point range of -80°C to 35°C. In some cooling applications, the boiling point range is preferably 0°C to 35°C.

[0123] The compounds or compositions disclosed herein include, in particular, R-123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R-11 (or CFC-11, trichlorofluoromethane), R-12 (or CFC-12, dichlorodifluoromethane), HFC-134a (1,1,1,2-tetratrifluoroethane), HFC-32 (difluoromethane), R-22 (chlorodifluoromethane), R-245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane). These may be useful as substitutes for currently used (e.g., "currently in use") refrigerants, including but not limited to R-114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R-236ea (or HFC-236ea, 1,1,1,2,3,3-hexafluoropropane), and R-124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane).

[0124] As used herein, the term “current refrigerant” is understood to mean the refrigerant for which a heat transfer system is designed to operate, or the refrigerant present within a heat transfer system.

[0125] In many cases, alternative refrigerants are most useful when they can be used for different refrigerants, for example, in the initial cooling system designed with minimal to no system changes. In many applications, some embodiments of the disclosed compositions are useful as refrigerants and provide at least equivalent cooling performance (meaning cooling capacity) to the refrigerant for which a substitute is needed.

[0126] Refrigeration capacity (sometimes called cooling capacity) is a term that defines the change in enthalpy of the refrigerant or working fluid in an evaporator per unit mass of circulating refrigerant or working fluid. Volumetric cooling capacity refers to the amount of heat removed by the refrigerant or working fluid per unit volume of refrigerant vapor leaving the evaporator. Refrigeration capacity is a measure of the ability of a refrigerant, working fluid, or heat transfer composition to produce cooling. Therefore, the higher the volumetric cooling capacity of the working fluid, the greater the cooling rate that can be produced in an evaporator with the maximum volumetric flow rate achievable by a given compressor. Cooling rate refers to the amount of heat removed per unit time by the refrigerant in the evaporator.

[0127] Similarly, volumetric heating capacity is a term that defines the amount of heat supplied by the refrigerant or working fluid in the condenser per unit volume of refrigerant or working fluid vapor entering the compressor. The higher the volumetric heating capacity of the refrigerant or working fluid, the greater the heating rate produced in the condenser with the maximum volumetric flow rate achievable by a given compressor.

[0128] In some embodiments, the application provides a method for operating a heat transfer system designed to operate with a current refrigerant or for transferring heat by filling an empty system with a composition disclosed herein or by substantially replacing the current refrigerant with a composition disclosed herein.

[0129] As used herein, the term “substantially replace” is understood to mean draining the active refrigerant from the system or pumping the active refrigerant out of the system and then filling the system with the compositions disclosed herein. The system may be flushed with one or more amounts of replacement refrigerant before filling. In some embodiments, it is understood that some small amount of active refrigerant may remain in the system even after the system has been filled with the compositions provided herein.

[0130] In another embodiment, a method is provided for refilling a heat transfer system containing a refrigerant and a lubricant, comprising the steps of: substantially removing the refrigerant from the heat transfer system while retaining a substantial portion of the lubricant in the system; and introducing one of the compositions provided herein into the heat transfer system. In certain embodiments, the lubricant in the system is partially replaced.

[0131] As used herein, the term “lubricant” means any composition or any material added to a compressor (and in contact with any heat transfer composition in use within any heat transfer system) that provides lubrication to the compressor to help prevent seizing of parts.

[0132] In some embodiments, the compositions provided herein may be used to replenish the refrigerant in a cooler. For example, if the performance of a cooler using R-449A deteriorates due to refrigerant leakage, the compositions disclosed herein may be added to the cooler to restore its performance to its original specifications.

[0133] In some embodiments, a heat exchange system is provided that contains any of the compositions of the Disclosure, selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, full-liquid evaporator coolers, direct expansion coolers, screw coolers, scroll coolers, centrifugal coolers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof. Furthermore, the compositions provided herein may be useful in a secondary loop system in which these compositions function as primary refrigerants to provide cooling for a secondary heat transfer fluid, and this secondary heat transfer fluid cools a remote area.

[0134] The compositions provided herein may have some temperature gradient in the heat exchangers described herein. This allows the system to operate more efficiently when the heat exchanger is operating in a counterflow mode or a transverse flow mode with a counterflow tendency. A counterflow tendency means that the closer the heat exchanger is to a counterflow mode, the more efficient the heat transfer is. Therefore, air conditioning heat exchangers, in particular evaporators, are designed to provide several embodiments of counterflow characteristics.

[0135] Accordingly, the following systems are provided herein: an air conditioning or heat pump system comprising one or more heat exchangers (e.g., evaporators, condensers, or both) operating in a counterflow mode or a transverse flow mode with a counterflow tendency.

[0136] In some embodiments, a refrigeration system is provided herein that includes one or more heat exchangers (e.g., evaporators, condensers, or both) operating in a countercurrent mode or a transverse mode with a countercurrent tendency.

[0137] In some embodiments, the refrigeration, air conditioning, or heat pump system is a stationary refrigeration, air conditioning, or heat pump system. In some embodiments, the refrigeration, air conditioning, or heat pump system is a mobile refrigeration, air conditioning, or heat pump system.

