Low-GWP composition containing HFO-1252ZC and its use

Abstract

This disclosure relates to compositions comprising HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions are useful in cooling methods, refrigeration systems including low temperature, medium temperature, and transport refrigeration, and methods for replacing existing refrigerants.

Description

[Technical Field]

[0001] This disclosure relates to compositions useful as refrigerants, particularly in refrigeration systems. The compositions of this disclosure are useful in methods for producing cooling, methods for replacing refrigerants, and in refrigeration systems, including low-temperature and medium-temperature refrigeration and transport refrigeration systems. [Background technology]

[0002] For the past several decades, the fluorocarbon industry has been working to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol. The solution for many applications has been to commercialize hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These newer compounds, such as HFC-134a and HFC-125, the most widely used HFC refrigerants at present, have zero ozone depletion potential (ODP) and are therefore unaffected by the current regulations that are being phased out as a result of the Montreal Protocol. In addition to the ozone depletion issue, another environmental concern for many of these applications, particularly in light of the Kigali Amendment, is global warming. According to the UN's IPCC Fourth Assessment Report (AR4), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWP) of 1,430 and 3,500, respectively.

[0003] This regulatory landscape is constantly evolving, and properties other than ODP and GWP are now being considered. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have a low global warming potential, but also provide excellent performance in a variety of applications and meet evolving regulatory standards. [Overview of the project] [Problems that the invention aims to solve]

[0004] This invention provides a refrigerant blend containing 1,1-difluoropropene that solves specific problems associated with conventional refrigerants and meets evolving regulatory requirements. [Means for solving the problem]

[0005] To meet the rapidly changing regulatory environment, the inventors have identified fluoroolefin compounds that offer performance characteristics that allow them to advance their use compared to existing refrigerants, taking into account the criteria of the evolving regulatory landscape.

[0006] Specific embodiments disclosed herein relate to fluoropropene compositions comprising 1,1-difluoropropene (also known as HFO-1252zc or R-1252zc). This compound is shown herein to have properties advantageous for use in refrigerant applications.

[0007] In one embodiment, a composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE is disclosed herein.

[0008] According to any of the embodiments described above, compositions comprising about 1 to 65 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 13 to 98 weight percent of HFO-1234zeE are also disclosed herein.

[0009] According to any of the embodiments described above, compositions comprising about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 98 weight percent of HFO-1234zeE are also disclosed herein.

[0010] According to any of the embodiments described above, compositions comprising about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 77 weight percent of HFO-1234zeE are also disclosed herein.

[0011] According to any of the embodiments described above, compositions comprising about 23 weight percent of HFO-1252zc, about 22 weight percent of HFC-32, and about 55 weight percent of HFO-1234zeE, or about 65 weight percent of HFO-1252zc, about 22 weight percent of HFC-32, and about 13 weight percent of HFO-1234zeE are also disclosed herein.

[0012] According to any of the embodiments described above, HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-374, n-butane, allene, 2-butene, cyclobutene, 2-methylpropene, HCFO-1 Compositions further comprising at least one additional compound selected from 122, HFO-1132, HFO-1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, propylene, HFO-1345, HFO-1252ze, HFO-1252yf, HFO-1252zf, HFO-1252ye, and E / Zt-BuO-CF=CH-CH3 are also disclosed herein.

[0013] According to any of the embodiments described above, compositions further comprising at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye are also disclosed herein.

[0014] According to any of the embodiments described above, compositions further comprising 0.1 to 200 ppm by weight of water, about 10 ppm to about 0.35 volume percent of oxygen, and / or about 100 ppm to about 1.5 volume percent of air or NAG are also disclosed herein.

[0015] According to any of the embodiments described above, compositions comprising a stabilizer are also disclosed herein.

[0016] According to any of the embodiments described above, compositions in which the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones are also disclosed herein.

[0017] According to any of the embodiments described above, compositions in which the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene are also disclosed herein.

[0018] According to any of the embodiments described above, compositions in which the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant are also disclosed herein.

[0019] According to any of the embodiments described above, compositions further comprising a lubricant are also disclosed herein.

[0020] According to any of the embodiments described above, compositions in which the lubricant is selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether are also disclosed herein.

[0021] According to any of the foregoing embodiments, a composition in which the lubricant is a polyol ester or a polyvinyl ether is also disclosed herein.

[0022] According to any of the foregoing embodiments, the lubricant has a volume resistivity of more than 10 10 Ω-m at 20°C, a surface tension of about 0.02 N / m to 0.04 N / m at 20°C, a kinematic viscosity of about 20 cSt to about 500 cSt at 40°C, an insulation breakdown voltage of at least 25 kV, and a hydroxyl value of at most 0.1 mg KOH / g. A composition having at least one property selected from the group consisting of these is also disclosed herein.

[0023] According to any of the foregoing embodiments, a composition containing at least one tracer is also disclosed herein.

