Compositions containing difluoropropene and their use

Abstract

This disclosure relates to compositions comprising HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions are useful in heating and cooling methods, air conditioning and heat pump systems, and methods for replacing existing refrigerants.

Description

[Technical Field]

[0001] The present disclosure relates to compositions useful as refrigerants, particularly in air conditioning and heat pump systems. The compositions of the present disclosure are useful in methods for producing cooling and heating, methods for replacing refrigerants, and air conditioning and heat pump systems. [Background Art]

[0002] Over the past few 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 the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents, and propellants. These new compounds, such as the currently most widely used HFC refrigerants HFC-134a and HFC-125, have an ozone depletion potential (ODP) of zero, so they are not affected by current regulations that mandate phase-outs pursuant to the Montreal Protocol. In addition to the problem of ozone depletion, another environmental concern in many of these applications is global warming. HFC refrigerants such as HFC-134a and HFC-125 have a global warming potential (GWP) of 1,430 and 3,500, respectively, according to the UN IPCC Fourth Assessment Report (AR4).

[0003] This regulatory situation is constantly evolving, and characteristics other than ODP and GWP are also 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 various applications and meet evolving regulatory standards. [Summary of the Invention] [Problem to be Solved by the Invention]

[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 such as air conditioning and heat pumps.

[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 0.5 to 65 weight percent of HFO-1252zc, about 1 to 22 weight percent of HFC-32, and about 13 to 78 weight percent of HFO-1234zeE are also disclosed herein.

[0009] According to any of the embodiments described above, compositions comprising about 1 to 65 weight percent of HFO-1252zc, about 21 to 22 weight percent of HFC-32, and about 13 to 78 weight percent of HFO-1234zeE are also disclosed herein.

[0010] According to any of the embodiments described above, a composition comprising about 30 weight percent of HFO-1252zc, about 21 weight percent of HFC-32, and about 49 weight percent of HFO-1234zeE is also disclosed herein.

[0011] 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.

[0012] According to any of the embodiments described above, compositions further comprising at least one additional compound selected from HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye are also disclosed herein.

[0013] According to any of the embodiments described above, compositions further comprising 0.1 ppm 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.

[0014] According to any of the embodiments described above, compositions comprising a stabilizer are also disclosed herein.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] According to any of the embodiments described above, compositions further comprising a lubricant are also disclosed herein.

[0019] 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.

[0020] According to any of the embodiments described above, compositions in which the lubricant is a polyol ester or a polyvinyl ether are also disclosed herein.

[0021] According to any of the embodiments described above, the lubricant is 10 at 20°C. 10A composition having at least one property selected from the group consisting of a volume resistivity exceeding Ω-m, a surface tension of from about 0.02 N / m to about 0.04 N / m at 20° C., a kinematic viscosity of from about 20 cSt to about 500 cSt at 40° C., a dielectric breakdown voltage of at least 25 kV, and a hydroxyl value of at most 0.1 mg KOH / g is also disclosed herein.

[0022] According to any of the foregoing embodiments, a composition comprising at least one tracer is also disclosed herein.

[0023] According to any of the foregoing embodiments, a composition wherein the tracer is present in an amount of from about 1.0 ppm by weight to about 1000 ppm by weight is also disclosed herein.

[0024] According to any of the foregoing embodiments, a composition 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 is also disclosed herein.

[0025] According to any of the foregoing embodiments, also disclosed herein is a composition wherein said at least one tracer is 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.

[0026] According to any of the foregoing embodiments, also disclosed herein is a composition that does not comprise or substantially does not comprise Group A fluorinated substances, and the decomposition products of the composition do not comprise or substantially do not comprise Group A fluorinated substances.

[0027] According to any of the foregoing embodiments, also disclosed herein is a method for cooling, the method comprising the steps of: evaporating the composition in the vicinity of an object to be cooled, and then condensing the composition, wherein said cooling is provided by an air conditioner or a heat pump.

[0028] According to any of the foregoing embodiments, also disclosed herein is a method for heating, the method comprising the steps of: evaporating the composition, and then condensing the composition in the vicinity of an object to be heated, wherein said heating is provided by a heat pump.

[0029] In any of the embodiments described above, a system for cooling or heating comprising a composition is also disclosed herein. In another embodiment, the system comprises an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle. In another embodiment, the air conditioner or heat pump is a residential, light commercial, or industrial air conditioner or heat pump. In another embodiment, the system may be a secondary loop system. [Modes for carrying out the invention]

[0030] 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).