[0138] Furthermore, in some embodiments, the compositions disclosed herein may function as primary refrigerants in secondary loop systems that provide cooling to a remote location by using secondary heat transfer fluids that may include water, saline solutions (e.g., calcium chloride), glycols, carbon dioxide, or fluorinated hydrocarbon fluids (e.g., HFCs, HCFCs, HFOs, HCFOs, CFOs, or PFCs). In this case, the secondary heat transfer fluid is the object being cooled, as it is adjacent to the evaporator and cooled before being transferred to the second remote object being cooled. In some embodiments, the compositions disclosed herein may function as secondary heat transfer fluids and thus transmit or provide cooling (or heating) to a remote location.

[0139] In some embodiments, the compositions provided herein include one or more non-refrigerant components (also referred to herein as additives) selected from the group consisting of lubricants, dyes (e.g., ultraviolet dyes), solubilizers, compatibilizers, stabilizers, tracers, perfluoropolyethers, anti-wear agents, extreme pressure additives, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof. In practice, many of these arbitrary non-refrigerant components may conform to one or more of these categories and possess qualities that help them achieve one or more performance characteristics.

[0140] In some embodiments, one or more non-refrigerant components are present in small amounts relative to the overall composition. In some embodiments, the concentration of additives(s) in the disclosed composition is between less than about 0.1 weight percent and about 5 weight percent of the total composition. In some embodiments of the present invention, additives are present in the disclosed composition in amounts of about 0.1 weight percent to about 5 weight percent, or about 0.1 weight percent to about 3.5 weight percent, of the total composition. The additive components(s) selected for the disclosed composition are selected based on practicality and / or the requirements of individual equipment components or systems.

[0141] In some embodiments, the lubricant is selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, silicone, silicate ester, phosphate ester, paraffin, naphthene, polyalpha-olefin, and combinations thereof.

[0142] The lubricants disclosed herein may be commercially available lubricants. For example, the lubricants include paraffinic mineral oil sold by BVA Oil as BVM100N, naphthenic mineral oil sold by Crompton Co. under the trademarks Suniso® 1GS, Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzene sold by Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500, branched alkylbenzene sold by Nippon Oil as HAB22, polyol ester (POE) sold by Castrol, United Kingdom under the trademark Castrol® 100, and Dow (Dow Polyalkylene glycols (PAGs) such as RL-488A from Chemical, Midland, Michigan, or mixtures thereof may also be used.

[0143] Despite the above weight ratios of the compositions disclosed herein, it is understood that in some heat transfer systems, additional lubricants may be obtained from one or more equipment components of such heat transfer systems while the compositions are in use. For example, in some refrigeration, air conditioning, and heat pump systems, lubricants may be filled into the compressor and / or compressor lubricant sump. Such lubricants are present in the refrigerant of such systems, in addition to any lubricating additives. While in use and present in the compressor, the refrigerant composition may capture a certain amount of equipment lubricant, thereby altering the refrigerant-lubricant composition from its starting ratio.

[0144] Non-refrigerant components used with the compositions of the present invention may include at least one dye. In some embodiments, the dye includes at least one ultraviolet (UV) dye. As used herein, “ultraviolet” dyes are defined as ultraviolet fluorescent or phosphorescent compositions that absorb light in the ultraviolet or “near” ultraviolet region of the electromagnetic spectrum. Fluorescence produced by ultraviolet fluorescent dyes can be detected under ultraviolet irradiation that emits at least some radiation having wavelengths in the range of about 10 nanometers to about 775 nanometers.

[0145] Ultraviolet dyes are useful components for detecting leakage of a composition because their fluorescence can be observed at or near the point of leakage within a device (e.g., a refrigeration unit, air conditioner, or heat pump). Ultraviolet emission (e.g., fluorescence from the dye) can be observed under ultraviolet light. Therefore, if a composition containing such an ultraviolet dye leaks from a given point in the device, fluorescence can be detected at or near the point of leakage.

[0146] In some embodiments, the ultraviolet dye may be a fluorescent dye. In some embodiments, the fluorescent dye is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and any mixture thereof.

[0147] In some embodiments, the compositions of the present invention include at least one solubilizer. In some embodiments, the solubilizer is selected to improve the solubility of one or more dyes in the composition of disclosure. In some embodiments, the weight ratio of dyes to solubilizer in the composition is in the range of about 99:1 to about 1:1. Exemplary solubilizers include, but are not limited to, at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and any mixtures thereof.

[0148] In some embodiments, the non-refrigerant component includes at least one compatibilizer. As used herein, the term “compatibilizer” refers to a compound that improves the solubility of the hydrofluorocarbons of the disclosed composition in a heat transfer system lubricant. In some embodiments, the compatibilizer improves oil return to the compressor. In some embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

[0149] In some embodiments, the non-refrigerant component includes at least one compatibilizer to improve the compatibility of one or more lubricants with the composition of disclosure. In some embodiments, the compatibilizer is selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and any mixtures thereof.