[0024] According to any of the foregoing embodiments, a composition in which the tracer is present in an amount of about 1.0 weight ppm to about 1000 weight ppm is also disclosed herein.

[0025] According to any of the foregoing embodiments, a composition in which the at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof is also disclosed herein.

[0026] According to any of the foregoing embodiments, the at least one tracer is also disclosed herein as a composition selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

[0027] According to any of the foregoing embodiments, compositions that do not contain or substantially do not contain Group A fluorinated substances are also disclosed herein, and the decomposition products of the compositions do not contain or substantially do not contain Group A fluorinated substances.

[0028] According to any of the foregoing embodiments, a method for cooling is also disclosed herein, the method comprising evaporating a composition according to any of claims 1 to 21 in the vicinity of an object to be cooled and then condensing the composition, wherein the cooling is provided by a refrigeration system.

[0029] According to any of the foregoing embodiments, a refrigeration system comprising a composition according to any of the foregoing embodiments is also disclosed herein.

[0030] According to any of the embodiments described above, a refrigeration system comprising the composition of any of the embodiments described above for use in high ambient temperature applications where the ambient temperature exceeds approximately 35°C is also disclosed herein.

[0031] According to any of the embodiments described above, a refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device is also disclosed herein, each operably connected to perform a vapor compression cycle.

[0032] According to any of the embodiments described above, a refrigeration system for residential, light commercial, or industrial use is also disclosed herein. In another embodiment, the refrigeration system comprises a composition of any of the embodiments described above, and the system is for medium-temperature refrigeration, low-temperature refrigeration, or transport refrigeration.

[0033] According to any of the embodiments described above, a refrigeration system comprising any of the compositions of the embodiments described above is also disclosed herein, the system being for medium-temperature refrigeration, low-temperature refrigeration, or transport refrigeration.

[0034] According to any of the embodiments described above, a method for replacing R-454C in a refrigeration system is also disclosed herein, the method comprising providing the system with a composition of any of the embodiments described above in place of R-454C.

[0035] According to any of the embodiments described above, it is disclosed herein that any of the compositions described above may be used as a refrigerant in a low-temperature refrigeration system, a medium-temperature refrigeration system, and / or a transport refrigeration system. [Modes for carrying out the invention]

[0036] The present invention relates to a composition containing 1,1-difluoropropene (HFO-1252zc), difluoromethane (HFC-32), and E-1,3,3,3-tetrafluoropropene (HFO-1234zeE). The composition may be a candidate to replace refrigerants such as R-454C, R-410A, or propane, and may have a low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0037] The composition comprises HFO-1252zc, HFC-32, and HFO-1234zeE. These blends provide refrigerant blends with a low global warming potential, an improved gradient compared to other proposed refrigerant blends, and an improved coefficient of performance compared to existing refrigerants and other proposed alternatives.

[0038] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas during the heat transfer cycle and then returns to a liquid state.

[0039] A heat transfer system is a system (or device) used to produce a heating or cooling effect in a specific space. A heat transfer system may be a mobile system or a fixed system.

[0040] Examples of heat transfer systems include, but are not limited to, any type of refrigeration and air conditioning systems, including, fixed heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, full-liquid evaporator heat pumps, direct expansion chiller heat pumps, chillers, full-liquid evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile heat transfer systems, mobile heat pumps (including heat pumps for comfortable heating and cooling of vehicle cabins), mobile air conditioning units (for cooling of vehicle cabins), dehumidifiers, and combinations thereof. The focus of this application is on refrigeration systems, including low-temperature refrigeration systems and medium-temperature refrigeration systems.

[0041] Volumetric capacity is the amount of heat absorbed or released divided by the theoretical compressor displacement. The heat removed or absorbed is the enthalpy difference across the heat exchanger multiplied by the refrigerant mass flow rate. The theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., the compressor suction density). More simply, volumetric capacity is the suction density multiplied by the heat exchanger enthalpy difference. A higher volumetric capacity allows for the use of a smaller compressor for the same heat load. In this specification, cooling capacity refers to volumetric capacity in cooling mode, and heating capacity refers to volumetric capacity in heating mode.

[0042] The coefficient of performance (COP) is calculated by dividing the amount of heat absorbed or released by the energy input required to operate the cycle (approximated by the compressor's capacity). COP is specific to the operating mode of the heat pump and therefore can be either the COP for heating or the COP for cooling. COP is directly related to the energy efficiency ratio (EER).

[0043] Supercooling refers to lowering the temperature of a liquid to below its saturation point under a given pressure. The saturation point is the temperature at which vapor completely condenses into a liquid. By cooling a liquid below its saturation temperature (or boiling point), the net cooling effect can be increased. Thus, supercooling improves the cooling capacity and energy efficiency of a system. The amount of supercooling is the amount of cooling below the saturation temperature (degrees).