[0031] The composition comprises HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions provide refrigerant blends having 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.

[0032] 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.

[0033] 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.

[0034] 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 vehicle cabins), dehumidifiers, and combinations thereof. The focus of this application is air conditioning and heat pump systems.

[0035] 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.

[0036] 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).

[0037] 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).

[0038] 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).

[0039] 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.

[0040] Net cooling effect is the amount of heat absorbed in the evaporator by one kilogram of each refrigerant in order to produce useful cooling.

[0041] 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.

[0042] 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.

[0043] 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 IPCC (United Nations Intergovernmental Panel on Climate Change) Fourth Assessment Report (AR4). The estimated GWP for 1252zc is 1.

[0044] 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.

[0045] 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).

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] Refrigerant composition In one embodiment, the composition comprises, consists of, or is essentially composed of HFO-1252zc, HFC-32, and HFO-1234zeE. These compositions provide a low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0053] In another embodiment, the composition comprises, consists of, or is essentially composed of, about 0.5 to 65 weight percent of HFO-1252zc, about 21 to 22 weight percent of HFC-32, and about 13 to 78 weight percent of HFO-1234zeE.

[0054] 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.

[0055] 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).

[0056] 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).

[0057] 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.

[0058] HFO-1252zc, when combined with HFC-32 and HFO-1234zeE, may provide estimated Class 2 or Class 2L flammability as defined by ANSI / ASHRAE standard 34 and ISO 817. Class 2 and Class 2L flammability may be controllable in refrigeration systems. Specific applications may have different requirements regarding flammability.

[0059] 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.

[0060] [Table 1-1]

[0061] [Table 1-2]

[0062] 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, HFC-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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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).

[0067] 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.

[0068] In another embodiment, compositions comprising, consisting of, or essentially comprising 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.

[0069] 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.

[0070] 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.

[0071] Tracers may be present in a composition containing, consisting of, or essentially consisting 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. The tracer may be a refrigerant compound, but it is present in the composition at a level that is unlikely to affect the performance of the refrigerant components of the composition.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] In 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 an air conditioning system or a heat pump system.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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).

[0083] 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.

[0084] 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.

[0085] 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)).

[0086] In one embodiment, as used herein, “Group A fluorinated substance” includes a substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to any H / Cl / Br / I atoms), and (ii) meets the criteria for persistence in soil / sediments and water, which are defined in Annex XIII (Section 1.1.1) of the European Union’s REACH Regulation (https: / / reachonline.eu / This is defined in reach / en / annex-xiii-1-1.1-1.1.1.html (accessed May 2, 2023) and referenced in the Regulatory Report 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 May 2, 2023). In one embodiment, the Group A fluorinated substance is, but is not limited to, trifluoroacetic acid (TFA).

[0087] In another embodiment, as used herein, "Group A fluorinated substance" has a Henry's Law constant of ≤250 Pa * m 3 The material comprises any substance in moles that contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to any H / Cl / Br / I atoms). In one embodiment, the Group A fluorinated substance is, but is not limited to, TFA.

[0088] Accordingly, according to some embodiments, compositions of the present invention comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are free from or substantially free from group A fluorinated substances such as TFA. In one embodiment, the term “free from” as used herein with respect to the presence of group A fluorinated substances in the compositions means that the amount of such substances in the compositions 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.

[0089] 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.

[0090] Methods and Systems Compositions comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE are useful in a number of methods and systems for providing air conditioning and heating.

[0091] In one embodiment, a cooling method is provided, comprising the steps of 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, wherein the cooling is provided by an air conditioner or a heat pump.

[0092] In one embodiment, the air conditioner may be a residential, commercial, or industrial air conditioning system. These may include, but are not limited to, systems located outside the building but connected to it, such as windows, ducted or unducted systems, packaged terminals, and rooftop systems. The method may be particularly useful in high ambient temperature regions due to the high critical temperatures of blends containing HFO-1252zc, HFC-32, and HFO-1234zeE.

[0093] In another embodiment, a heating method is provided, comprising the steps of evaporating a composition comprising HFO-1252zc, HFC-32, and HFO-1234zeE, and then condensing the composition in the vicinity of an object to be heated, wherein the heating is provided by a heat pump.