[0150] In some embodiments, the solubilizer and / or compatibilizer is selected from the group consisting of hydrocarbon ethers. In some embodiments, the hydrocarbon ether consists of an ether containing only carbon, hydrogen, and oxygen, such as dimethyl ether (DME).

[0151] In some embodiments, the compatibilizer can be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing 3 to 15 carbon atoms. In some embodiments, the compatibilizer includes at least one hydrocarbon selected from the group consisting of propane including propylene and propane, butane including n - butane and isobutane, pentane including n - pentane, isopentane, neopentane, and cyclopentane, hexane, octane, nonane, decane, and the like. In some embodiments, the compatibilizer is one sold under the trade name Isopar® H by Exxon Chemical (USA), a mixture of undecane (C 11 ) and dodecane (C 12 ) (high purity C 11 ~C 12 iso - paraffin), Aromatic150 (C9 - C 11 aromatic) (Aromatic200 (C9 - C 15 aromatic) and Naptha140 (C5 - C 11 mixture of paraffin, naphthene, and aromatic hydrocarbon), and commercially available hydrocarbons including but not limited to these mixtures.

[0152] In some embodiments, the compatibilizer may include at least one polymer compatibilizer. In some embodiments, the polymer compatibilizer can be a random copolymer of fluorinated acrylate and non - fluorinated acrylate, and this polymer includes 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, and R1 , R 3 , and R 5 However, R is independently selected from the group consisting of H and C1-C4 alkyl radicals. 2 , R 4 , and R 6 However, it is independently selected from the group consisting of carbon chain radicals containing C and F, and may further contain H, Cl, ether oxygen, or sulfur in the form of thioethers, sulfoxides, or sulfones, and mixtures thereof). An example of such a polymer compatibilizer is the one commercially available under the trademark name Zonyl® PHS from EIdu Pont de Nemours and Company (Wilmington, DE, 19898, USA). Zonyl® PHS contains 40% by weight of CH2=C(CH3)CO2CH2CH2(CF2CF2) m F (also known as Zonyl(registered trademark) fluoromethacrylate or ZFM), where m is 1 to 12, mainly 2 to 8, and 60% by weight of lauryl methacrylate (CH2=C(CH3)CO2(CH2) 11 It is a random copolymer produced by polymerizing CH3 (also known as LMA).

[0153] In some embodiments, the compatibilizer component contains approximately 0.01 to 30% by weight of additives (based on the total amount of compatibilizer) that reduce the surface energy of metallic copper, aluminum, steel, or other metals and their alloys found in the heat exchanger by reducing the lubricant's adhesion to the metal. Examples of additives that reduce metal surface energy include those commercially available from DuPont under the trademark names Zonyl®FSA, Zonyl®FSP, and Zonyl®FSJ.

[0154] In some embodiments, the compositions provided herein further comprise a non-refrigerant component that is a metal surface deactivator. In some embodiments, the metal surface deactivator is selected from the group consisting of areoxalyl bis(benzylidene)hydrazide (CAS Registry No. 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS Registry No. 32687-78-8), 2,2,'-oxamide bis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (CAS Registry No. 70331-94-1), N,N'-(disalicyclidene)-1,2-diaminopropane (CAS Registry No. 94-91-7), ethylenediaminetetraacetic acid (CAS Registry No. 60-00-4), or salts of any of the above, and mixtures thereof.

[0155] The non-refrigerant components provided herein may further include stabilizers selected from the group consisting of hindered phenols, thiophosphates, butylated triphenyl phosphorothionates, organophosphates, organophosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethanes, alkylsilanes, benzophenone derivatives, aryl sulfides, divinylterephthalic acid, diphenylterephthalic acid, hydrazones such as acetaldehyde dimethylhydrazone, ionic liquids, and mixtures thereof.