[0044] Superheating refers to raising the temperature of a vapor above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. Superheating continues to heat the vapor to a higher temperature at a given pressure. By heating the vapor above its saturation temperature (or dew point temperature), the net cooling effect can be increased. Thus, when superheating occurs in an evaporator, it improves the cooling capacity and energy efficiency of the system. Superheating in a suction line does not add a net cooling effect and may reduce efficiency and capacity. The amount of superheating is the amount of heating above the saturation temperature (degrees).

[0045] A temperature gradient (sometimes simply referred to as "gradient") is the absolute difference between the start and end temperatures of the phase change process by the refrigerant in the condenser of a refrigerant system, excluding any supercooling or superheating. In the case of an evaporator, the gradient is the temperature difference between the dew point and the evaporator inlet. The gradient can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to the temperature gradient of an air conditioning system or heat pump system, it is common to provide the mean temperature gradient, which is the average value of the temperature gradient in the evaporator and the temperature gradient in the condenser. The gradient is applicable to blended refrigerants, i.e., refrigerants composed of at least two components.

[0046] Net cooling effect is the amount of heat absorbed in the evaporator by one kilogram of each refrigerant in order to produce useful cooling.

[0047] Mass flow rate is the amount (in kilograms) of refrigerant circulating through a refrigeration, heat pump, or air conditioning system over a given period of time.

[0048] 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 hydrodynamic lubrication to the compressor to help prevent seizing of parts.

[0049] The Global Warming Potential (GWP) is an index used to estimate the relative contribution to global warming caused by one kilogram of atmospheric emissions of a particular greenhouse gas 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 for a 100-year period is a commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In this specification, GWP values ​​are those reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4). The estimated GWP for 1252zc is 1.

[0050] The ozone depletion potential (ODP) is a numerical value that indicates the amount of ozone depletion caused by a substance. ODP is the ratio of the effect of a chemical substance on ozone compared to the effect of a similar mass of CFC-11 (fluorotrichloromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs in the range of 0.01 to 1.0. The ODPs of hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein are zero because they do not contain chlorine, bromine, or iodine, which are known to contribute to ozone decomposition and depletion. The ozone depletion potential of HFO-1252zc is zero.

[0051] 1,1-Difluoropropene (HFO-1252zc or R-1252zc) can be prepared by hydrogenating 3,3,3-trifluoropropene (HFO-1243zf) on a carbon-based palladium catalyst to form 1,1,1-trifluoropropane (HFC-263fb), followed by dehydrofluoridation of HFC-263fb on a chromium catalyst, or by thermal decomposition at high temperatures (see Agent Reference No. FL2084, filed together with this Specified and incorporated herein by reference).

[0052] E-1,3,3,3-tetrafluoropropene (HFO-1234zeE or R-1234zeE) is commercially available from Honeywell (Charlotte, North Carolina, USA). Difluoromethane (HFC-32 or R-32) is also commercially available from various suppliers worldwide.

[0053] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, but may include other elements not expressly enumerated, or other elements inherent in such composition, process, method, article, or apparatus.

[0054] The transitional phrase "consisting of..." excludes any unspecified elements, processes, or components. In the context of patent claims, such phrases would close the claim to materials other than those listed, with the exception of impurities normally associated with the materials. If the phrase "consisting of..." appears within a clause in the body of a claim rather than immediately following the preamble, it limits the elements described within that clause only, and does not exclude other elements from the claim as a whole.

[0055] The transitional phrase "essentially consists of" is used to define a composition, method, or apparatus that includes materials, processes, features, components, or elements in addition to what is literally disclosed, provided that these additionally included materials, processes, features, components, or elements do not substantially affect the fundamental and novel characteristics of the claimed invention. The term "essentially consists of" has an intermediate meaning between "includes" and "consists of." Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain small amounts (e.g., less than about 0.5 weight percent total) of impurities and / or by-products (e.g., from the manufacture of refrigerant components or the reuse of refrigerant components from other systems) that do not substantially affect the novel and fundamental characteristics of the refrigerant mixture.

[0056] 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 read as including one or at least one, and the singular form also includes the plural form unless it is obvious that a different meaning is intended.

[0057] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials to those described herein may be used in the practice or testing of embodiments of the disclosed compositions, but preferred methods and materials are described below. All publications, patent applications, patents, and other references referred herein are incorporated herein by reference in their entirety unless a specific section is cited. In the event of any inconsistency, including definitions, this specification shall prevail. Furthermore, the materials, methods, and examples are illustrative and not intended to be limiting.

[0058] Refrigerant composition In one embodiment, the composition comprises, consists of, or is essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions offer lower global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP) compared to existing refrigerants.

[0059] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 1 to 65 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 13 to 98 weight percent of HFO-1234zeE. In another embodiment, the composition comprises, consists of, or is essentially composed of, about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 98 weight percent of HFO-1234zeE. In yet another embodiment, the composition comprises, consists of, or is essentially composed of, about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 77 weight percent of HFO-1234zeE. In another embodiment, the composition comprises, consists of, or is essentially composed of, about 23 weight percent of HFO-1252zc, about 22 weight percent of HFC-32, and about 55 weight percent of HFO-1234zeE, or about 65 weight percent of HFO-1252zc, about 22 weight percent of HFC-32, and about 13 weight percent of HFO-1234zeE.