[0094] The claimed compositions, comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, provide heating and cooling performance with desirable results. These compositions provide cooling and / or heating capabilities within 13% or 10% of the cooling and / or heating capabilities of R-454C under similar operating conditions. Furthermore, compositions comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE provide improved COP compared to R-454C under similar operating conditions.

[0095] In one embodiment, the heat pump is a residential, light commercial, or industrial heat pump system. These may include, but are not limited to, residential heat pumps that provide comfortable air conditioning and heating, hot water heat pumps for heating air (by secondary loop) or water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high-temperature heat pumps. Due to the high critical temperatures of blends containing HFO-1252zc, HFC-32, and HFO-1234zeE, it is possible to heat water to a higher temperature than propane or R-454C.

[0096] In another embodiment, the method for generating cooling is particularly useful in areas where the ambient temperature may exceed at least 35°C.

[0097] In geographical regions with high ambient temperatures, air conditioning is essential, and refrigerant compositions with high critical temperatures and high thermal stability are desirable. Currently available hydrofluorocarbon (HFC) refrigerants such as R-410A, R-407C, or R-32 have relatively low critical temperatures. As a result, these refrigerants do not perform well in extremely hot environments. The energy efficiency of a refrigerant generally decreases when the condensation temperature reaches the refrigerant's critical temperature during operation at high ambient temperatures. In hot climates, R-22 has continued to be the refrigerant of choice for many air conditioning and refrigeration applications because it is non-flammable and has a higher critical temperature that provides higher cooling capacity and higher energy efficiency compared to R-410A or R-32 in hot climates. However, R-22 is designated as an ozone-depleting substance under the Montreal Protocol to Reduce Ozone Depletion. Therefore, the manufacture and use of R-22 for air conditioning and refrigeration applications are mandated and mandated by law. There is interest in finding refrigerants that have the lowest possible direct GWP and that perform well even in hot climate (or high ambient) temperature regions.

[0098] In a method for producing cooling, the object to be cooled can be defined as any space, place, object, or body for which cooling is desirable. Examples include open or enclosed spaces requiring cooling, such as apartments or multi-unit dwellings, university dormitories, townhouses or other terraced houses, or single-family homes; or the object to be cooled could be any other building, such as an office building, supermarket, college or university classroom, or government building.

[0099] In another embodiment, a method for generating air conditioning at high ambient temperatures is provided. This method comprises the steps of evaporating a composition containing, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE, and then condensing the composition. This method is particularly useful in areas where ambient temperatures may exceed 35°C.

[0100] In another embodiment, a method is provided for replacing HCFC-22 in a high-ambient air conditioning system, the method comprising supplying the system with a composition comprising, consisting of, or essentially comprising HFO-1252zc, HFC-32, and HFO-1234zeE. The method for replacing HCFC-22 is particularly useful in areas where ambient temperatures may exceed 35°C.

[0101] Similarly, some industrial air conditioning systems must release heat in environments with high ambient temperatures. HCFC-124 has been used as a working fluid in such applications. HCFC-124 is also regulated as an ozone-depleting substance under the Montreal Protocol, and more environmentally sustainable alternatives are desired. Therefore, a method for replacing HCFC-124 in industrial air conditioning systems is provided, comprising supplying the system with a composition containing, essentially derived from, or consisting of HFO-1252zc, HFC-32, and HFO-1234zeE. The method for replacing HCFC-124 is particularly useful in areas where ambient temperatures may exceed 35°C.

[0102] In another embodiment, a method for generating cooling, and a method for replacing HCFC-22 or HCFC-124, is useful for systems operating at ambient temperatures of 40°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 45°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 50°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 55°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 60°C or higher. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 35°C to 50°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 35°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 40°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 45°C to 60°C. In another embodiment, a method for generating cooling is useful for systems operating at ambient temperatures of 50°C to 60°C.

[0103] In another embodiment, a system for cooling or heating is provided, comprising a composition containing HFO-1252zc, HFC-32, and HFO-1234zeE, and optionally a lubricant. The system comprises an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle.

[0104] Air conditioners or heat pump systems may be for residential, light commercial, or industrial use. Various such systems are described herein.

[0105] In another embodiment, an air conditioning or heat pump system comprising a composition containing, consisting of, or essentially consisting of HFO-1252zc, HFC-32, and HFO-1234zeE may be a secondary loop system.