[0156] In some embodiments, the stabilizers include tocopherol; hydroquinone; t-butylhydroquinone; monothiophosphate; and dithiophosphate (commercially available from Ciba Specialty Chemicals, Basel, Switzerland (hereinafter "Ciba") under the trademark name Irgalube® 63); dialkylthiophosphate (commercially available from Ciba under the trademark names Irgalube® 353 and Irgalube® 350, respectively); butylated triphenylphosphorothionate (commercially available from Ciba under the trademark name Irgalube® 232); and amine phosphate (commercially available from Ciba under the trademark name Irgalube® 349 (Cib a) commercially available as); hindered phosphite (commercially available from Ciba as Irgafos® 168), and tris-(di-tert-butylphenyl) phosphite (commercially available from Ciba as Irgafos® OPH); (Di-n-octyl phosphite); and isodecyldiphenyl phosphite (commercially available from Ciba as Irgafos® DDPP); trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, and Trialkyl phosphates such as tri(2-ethylhexyl) phosphate; triaryl phosphates containing triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate, and mixed alkylaryl phosphates containing isopropylphenyl phosphate (IPPP) and bis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenyl phosphates such as Syn-O-Ad® 8784 and other products marketed under the trademark name Syn-O-Ad®. phosphate; tert-butylated triphenyl phosphate, such as the one marketed under the trademark name Durad® 620; isopropyltriphenyl phosphate, such as the one marketed under the trademark names Durad® 220 and Durad® 110; anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; myrcene, allocimene, limonene (especially d-limonene); retinal; pinene; menthol; geraniol; farnesol;Phytol; Vitamin A; Terpinene; δ-3-carene; Terpinolene; Phellandrene; Fenchen; Dipentene; Caratenoids such as lycopene, β-carotene, and xanthophylls such as zeaxanthin; Retinoids such as hepaxanthin and isotretinoin; Bornane; 1,2-Propylene oxide; 1,2-Butylene oxide; n-Butyl glycidyl ether; Trifluoromethyloxirane; 1,1-Bis(trifluoromethyl)oxirane; 3-Ethyl-3-Hydroxymethyl-Oxetane (e.g., OXT-101 (Toagosei Co.,Ltd)); 3-Ethyl-3-((Phenoxy)methyl)-Oxetane (e.g., OXT-211 (Toagosei Co.,Ltd)); 3-Ethyl-3-((2-Ethyl-hexyloxy)methyl)-Oxetane (e.g., OXT-212 (Toagosei Co.,Ltd)); Co., Ltd.); Ascorbic acid; Methanethiol (methyl mercaptan); Ethanethiol (ethyl mercaptan); Coenzyme A; Dimercaptosuccinate (DMSA); Grapefruit mercaptan ((R)-2-(4-methylcyclohexa-3-enyl)propane-2-thiol)); Cysteine ​​((R)-2-amino-3-sulfanyl-propanoic acid); Lipoamide (1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or 3,4)-dimethylphenyl]-2(3H)-benzofuranone (commercially traded by Ciba as Irganox® HP-136); Benzylphenyl sulfide; Diph Phenyl sulfide; diisopropylamine; dioctadecyl 3,3'-thiodipropionate, marketed by Ciba under the trademark name Irganox® PS802 (Ciba); didodecyl 3,3'-thiopropionate (marketed by Ciba under the trademark name Irganox® PS800); di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (marketed by Ciba under the trademark name Tinuvin® 770); poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate, marketed by Ciba under the trademark name Tinuvin® 622LD (Ciba)); methylbistaloamine;Selected from the group consisting of bistaloamine; phenol-α-naphthylamine; bis(dimethylamino)methylsilane (DMAMS); tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane; vinyltrimethoxysilane; 2,5-difluorobenzophenone; 2',5'-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone; benzylphenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionic liquids; and any mixture thereof.

[0157] In some embodiments, the compositions provided herein further include an additive which is an ionic liquid stabilizer. In some embodiments, the ionic liquid stabilizer is selected from the group consisting of organic salts that are liquid at room temperature (about 25°C). In other embodiments, the organic salt is a cation selected from the group consisting of pyridinium, pyridazinium, pyrimidinium, pyradium, imidazolium, pyrazolium, thiazolium, oxazolium, and triazolium, and any mixture thereof, and BF4 - PF6 - SbF6 - CF3SO3 - (HCF2CF2SO3) - (CF3HFCCF2SO3) - (HCClFCF2SO3) - [(CF3SO2)2N] - [(CF3CF2SO2)2N] - [(CF3SO2)3C] - (CF3CO2) - , and F -The ionic liquid stabilizer comprises an anion selected from the group consisting of , and any mixture thereof. In some embodiments, the ionic liquid stabilizer is selected from the group consisting of emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate), bmim BF4 (1-butyl-3-methylimidazolium tetraborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma-Aldrich).

[0158] In some embodiments, the compositions provided herein further comprise a stabilizer which is a hindered phenol. In some embodiments, the hindered phenol is hydroquinone and alkylated hydroquinone, including t-butylhydroquinone, other derivatives of hydroquinone, such as 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; tocopherol; hydroxylated thiodiphenyl ethers including 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis Alkylidene-bisphenols containing 4,4'-methylenebis(2,6-di-tert-butylphenol), such as (3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenoldiol derivatives; 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-biphenyldiol (2,2'-methylenebis(4-ethyl-6-tert-butylphenol), etc.); Butyl Acylaminophenols such as hydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol), bisphenols containing heteroatoms including (2,6-di-tert-alpha-dimethylamino-p-cresol, 4,4-thiobis(6-tert-butyl-m-cresol); 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); and sulfides such as bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide;This is any substituted phenol compound containing one or more substituted or cyclic, linear, or branched aliphatic substituents, such as bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and alkylated monophenols containing any mixture thereof.

[0159] In some embodiments, the compositions provided herein further include a non-refrigerant component that is a tracer. In some embodiments, the tracer includes two or more tracer compounds, either of the same classification or different classifications. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm, based on the weight of the entire composition. In other embodiments, the tracer is present in the composition at a total concentration of about 50 ppm to about 500 ppm. In some embodiments, the tracer is present in the composition at a total concentration of about 100 ppm to about 300 ppm.