[0060] Flammability is a term used to describe the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (LFL) is the lowest concentration of a heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the test conditions specified in ASTM (American Society of Testing and Material) E681. The upper flammability limit (UFL) is the highest concentration of a heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the same test conditions.

[0061] For a refrigerant to be classified as low flammability (Class 2L) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), and 2) have a flammability rating of >0.0062 lb / ft 3 (0.10 kg / m 3 ) must have an LFL of <8169 Btu / lb (19,000 kJ / kg), and 4) have a maximum burning rate of ≤3.9 inches / second (10 cm / second) when tested in dry air at 73.4°F (23.0°C) and 14.7 psia (101.3 kPa).

[0062] For a refrigerant to be classified as flammable (Class 2) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), and 2) have a flammability of >0.0062 lb / ft 3 (0.10 kg / m 3 ) It has an LFL of ) and 3) the heat of combustion must be <8169 Btu / lb (19,000 kJ / kg).

[0063] To classify a refrigerant according to ANSI / ASHRAE standard 34 Class 3, the refrigerant must 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), and 2) have a load of <0.0062 lb / ft3 (0.10 kg / m 3 It has an LFL of ) and a combustion heat of >8169 Btu / lb (19,000 kJ / kg).

[0064] ASHRAE Standard 34 provides a methodology for calculating the heat of combustion of a refrigerant blend using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with sufficient oxygen for a stoichiometric reaction.

[0065] Compositions containing, consisting of, or essentially consisting of HFO-1252zc, HFC-32, and HFO-1234zeE may further contain at least one additional compound from the list in Table 1.

[0066] [Table 1]

[0067] In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound comprising HFO-1234yf. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound comprising HFO-1243zf. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE may further comprise at least one additional compound comprising HFO-263fb.

[0068] Some of the compounds present in the compositions of the present invention specified in Table 1 may exist as different stereoisomers or stereoisomers. The present invention is intended to include all single stereoisomers, single stereoisomers, or any combination or mixture thereof. For example, 1,2-difluoroethene (HFO-1132) means that it represents the cis-isomer (Z), the trans-isomer (E), or any combination or mixture of both isomers in any ratio. Single or multiple isomers of the same compound can be used in any proportion.

[0069] The amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 ppm but less than 5,000 ppm, and in particular, may be in the range of greater than 0 to about 1,000 ppm, about 5 to about 500 ppm, and about 1 to about 100 ppm.

[0070] In one embodiment, the amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 to less than 1% by weight of the refrigerant composition, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight.

[0071] Compositions containing, consisting of, or essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE function more consistently and are more stable in the presence of small amounts of water. Therefore, the composition may further contain less than 100 ppm (by weight) of water, preferably less than 20 ppm (by weight), and more preferably less than 10 ppm (by weight).

[0072] Furthermore, compositions containing, consisting of, or essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE function more consistently and are more stable in the presence of only small amounts of oxygen or air. Accordingly, the claimed composition may further contain less than about 5 volume percent of non-adsorbable gas (NAG), preferably less than 3 volume percent of NAG, more preferably less than 1.5 volume percent of NAG. Furthermore, the claimed composition contains less than 1 volume percent of oxygen, preferably less than 0.5 volume percent of oxygen, more preferably less than 0.3 volume percent of oxygen, due to the presence of air or NAG.

[0073] In another embodiment, a composition containing, consisting of, or essentially consisting of HFO-1252zc, HFC-32, and HFO-1234zeE may contain stabilizers. Such stabilizer compounds are present in small amounts and are intended to prevent decomposition due to the presence of water, air, NAG, or oxygen in the system during use or while the composition is stored. HFO-type refrigerants are thermally unstable due to the presence of double bonds and may decompose even under extreme use, handling, or storage conditions. Therefore, there may be advantages to adding stabilizers to HFO-type refrigerants. In particular, examples of stabilizers include nitromethane; ascorbic acid; terephthalic acid; azoles such as toltriazole or benzotriazole; phenol compounds such as tocopherol; hydroquinone; t-butylhydroquinone; 2,6-di-tert-butyl-4-methylphenol; epoxides such as n-butylglycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, and butylphenyl glycidyl ether (in some cases, fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides); cyclic monoterpenes; terpenes such as d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, or β-pinene; phosphites; phosphates; phosphonates; thiols; and lactones. Examples of suitable stabilizers are disclosed in International Publication Nos. 2019213004, 2020222864, and 2020222865, which are incorporated herein by reference.

[0074] If the composition contains a stabilizer, it may contain any of the stabilizers listed above in any amount between 0.001% and 1% by weight, preferably about 0.001% to about 0.5% by weight, and more preferably about 0.001% to about 0.3% by weight.