[0106] The following embodiments are provided to illustrate specific aspects of the present invention and are not intended to limit the scope of the appended claims. [Examples]

[0107] (Example 1) The claimed composition was compared with R-454C (ASHRAE designation for a refrigerant containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32) under the residential heat pump conditions described below. Table 2 provides the calculation results.

[0108] [Table 2]

[0109] [Table 3-1]

[0110] [Table 3-2]

[0111] [Table 3-3]

[0112] [Table 3-4]

[0113] [Table 3-5]

[0114] The data demonstrates that compositions containing HFO-1252zc, HFC-32, and HFO-1234zeE provide a higher COP (measure of energy efficiency) than either propane or R-454C in both cooling and heating modes. Furthermore, the cooling and heating capacities are within 13%, or even within 10%, of the capacity of R-454C. Therefore, the compositions of the present invention provide a suitable alternative to R-454C.

[0115] (Example 2) The claimed composition was compared to R-454C (ASHRAE designation for a refrigerant containing 78.5% by weight of HFO-1234yf and 21.5% by weight of HFC-32) under the residential air conditioning conditions described below. Table 3 provides the calculation results under the following conditions.

[0116] Average condenser temperature = 46.1℃ [115°F], Average evaporator temperature = 10.0℃ [50°F] Supercooling=8.3K[15°F], Superheat = 11.1K [20°F], Compressor efficiency = 0.70

[0117] [Table 4]

[0118] The composition of the present invention, containing HFO-1252zc, HFC-32, and HFO-1234zeE, provides similar performance (within 10%) to R-454C, which is higher than that of propane. Furthermore, this composition provides an improved COP compared to R-454C, which is slightly better than that of propane. All of this is achieved while maintaining a GWP of less than 150 and a reasonable average temperature gradient.

Claims

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

2. The composition according to claim 1, comprising about 0.5 to 65 weight percent of HFO-1252zc, about 21 to 22 weight percent of HFC-32, and about 13 to 78 weight percent of HFO-1234zeE.

3. The composition according to claim 1, comprising about 30 weight percent of HFO-1252zc, about 21 weight percent of HFC-32, and about 49 weight percent of HFO-1234zeE.

4. 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 3, further comprising at least one additional compound selected from the above.

5. The composition according to any one of claims 1 to 4, 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.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises 0.1 ppm 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.

7. The composition according to any one of claims 1 to 3, wherein the composition comprises a stabilizer.

8. The composition according to claim 7, 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.

9. The composition according to any one of claims 7 or 8, 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.

10. The composition according to any one of claims 7 to 9, wherein the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant.

11. The composition according to any one of claims 1 to 10, wherein the composition further comprises a lubricant.

12. The composition according to claim 11, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether.

13. The composition according to claim 11 or 12, wherein the lubricant is a polyol ester or a polyvinyl ether.

14. The aforementioned lubricant is 10 at 20°C １０ The composition according to any one of claims 11 to 13, 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 hydroxy value of up to 0.1 mg KOH / g.

15. The composition according to any one of claims 1 to 14, wherein the composition comprises at least one tracer.

16. The composition according to claim 15, wherein the tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight.

17. The composition according to any one of claims 15 or 16, 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.

18. 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, HCF C-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 A composition according to any one of claims 15 to 17, selected from the group consisting of HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

19. The composition according to any one of claims 1 or 18, 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.

20. A method for cooling, comprising the steps of evaporating a composition according to any one of claims 1 to 19 in the vicinity of an object to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

21. A method for heating, comprising the steps of evaporating a composition according to any one of claims 1 to 19, and then condensing the composition in the vicinity of an object to be heated, wherein the heating is provided by a heat pump.

22. A system for cooling or heating comprising the composition according to any one of claims 1 to 19.

23. The system according to claim 22, comprising an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle.

24. The system according to claim 22 or 23, wherein the air conditioner or heat pump is an air conditioner or heat pump for residential, light commercial, or industrial use.

25. A method for replacing R-454C or propane in an air conditioning or heat pump system, comprising providing the system with a composition according to any one of claims 1 to 19 instead of R-454C or propane.

26. Use of the composition according to any one of claims 1 to 19 as a refrigerant in an air conditioning or heat pump system.

27. The system according to any one of claims 22 to 24, wherein the system is a secondary loop system.

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