[0160] In some embodiments, the tracer is selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodate compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof. In some embodiments, the tracer is selected from the group consisting of fluoroethane, 1,1,-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tridecafluoroheptane, iodotrifluoromethane, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O), and any mixtures thereof. In some embodiments, the tracer may be added to the composition of the present invention in a predetermined amount to enable detection of any dilution, contamination, or other alteration of the composition.

[0161] In some embodiments, the compositions provided herein further include an additive which is a perfluoropolyether described in U.S. Patent Publication No. 2007-0284555, the disclosure of which is incorporated herein by reference in its entirety.

[0162] It will be recognized that certain additives referred herein as suitable for non-refrigerant components are identified as potential refrigerants. However, according to the present invention, when these additives are used, they are not present in amounts that would affect the novel and fundamental characteristics of the refrigerant mixture of the present invention.

[0163] As described herein, compositions prepared according to the process of the present invention have zero ozone depletion potential and a low global warming potential (GWP). Furthermore, the compositions provided in the present invention may have a lower global warming potential than many hydrofluorocarbon refrigerants currently in use. Accordingly, according to the present invention, the compositions described herein may be useful in methods for producing cooling, methods for producing heating, and methods for transferring heat. [Examples]

[0164] The present invention will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way.

[0165] Example 1. Preparation of a composition having reduced effective GWP Since GWP is a measure of how much energy is absorbed by one ton of gas emissions over a given period, compounds (e.g., hydrofluorocarbons or hydrofluoroolefins) that are reused from use in an apparatus or system and subsequently recycled and / or purified contribute to the minimum or zero "effective GWP" compared to newly produced compounds. For example, as shown in Table 9, composition R-449A is a refrigerant mixture containing 24.3 wt% HFC-32, 24.7 wt% HFC-125, 25.7 wt% HFC-134a, and 25.3 wt% HFO-1234yf, with a GWP of 1282. By preparing R-449A using one or more recycled / reused / purified components (e.g., components recovered from a refrigerant apparatus or system, subsequently purified and blended to formulate R-449A), the GWP of R-449A can be reduced by up to 99%. Based on the data provided in Table 9, the recovered / recycled / reused portion of the refrigerant blend is considered to have zero contribution to the effective GWP of the refrigerant blend.

[0166] [Table 13]

[0167] Tables 10-11 show that the GWP of R-513A (44 wt% HFC-134a, 56 wt% HFO-1234yf) and R-452B (67 wt% HFC-32, 7 wt% HFC-125, 26 wt% HFO-1234yf) can be reduced by 99.9% and 40%, respectively, using recovered / recycled / reused HFC components.

[0168] [Table 14]

[0169] [Table 15]

[0170] Example 2. Process for preparing R-449A using virgin raw materials. Refrigerant R-449A is nominally a mixture of 24.3 wt percent HFC-32, 24.7 wt percent HFC-125, 25.7 wt percent HFC-134a, and 25.3 wt percent HFO-1234yf. When blended using virgin raw materials of the four components (i.e., newly manufactured components), R-449A has a GWP of approximately 1281. An exemplary process for preparing 1 kg of R-449A is described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line from the blending container to the HFC-134a supply container. 3.253g of HFC-134a is weighed into a blending container and then transferred. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.257g of HFO-1234yf by weighing it into a blending container. 6. Attach a transfer line from the blending container to the HFC-125 supply container. 7.247g of HFC-125 is weighed into a blending container and then transferred. 8. Attach a transfer line from the blending container to the HFC-32 supply container. 9.243g of HFC-32 is weighed into a blending container and then transferred. 10. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 11. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by gas chromatography (GC) to confirm that the measured composition of the prepared R-449A is within acceptable specifications and tolerances.