[0075] In some embodiments, compositions comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234ze may contain a tracer compound or tracer. The tracer may comprise two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million (ppm) to about 1000 ppm, based on the weight of the total composition. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0076] Tracers may be present in a composition containing, consisting of, or essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE in predetermined amounts, enabling the detection of any dilution, contamination, or other change of the composition. The presence of a particular compound in the composition may indicate by what method or process one of the components was produced. Alternatively, a specified amount of tracer may be added to the composition to identify the source of the composition. In this way, detection of patent infringement can be achieved. Tracers may be refrigerant compounds, but they are present in the composition at levels unlikely to affect the performance of the refrigerant components of the composition.

[0077] The tracer compound may be hydrofluorocarbon, hydrofluoroolefin, hydrochlorocarbon, hydrochloroolefin, hydrochlorofluorocarbon, hydrochlorofluoroolefin, hydrochlorocarbon, hydrochloroolefin, chlorofluorocarbon, chlorofluoroolefin, hydrocarbon, perfluorocarbon, perfluoroolefin, or combinations thereof. Examples of tracer compounds include HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-2 36ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1-trifluoro-2-methylpropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane), CFC-12 (dichlorodifluoromethane), CFC-11 ( HCFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (1,1,-dichloro-1,2,2,2-tetrafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1-difluoroethane), HCFC-151a (1-chloro-1-fluoroethane), HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (fluoroethene), HCFO-1130 (1,2-dichloroethene), HCFO-1130a (1,1-dichloroethene), HCFO-1131 (1-chloro-2-fluoroethene), HCFO-1122 (2-chloro-1,1-difluoroethene), HFO-1123 (1,1,2-trifluoroethene), HFO-1234ye (1,2,3,3-tetrafluoropropene) Examples include, but are not limited to, HFO-1243zf (3,3,3-trifluoropropene), HFO-1225ye (1,2,3,3,3-pentafluoropropene), HFO-1225zc (1,1,3,3,3-pentafluoropropene), PFC-116 (hexafluoroethane), PFC-C216 (hexafluorocyclopropane), PFC-218 (octafluoropropane), PFC-C318 (octafluorocyclobutane), PFC-1216 (hexafluoroethane), PFC-31-10mc (1,1,1,2,2,3,3,4,4,4-decafluorobutane), PFC-31-10my (1,1,1,2,3,3,3-heptafluoro-2-trifluoromethylpropane), and combinations thereof.

[0078] In another embodiment of the present disclosure, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE further comprises at least one lubricant. The lubricant may be selected from polyol esters, polyvinyl ethers, and polyalkylene glycols. The lubricant may also include what is commonly known as “mineral oil” in the field of compression refrigeration lubrication. Mineral oil comprises paraffins (i.e., saturated hydrocarbons of linear and branched carbon chains), naphthenes (i.e., cyclic or cyclic saturated hydrocarbons which may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention further comprise what is commonly known as “synthetic oil” in the field of compression refrigeration lubrication. Synthetic oil comprises alkylaryls (i.e., linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and polyalphaolefins. Typical conventional lubricants of the present invention include commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oil sold by Crompton Co. under the trademarks 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 alkylbenzenes sold by Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkylbenzenes sold by Nippon Oil under the trademark HAB 22.

[0079] The lubricants of the present invention are designed for use with hydrofluorocarbon refrigerants and further include those that are miscible with the refrigerants of the present invention under the operating conditions of compressed refrigeration and air conditioning systems. Examples of lubricants include, but are not limited to, polyol esters (POE), such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAG), such as RL-488A from Dow Chemical (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVE), such as PVE-FVC68D.

[0080] One particular embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234ze, is combined with a PAG lubricant, PVE lubricant, or POE lubricant for use in low-temperature or medium-temperature refrigeration systems.

[0081] In a composition containing, consisting of, or essentially consisting of HFO-1252zc, HFC-32, and HFO-1234zeE, which also contains a lubricant, the lubricant may be present in an amount of less than 80 weight percent of the total composition. The lubricant may further be present in an amount of less than 60 weight percent of the total composition. In other embodiments, the amount of lubricant may be about 0.1 to 50 weight percent of the total composition. The lubricant may also be about 0.1 to 20 weight percent of the total composition. The lubricant may also be about 0.1 to 5 weight percent of the total composition.

[0082] In another aspect of the present invention, compositions of the present invention comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are used to introduce lubricants, and / or alternatively other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants, into air conditioning or heat pump systems. In one preferred embodiment, the composition comprises an acid scavenger.

[0083] Examples of acid scavengers that may be included in this composition include, but are not limited to, the stabilizers and / or epoxide components of stabilizers disclosed in U.S. Patent No. 8,535,555, and the acid scavengers disclosed in International Publication No. 2020 / 222864, each of which is incorporated herein by reference in whole.

[0084] In some embodiments, the acid scavenger may include one or more epoxides, one or more amines, and / or one or more hindered amines, such as, but not limited to, epoxybutane.