[0171] Example 3. Process for preparing R-449A using recycled R-134a. 1 kg of R-449A prepared using 26% recovered / recycled / reused HFC content exhibits approximately 26% lower “effective” GWP when prepared using recovered and reused and / or recycled R-134a according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line from the empty, evacuated blend container to the recycled or reused HFC-134a supply container. Transfer 3.253 grams of recycled or reused HFC-134a by weighing it into a blending container. a. Recovered HFC-134a can be obtained by removing spent HFC-134a from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in the recovered HFC-134a must be removed before using it to prepare a new blend. c. Impurities include, but are not limited to, any solid, liquid, or gaseous matter that is undesirable to be present in a new refrigerant blend, including, but not limited to, rust, oil(s), dirt, water, air, and other non-condensable gases. d. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.257g of HFO-1234yf by weighing it into a blending container. 6. Attach a transfer line from the blending container to the HFC-125 supply container. 7.247g of HFC-125 is weighed into a blending container and then transferred. 8. Attach a transfer line from the blending container to the HFC-32 supply container. 9.243g of HFC-32 is weighed into a blending container and then transferred. 10. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 11. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-449A is within acceptable specifications and tolerances. 12. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0172] Example 4. Process for preparing R-449A using recycled R-410A. 1 kg of R-449A prepared using 49% recycled / recycled HFC content exhibits approximately 73% lower “effective” GWP when prepared using recycled and / or reused R-410A according to the exemplary procedure described below. 1. Follow steps 1-5 of Example 3. 2. After filling the blend container with HFC-134a and HFO-1234yf, instead of continuing by adding HFC-125 and HFC-32 as individual components, the following recovered / recycled / reused R-410A is added: 3. Attach a transfer line to the supply container of R-410A (50 / 50 wt% blend of R-125 and R-32) recovered from the empty, evacuated blend container. 4.490g of R-410A is weighed into the blending container and then transferred. a. Recovered R-410A can be obtained by removing spent R-410A from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in recovered R-410A, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered R-410A before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 5. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 6. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-449A is in line with the acceptable specifications and tolerances. 7. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0173] Example 5. Process for preparing R-449A using recycled R-407A. 1 kg of R-449A, prepared using a 62% recycled / recycled HFC content, exhibits approximately 93% lower “effective” GWP when prepared using recovered and recycled R-407A (a mixture of 20 / 40 / 40 wt% HFC-32 / HFC-125 / HFC-134a, respectively) according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line from the blending container to the HFO-1234yf supply container. Transfer 3.250g of HFO-1234yf by weighing it into a blending container. 4. Attach a transfer line from the blending container to the R-407A supply container. The recovered R-407A (5.625g) is weighed into a cylinder and then transferred. a. Recovered R-407A can be obtained by removing spent R-407A from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in the recovered R-407A purity, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered R-407A before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 6. Attach a transfer line from the blending container to the HFC-32 supply container. Transfer 7.125g of HFC-32 by weighing it into the blending container. 8. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 9. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-449A is in line with the acceptable specifications and tolerances. 10. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0174] Example 6. Process for preparing R-449A using recycled R-134a and recycled R-410A. 1 kg of R-449A prepared using 75% recycled / reused HFC content exhibits a more than 99% lower “effective” GWP when prepared using recovered, reused, and / or recycled R-134a and R-410A according to the exemplary procedures described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line to the supply container for the HFC-134a recovered from the blend container. The recovered HFC-134a is transferred by weighing it into a cylinder at a rate of 3.253 grams. a. Recovered HFC-134a can be obtained by removing spent HFC-134a from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in recovered HFC-134a, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered HFC-134a before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.257g of HFO-1234yf by weighing it into a blending container. 6. Attach a transfer line to the supply container for R-410A recycled / reused / recovered from the blending container. 7.490g of R-410A is weighed into the cylinder and then transferred. a. Recovered R-410A can be obtained by removing spent R-410A from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in recovered R-410A, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered R-410A before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 8. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 9. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-449A is within acceptable specifications and tolerances.

[0175] Example 7. Process for preparing R-513A using recycled R-134a. 1 kg of R-513A prepared using 44% recycled / recycled HFC content exhibits a more than 99% lower “effective” GWP when prepared using recovered, reused, and / or recycled R-134a according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line to the supply container for the HFC-134a recovered from the blend container. 3.440g of recovered HFC-134a is weighed into a blending container and then transferred. a. Recovered HFC-134a can be obtained by removing spent HFC-134a from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration or air conditioning systems). b. Impurities in the purity of recovered HFC-134a, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered HFC-134a before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.560g of HFO-1234yf by weighing it into a blending container. 6. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 7. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-513A is within acceptable specifications and tolerances. 8. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0176] Example 8. Process for preparing R-454A using recycled HFC-32. One kilogram of R-454A prepared using a 35% recycled / recycled HFC content will exhibit a “effective” GWP of less than 99% when prepared using recycled and / or recycled R-32 according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line to the supply container for HFC-32 recovered from the blending container. 3.350g of recovered HFC-32 is weighed into a cylinder and then transferred. a. Recovered HFC-32 can be obtained by removing spent HFC-32 from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in the recovered HFC-32 purity, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered HFC-32 before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.650g of HFO-1234yf by weighing it into a blending container. 6. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 7. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-454A is within specifications and tolerances. 8. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0177] Example 9. Process for preparing R-454B using recycled HFC-32. One kilogram of R-454B prepared using 68.9% recycled / recycled HFC content exhibits a “effective” GWP of less than 99% when prepared using recycled and / or recycled R-32 according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line to the supply container for HFC-32 recovered from the empty, evacuated container. 3.689g of recovered HFC-32 is weighed into a blending container and then transferred. a. Recovered HFC-32 can be obtained by removing spent HFC-32 from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in the recovered HFC-32 purity, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered HFC-32 before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blending container to the HFO-1234yf supply container. Transfer 5.311g of HFO-1234yf by weighing it into a blending container. 6. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 7. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-454B is within specifications and tolerances. 8. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0178] Example 10. Process for preparing R-454C using recycled HFC-32. One kilogram of R-454C prepared using a 21.5% recycled / recycled HFC content exhibits a “effective” GWP of less than 99% when prepared using recycled and / or recycled R-32 according to the exemplary procedure described below. 1. Prepare the refrigerant container by washing, drying, and evacuating the blending container. 2. Attach a transfer line to the supply container for HFC-32 recovered from the blending container. 3.215g of recovered HFC-32 is weighed into a blending container and then transferred. a. Recovered HFC-32 can be obtained by removing spent HFC-32 from refrigeration equipment or systems (e.g., appliances, automobiles, or any other refrigeration, air conditioning, or heat pump systems). b. Impurities in the recovered HFC-32 purity, including but not limited to rust, oil(s), dirt, water, air, and other non-condensable gases, must be removed from the recovered HFC-32 before it can be used to prepare a new refrigerant blend. c. Removal of impurities can be achieved by a variety of methods, including but not limited to filtration, drying with molecular sieves, distillation, and vapor space purging. 4. Attach a transfer line from the blend container to the HFO-1234yf supply container. Transfer 5.785g of HFO-1234yf by weighing it into a blending container. 6. Mix the ingredients in the blending container thoroughly for about 1 hour by rolling or other means. 7. Obtain a sample of the liquid phase of the refrigerant from the blending container and analyze it by GC to confirm that the measured composition of the prepared R-454C is within specifications and tolerances. 8. It may be necessary to add one or more of the individual components to the prepared mixture in the blending container to bring the overall composition within the specified range.

[0179] Other Embodiments 1. In some embodiments, the present application relates to a process for preparing a refrigerant blend comprising one or more purified hydrofluorocarbon compounds, (a) A process of recovering one or more hydrofluorocarbons from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 20 to form a refrigerant blend, The present invention provides a process in which one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof. 2. The process according to Embodiment 1, wherein each of the 2.1 or more hydrofluoroolefins has an effective global warming potential of less than about 10. 3. The process according to Embodiment 1, wherein each of the 1 or more hydrofluoroolefins has an effective global warming potential of less than about 2. 4. The process according to Embodiment 1, wherein each of the 4.1 or more hydrofluoroolefins has an effective global warming potential of less than about 1. 5. The process according to any one of Embodiments 1 to 4, wherein step (b) is performed once or more before the mixing of step (c). 6. (d) A process of reusing one or more hydrofluoroolefins from one or more refrigeration, air conditioning, or heat pump systems, (e) The process according to any one of Embodiments 1 to 5, further comprising the step of purifying one or more hydrofluoroolefins to form one or more purified hydrofluoroolefins. 7. The process according to Embodiment 6, wherein steps (d) and (e) are performed before the blending in step c). 8. The process according to any one of Embodiments 1 to 7, wherein each of 8.1 or more purified hydrofluorocarbons or purified hydrofluoroolefin compounds has an effective global warming potential of about 0. 9. The process according to any one of Embodiments 1 to 8, wherein the hydrofluoroolefin is selected from the group consisting of (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)), (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)), trifluoroethylene (HFO-1123), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)), and 3,3,3-trifluoropropene (HFO-1243zf), or any mixture thereof. 10. The process according to any one of Embodiments 1 to 9, wherein the hydrofluorocarbon compound is difluoromethane (R-32). 11. The process according to any one of Embodiments 1 to 10, wherein the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf). 12. The refrigerant blend is Approximately 21-22 weight percent purified difluoromethane (R-32), The process according to any one of Embodiments 1 to 11, comprising approximately 78 to approximately 79 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf). 13. The refrigerant blend is Approximately 68-69 weight percent purified difluoromethane (R-32), The process according to any one of Embodiments 1 to 11, comprising approximately 30 to approximately 31 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf). 14. The refrigerant blend is Approximately 34 to 36 weight percent of purified difluoromethane (R-32), The process according to any one of Embodiments 1 to 11, comprising approximately 64 to approximately 66 weight percent of 2,3,3,3-tetrafluoropropene (HFO-1234yf). 15. The process according to any one of Embodiments 1 to 9, wherein the hydrofluorocarbon is a mixture of difluoromethane (R-32) and pentafluoroethane (R-125). 16. The process according to any one of Embodiments 1 to 9 and 15, wherein the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf). 17. The refrigerant blend is about 66 to about 68% by weight of purified difluoromethane (R-32), about 6 to about 8% by weight of purified pentafluoroethane (R-125), about 25 to about 27% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), and the process according to any one of Embodiments 1 to 9, 15, and 16. 18. The process according to any one of Embodiments 1 to 9, wherein the one or more hydrofluorocarbon compounds are a mixture of difluoromethane (R-32), pentafluoroethane (R-125), and 1,1,1,2-tetrafluoroethane (R-134a). 19. The process according to any one of Embodiments 1 to 9 and 18, wherein the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf). 20. The refrigerant blend is about 24 to about 25% by weight of purified difluoromethane (R-32), about 24 to about 25% by weight of purified pentafluoroethane (R-125), about 25 to about 26% by weight of purified 1,1,1,2-tetrafluoroethane (R-134a), about 25 to about 26% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), and the process according to any one of Embodiments 1 to 9, 18, and 19. 21. The process according to any one of Embodiments 1 to 9, wherein the hydrofluorocarbon compound is 1,1,1,2-tetrafluoroethane (R-134a). 22. The process according to any one of Embodiments 1 to 9 and 21, wherein the hydrofluoroolefin is 2,3,3,3 - tetrafluoropropene (HFO - 1234yf). 23. The refrigerant blend is about 43 to about 45 weight percent of purified 1,1,1,2 - tetrafluoroethane (R - 134a) and about 55 to about 57 weight percent of 2,3,3,3 - tetrafluoropropene (HFO - 1234yf), and the process according to any one of Embodiments 1 to 9, 21, and 22. 24. The refrigeration system includes an air conditioner, a refrigerator, a freezer, a chiller, a heat pump, a mobile refrigerator, a mobile air - conditioning unit, an immersion cooling system, a data - center cooling system, or any combination thereof, and the process according to any one of Embodiments 1 to 23. 25. The air conditioner is an automotive air conditioner, and the process according to Embodiment 24. 26. The heat pump is a high - temperature heat pump, and the process according to Embodiment 24. 27. The chiller is a water chiller, a flooded evaporator chiller, a direct - expansion chiller, a screw chiller, a scroll chiller, or a centrifugal chiller, and the method according to Embodiment 24. 