[0085] Acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration, resulting in a relatively low total acid number, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof.

[0086] Preferably, the acid scavenger is present at a concentration of more than about 0.0050% by weight, more preferably more than about 0.05% by weight, and even more preferably more than about 0.1% by weight (e.g., more than about 0.5% by weight) based on the total weight of the refrigerant composition. The acid scavenger is present at a concentration of less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably more than about 2% by weight (e.g., less than about 1.8% by weight) based on the total weight of the refrigerant composition.

[0087] Preferred additives include those described in U.S. Patents No. 5,152,926 and No. 4,755,316, which are incorporated herein by reference. Specifically, preferred extreme pressure additives include mixtures of (A) tolyltriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) (i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphoric acid alcohol (e.g., ZELEC 3337), or (iii) zinc dialkyldithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadianazole derivative (e.g., Curvan 826), or a mixture thereof. Further examples of additives that may be used are provided in U.S. Patent No. 5,976,399 (Schnur, 5:12–6:51, incorporated herein by reference).

[0088] The acid value is measured in mg KOH / g units according to ASTM D664-01. The total halide concentration, fluoride ion concentration, and total organic acid concentration are measured by ion chromatography. The chemical stability of the refrigerant system is measured according to ASHRAE 97:2007 (RA 2017) "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems". The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

[0089] Mouli et al. (International Publication Nos. 2008 / 027595 and 2009 / 042847) teach the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives have also been used in certain refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application No. 11 / 575,256, published as U.S. Patent Application Publication No. 2007 / 0290164) and Singh et al. (U.S. Patent Application No. 11 / 250,219, published as U.S. Patent Application Publication No. 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference.

[0090] Preferred flame inhibitors include flame retardants described by reference in the patent application "Refrigerant compositions containing fluorine substituted olefins" (Canadian Patent No. 2557873(A1)), and fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox® lubricants described by reference in the patent application "Refrigerant compositions comprising fluoroolefins and uses thereof" (International Publication No. 2009018117(A1)).

[0091] In one embodiment, as used herein, "Group A fluorinated substances" include (i) substances containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (where no H / Cl / Br / I is bonded to the carbon), and (ii) substances that meet the criteria for persistence in soil / sediment and water, which criteria are defined in Annex XIII (Section 1.1.1) of the REACH Regulation of the European Union (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed on May 2, 2023) and are referred to in the Regulation Report of Annex XV dated March 22, 2023, the disclosure of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed on May 2, 2023). In one embodiment, Group A fluorinated substances include, but are not limited to, trifluoroacetic acid (TFA).

[0092] In another embodiment, as used herein, "Group A fluorinated substances" include any substance having a Henry's law constant of ≤ 250 Pa * m 3 / mol and containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (where no H / Cl / Br / I is bonded to the carbon). In one embodiment, Group A fluorinated substances include, but are not limited to, TFA.

[0093] Accordingly, according to some embodiments, compositions of the present invention comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE do not contain or substantially contain group A fluorinated substances such as TFA. In one embodiment, the term “does not contain” as used herein with respect to the presence of group A fluorinated substances in the composition means that the amount of such substances in the composition is so small that it is undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. In one embodiment, with respect to the presence of Group A fluorinated substances in the composition, the phrase "substantially absent" as used herein means that the amount of such substances in the composition can be determined by gas chromatography (GC) techniques, such as gas chromatography (GC) using a flame ionization detector or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (high-performance liquid chromatography-mass spectrometry). This means that, when measured by spectrometry (HPLC-MS) techniques, the values ​​are >0 wt% to ≤5 wt%, or >0 wt% to ≤4 wt%, or >0 wt% to ≤3 wt%, or >0 wt% to ≤2 wt%, or >0 wt% to ≤1 wt%, as well as all values ​​and ranges in between.TFA analytical standards can be used with either gas chromatography or ion chromatography and are available, for example, from Sigma Aldrich.

[0094] Furthermore, in some embodiments, the decomposition products of such compositions of the present invention, comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, do not contain or substantially contain Group A fluorinated substances such as TFA. In one embodiment, the term “does not contain” as used herein with respect to the formation of Group A fluorinated substances by the composition means that the theoretical molar yield of such substances in the air, soil / sediment and water environmental compartments generated during the tropospheric decomposition of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques, e.g., GC or GC / MS methods using flame ionization detectors or electron capture detectors, IC or IC-MS techniques, or HPLC or HPLC-MS techniques. In one embodiment, the term “substantially free” as used herein with respect to the formation of Group A fluorinated substances by the Composition means that the theoretical molar yield of such substances in the air, soil / sediment, and water environmental compartments generated during the tropospheric decomposition of the Composition is >0% to ≤5%, or >0% to ≤4%, or >0% to ≤3%, or >0% to ≤2%, or >0% to ≤1%, and all values ​​and ranges in between, when measured by GC techniques, e.g., GC or GC / MS using a flame ionization detector or electron capture detector, IC or IC-MS techniques, or HPLC or HPLC-MS techniques.