28. The refrigerator is a walk - in refrigerator, and the process according to Embodiment 24. 29. The freezer is a walk - in freezer, and the process according to Embodiment 24. 30. The purification in step (b) includes removing solid impurities from one or more hydrofluorocarbon compounds, and the process according to any one of Embodiments 1 to 29. 31. The solid impurities are removed by one or more purification techniques selected from pressure filtration, vacuum filtration, membrane centrifugal filtration, gravity filtration, depth - filter filtration, granular - bed filtration, cartridge filtration using carbon, fiber, or metal filtration, and pre - coat filtration, and the process according to any one of Embodiments 1 to 30. 32. The process according to any one of Embodiments 1 to 31, wherein the purification in step (b) includes removing liquid impurities, gaseous impurities, or a combination thereof from one or more hydrofluorocarbon compounds. 33. The process according to any one of Embodiments 1 to 32, wherein liquid impurities, gaseous impurities, or a combination thereof are removed by one or more purification techniques selected from distillation, decantation, contact with a molecular sieve, and vapor space purging. 34. The process according to any one of Embodiments 7 to 33, wherein the purification in step (e) includes removing solid impurities from one or more hydrofluoroolefins. 35. The process according to Embodiment 34, wherein solid impurities are removed by one or more purification techniques selected from pressure filtration, vacuum filtration, membrane centrifugation filtration, gravity filtration, deep filter filtration, granular bed filtration, cartridge filtration using carbon, fiber, or metal filtration, and pre-coat filtration. 36. The process according to any one of Embodiments 7 to 35, wherein the purification in step (e) includes removing liquid impurities, gaseous impurities, or a combination thereof from one or more hydrofluoroolefins. 37. The process according to Embodiment 36, wherein liquid impurities, gaseous impurities, or combinations thereof are removed by one or more purification techniques selected from distillation, decantation, contact with molecular sieves, and vapor space purging. 38. In some embodiments, the present application relates to a process for reducing the global warming potential of a refrigerant blend, (a) A step of selecting one or more hydrofluorocarbons recovered from one or more refrigeration, air conditioning, or heat pump systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than approximately 20 to form a purified refrigerant blend, The purified refrigerant blend has a lower global warming potential compared to a refrigerant blend containing one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). The present invention further provides a process in which one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). 39. The process according to Embodiment 38, wherein one or more hydrofluoroolefins are selected from the group consisting of (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(Z)), (E)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz-(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze-(E)), trifluoroethylene (HFO-1123), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye-(E)), and 3,3,3-trifluoropropene (HFO-1243zf), or any mixture thereof. 40. The method according to Embodiment 38 or 39, wherein the refrigerant blend has an effective global warming potential of about 10% or less compared to a refrigerant blend comprising one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). 41. The method according to Embodiment 38 or 39, wherein the purified refrigerant blend has an effective global warming potential of about 5% or less compared to a refrigerant blend comprising one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). 42. The method according to Embodiment 38 or 39, wherein the refrigerant blend has an effective global warming potential of about 1% or less compared to a refrigerant blend comprising one or more hydrofluoroolefins and one or more hydrofluorocarbon compounds that have not been recovered and purified according to steps (b) to (c). 43. A refrigeration, air conditioning, or heat pump system comprising a refrigerant blend prepared according to the process described in any one of Embodiments 1 to 42.

[0180] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, and not limit, the scope of the invention as defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art that any feature described herein with respect to any particular aspect and / or embodiment of the invention can be combined with one or more other features of any other aspect and / or embodiment of the invention described herein, and can be modified as appropriate to ensure the suitability of the combination. Such combinations are considered to be part of the invention as contemplated by this disclosure.

Claims

[Claim 1] A process for preparing a refrigerant blend containing one or more recovered hydrofluorocarbon compounds, (a) A step of recovering one or more hydrofluorocarbons from one or more refrigeration systems, (b) A step of purifying one or more hydrofluorocarbon compounds to form one or more purified hydrofluorocarbon compounds, (c) A step of blending one or more purified hydrofluorocarbon compounds with one or more hydrofluoroolefins having a global warming potential of less than about 20 to form the refrigerant blend, A process in which the one or more hydrofluorocarbon compounds are selected from difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or any mixture thereof.

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