[0095] The compositions of the present invention can be prepared by any convenient method for combining desired amounts of individual components. A preferred method is to weigh out the desired amounts of components and then combine them in a suitable container. Stirring may be used if desired. In another embodiment, any of the aforementioned refrigerant compositions can be prepared by blending HFO-1252zc, HFC-32, and HFO-1234zeE, and optionally at least one additional compound.

[0096] In further embodiments, the composition may be prepared from recycled or regenerated refrigerants. One or more components can be recycled or regenerated by removing contaminants such as lubricants or residues that may contain particulate matter from air, water, or system components. Means for removing contaminants can vary widely but may include distillation, decantation, filtration, and / or drying using molecular sieves or other absorbents. The recycled or regenerated components may then be combined with the other components as described above.

[0097] Methods and Systems Compositions containing, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are useful in a number of methods and systems for providing refrigeration and freezing.

[0098] In one embodiment, a cooling method is provided, comprising evaporating a composition containing, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE in the vicinity of an object to be cooled, and then condensing the composition. In another embodiment, cooling is provided by a refrigeration system.

[0099] In one embodiment, a refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, refrigerated cases in supermarkets and convenience stores for beverages, dairy products, and agricultural products and processed foods. Low-temperature and medium-temperature refrigeration systems include refrigerator and freezer cabinets and displays in supermarkets and convenience stores, ice makers, beverage coolers, built-in coolers and freezers such as walk-in and reach-in coolers and freezers, supermarket racks and distributed systems, and refrigerated or frozen food transport.

[0100] In another embodiment, a refrigeration system is provided comprising a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE. In another embodiment, the composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE contained within the refrigeration system further comprises a lubricant. The refrigeration system comprises an evaporator, a compressor, a condenser, and an expansion unit, each operably connected to perform a vapor compression cycle.

[0101] In one embodiment, the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, refrigerated cases in supermarkets and convenience stores for beverages, dairy products, and agricultural products and processed foods. The refrigeration system may be for providing low-temperature refrigeration, medium-temperature refrigeration, and / or transport refrigeration. Low-temperature and medium-temperature refrigeration systems include refrigerator and freezer cabinets and displays in supermarkets and convenience stores, ice makers, beverage coolers, built-in coolers and freezers such as walk-in and reach-in coolers and freezers, supermarket racks and distributed systems, and transport of refrigerated or frozen foods.

[0102] In another embodiment, the refrigeration system is a secondary loop system.

[0103] Compositions containing, consisting of, or essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE have been found to have some temperature gradient in a heat exchanger. This allows the system to operate more efficiently when the heat exchanger is operating in counterflow mode or transverse flow mode with a counterflow tendency. Counterflow tendency means that the closer the heat exchanger is to counterflow mode, the more efficient heat transfer can be. Therefore, air conditioning heat exchangers, in particular evaporators, are designed to provide several embodiments of counterflow tendency. Accordingly, air conditioning or heat pump systems are provided herein, which include one or more heat exchangers (either evaporators, condensers, or both) operating in counterflow mode or transverse flow mode with a counterflow tendency.

[0104] Furthermore, the compositions of the present invention can be used in systems equipped with a heat exchanger operating in countercurrent mode.

[0105] In another embodiment, a refrigeration system is provided herein comprising a composition containing, consisting of, or essentially consisting of HFO-1252zc, HFC-32, and HFO-1234zeE, the system comprising one or more heat exchangers (either evaporators, condensers, or both) operating in counterflow mode, transverse flow mode, or transverse flow mode with a counterflow tendency.

[0106] In one embodiment, a method is provided for replacing R-454C in a refrigeration system, the method comprising providing the system with a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE in place of R-454C.

[0107] In one embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE is useful as a refrigerant in low-temperature refrigeration systems, medium-temperature refrigeration systems, and / or transport refrigeration systems. In another embodiment, a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE is useful as a refrigerant in any of the refrigeration systems described herein. [Examples]

[0108] (Example 1) The refrigeration performance is determined for compositions containing HFO-1252zc, HFC-32, and HFO-1234zeE, compared to R-454C (ASHRAE designation for refrigerants containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32), particularly compositions classified as flammability class 2L by ASHRAE. The calculation conditions are as follows.

[0109] [Table 2]

[0110] [Table 3]

[0111] The data demonstrates that these compositions have a GWP of less than 150, an improved COP compared to R-454C, and maintain Class 2L flammability. Although the capacity is reduced, many of the claimed compositions are within 20% of the capacity of R-454C.

[0112] (Example 2) The refrigeration performance is determined for compositions containing HFO-1252zc, HFC-32, and HFO-1234zeE, compared to R-454C (ASHRAE designation for refrigerants containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32), particularly compositions classified as flammability class 2 by ASHRAE. The calculation conditions are as follows.

[0113] [Table 4]

[0114] [Table 5]

[0115] The data demonstrates that these compositions have a GWP of less than 150, an improved COP compared to R-454C, and maintain Class 2 flammability. Although the capacity is reduced, some of the claimed compositions are within 15% of the capacity of R-454C, and many others are within 20% of the capacity of R-454C.

[0116] (Example 3) The refrigeration performance of compositions containing HFO-1252zc, HFC-32, and HFO-1234zeE will be determined by comparing them to R-404A (ASHRAE designation for a refrigerant containing 44% by weight of HFC-125, 52% by weight of HFC-143a, and 4% by weight of HFC-134a) under typical transport refrigeration conditions. The calculation conditions are as follows.

[0117] [Table 6]

[0118] [Table 7]

[0119] The data demonstrates that these compositions have a GWP of less than 150, an improved COP compared to R-404A, and maintain Class 2L flammability. Although the capacity is reduced, some of the claimed compositions are within 25% of the capacity of R-404A, and all others are within 30% of the capacity of R-404A.

Claims

1. A composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE.

2. The composition according to claim 1, comprising about 1 to 65 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 13 to 98 weight percent of HFO-1234zeE.

3. The composition according to claim 1, comprising about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 98 weight percent of HFO-1234zeE.

4. The composition according to claim 1, comprising about 1 to 23 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 55 to 77 weight percent of HFO-1234zeE.

5. The composition according to claim 1, comprising approximately 23 weight percent of HFO-1252zc, approximately 22 weight percent of HFC-32, and approximately 55 weight percent of HFO-1234zeE, or approximately 65 weight percent of HFO-1252zc, approximately 22 weight percent of HFC-32, and approximately 13 weight percent of HFO-1234zeE.

6. HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-374, n-butane, allene, 2-butene, cyclobutene, 2-methyl Lupropene, HCFO-1122, HFO-1132, HFO-1132a, HFO-1141, Ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, Propylene, HFO-1345, HFO-1252ze, HFO-1252yf, HFO-1252zf, HFO-1252ye, and E / Z-t-BuO-CF=CH-CH ３ The composition according to any one of claims 1 to 5, further comprising at least one additional compound selected from the above.

7. The composition according to any one of claims 1 to 6, further comprising at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

8. The method according to any one of claims 1 to 7, wherein the composition further comprises 0.1 to 200 ppm by weight of water, about 10 ppm to about 0.35 volume percent of oxygen, and / or about 100 ppm to about 1.5 volume percent of air or NAG.

9. The method according to any one of claims 1 to 8, wherein the composition comprises a stabilizer.

10. The method according to claim 9, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azole, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

11. The method according to claim 9 or 10, wherein the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

12. The method according to any one of claims 9 to 11, wherein the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant.

13. The method according to any one of claims 1 to 12, wherein the composition further comprises a lubricant.

14. The method according to claim 13, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether.

15. The method according to claim 13 or 14, wherein the lubricant is a polyol ester or a polyvinyl ether.

16. The aforementioned lubricant is 10 at 20°C １０ The method according to any one of claims 13 to 15, having at least one property selected from the group consisting of a volume resistivity greater than Ω-m, a surface tension of about 0.02 N / m to 0.04 N / m at 20°C, a kinematic viscosity of about 20 cSt to about 500 cSt at 40°C, a dielectric breakdown voltage of at least 25 kV, and a hydroxyl value of up to 0.1 mg KOH / g.

17. The method according to any one of claims 1 to 16, wherein the composition comprises at least one tracer.

18. The method according to claim 17, wherein the tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight.

19. The method according to claim 17 or 18, wherein the at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

20. The at least one tracer is HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC -272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, C FC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HC FC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCF O-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243z The method according to any one of claims 17 to 19, selected from the group consisting of f, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

21. The composition according to claim 1 or 20, wherein the composition does not contain or substantially contains a group A fluorinated substance, and the decomposition product of the composition does not contain or substantially contains a group A fluorinated substance.

22. A method for cooling, comprising evaporating a composition according to any one of claims 1 to 21 in the vicinity of an object to be cooled, and then condensing the composition, wherein the cooling is provided by a refrigeration system.

23. A refrigeration system comprising the composition according to any one of claims 1 to 21.

24. A refrigeration system comprising the composition according to any one of claims 1 to 21, for use in high ambient temperature applications where the ambient temperature exceeds approximately 35°C.

25. The system according to claim 23, comprising an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle.

26. The system according to claim 23 or 24, wherein the refrigeration system is for residential, light commercial, or industrial refrigeration.

27. The system according to any one of claims 23 to 25, wherein the system is for medium-temperature refrigeration, low-temperature refrigeration, or transport refrigeration.

28. A method for replacing R-454C in a refrigeration system, comprising providing the system with a composition according to any one of claims 1 to 21 instead of R-454C.

29. Use of the composition according to any one of claims 1 to 21 as a refrigerant in a low-temperature refrigeration system, a medium-temperature refrigeration system, and / or a transport refrigeration system.

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