Compositions comprising difluoropropene, tetrafluoropropene and difluoromethane and uses thereof

Abstract

Disclosed herein are compositions comprising at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, HFC-32. The compositions have low GWP and can be used in methods of cooling and heating, air conditioning and heat pump systems or equipment, and methods of replacing current refrigerants.

Description

Technical Field

[0001] This disclosure relates to compositions that can be used as refrigerants, and particularly for use in air conditioning systems and heat pump systems. The compositions of this disclosure can be used in methods of refrigeration and heating, and in methods of replacing refrigerants in air conditioning systems and heat pump systems. Background Technology

[0002] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of HFC compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fourth Assessment Report (AR4), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,430 and 3,500, respectively.

[0003] This regulatory environment is constantly evolving, and the nature of consideration is no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also provide excellent performance in a wide range of applications and meet evolving regulatory standards.

[0004] This invention addresses certain problems associated with conventional refrigerants and provides refrigerant blends containing 1,1-difluoropropylene that meet the evolving regulatory environment. Summary of the Invention

[0005] To meet the rapidly changing regulatory environment, the inventors have identified a fluoroolefin compound that provides properties associated with existing refrigerants and can continue to be used even with the standards of an evolving regulatory environment.

[0006] The compositions disclosed herein relate to fluoropropylene compositions comprising 1,1-difluoropropylene (also known as HFO-1252zc or R-1252zc). This document shows that the compound possesses advantageous properties for refrigerant applications such as air conditioning and heat pumps. According to one embodiment, this document discloses compositions comprising at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, or HFC-32, comprising:

[0007] HFO-1252zc, HFO-1234zeE, HFC-32 and HFC-134; or

[0008] HFO-1252zc, HFO-1234zeE, HFC-32 and CO2; or

[0009] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134 and CO2; or

[0010] HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or

[0011] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and HFC-134a; or

[0012] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134a and CO2.

[0013] The composition of the above embodiments has an AGW of less than 300, less than 150, or less than 149.

[0014] The composition of the above embodiments has an average temperature glide of no more than 10.0 K.

[0015] The flammability of the compositions described above is classified as Class 1, Class 2L, Class 2, or Class 3 according to ASHRAE.

[0016] According to one embodiment, the composition of any of the above embodiments further comprises at least one additional compound selected from the group consisting of: HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-134a, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, H FO-374, n-butane, propadiene, 2-butene, cyclobutene, 2-methylpropene, 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 / Zt-BuO-CF=CH-CH3.

[0017] According to one embodiment, the composition of any of the above embodiments further comprises at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, or HFO-1252ye.

[0018] According to one embodiment, the composition of any of the above embodiments further comprises 0.1 ppm to 200 ppm of water by weight; about 10 ppm to about 0.35% by volume of oxygen by volume; and / or about 100 ppm to about 1.5% by volume of air or NAG.

[0019] According to the embodiments, the composition of any of the above embodiments further comprises a stabilizer, preferably selected from one or more of the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones, or preferably selected from one or more of the group consisting of toluenetriazole, benzotriazole, tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene. When present, the stabilizer is present in an amount of about 0.001% by weight to 1.0% by weight based on the weight of the refrigerant.

[0020] According to the embodiments, the composition of any of the above embodiments further comprises a lubricant, preferably selected from one or more of the group consisting of polyalkylene glycols, polyol esters, poly-α-olefins and polyethylene ethers, or preferably polyol esters or polyethylene ethers.

[0021] According to the embodiments, the composition of any one of the above embodiments includes a lubricant having at least one property selected from the group consisting of: greater than 10 at 20°C. 10 Volume resistivity in Ω-m; surface tension of about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of about 20 cSt to about 500 cSt at 40 °C; breakdown voltage of at least 25 kV; and hydroxyl value of up to 0.1 mg KOH / g.

[0022] According to the embodiments, the composition of any of the above embodiments comprises at least one tracer, which is preferably present in an amount of about 1.0 ppm to about 1000 ppm by weight, and is preferably selected from one or more of the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

[0023] According to the embodiments, any one of the compositions in the above embodiments further comprises at least one tracer, said at least one tracer being 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.

[0024] According to the implementation scheme, the composition of any of the above implementation schemes is free of or substantially free of Group A fluorinated substances, and the degradation products of the composition are free of or substantially free of Group A fluorinated substances.

[0025] According to the embodiments, this document also discloses a method for cooling, which includes evaporating a composition of any of the above embodiments near a body to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0026] According to the embodiments, this document also discloses a method for heating, which includes evaporating the composition of any of the above embodiments and then condensing the composition near the body to be heated, wherein the heating is provided by a heat pump.

[0027] According to embodiments, this document also discloses a system for cooling or heating, comprising a composition of any of the embodiments described above. In another embodiment, the system includes an evaporator, a compressor, a condenser, and an expander, each operatively 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 yet another embodiment, the system may be a secondary system.

[0028] According to the embodiments, this document also discloses a method for replacing R-454C, propane, or R-410A in an air conditioning or heat pump system, the method comprising providing a composition of any of the embodiments described above.

[0029] According to the embodiments, the use of the composition of any of the above embodiments in an air conditioning or heat pump system is also disclosed herein. Detailed Implementation

[0030] This invention relates to compositions containing at least one of 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), or carbon dioxide (CO2) and 1,1-difluoropropylene (HFO-1252zc), difluoromethane (HFC-32), or E-1,3,3,3-tetrafluoropropylene (HFO-1234zeE). Such compositions may be candidates for alternative refrigerants such as R-454C, R-410A, or propane, exhibiting low global warming potential (GWP), improved environmental fate characteristics, and improved coefficient of performance (COP).

[0031] The composition comprises, consists of, or is substantially composed of at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, or HFC-32. These refrigerant blends provide low global warming potential values ​​and improved coefficients of performance compared to existing refrigerants and other proposed alternatives.

[0032] Refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas during a cycle used to transfer heat and then returns to the original state.

[0033] A heat transfer system is a system (or device) used to produce a heating or cooling effect in a specific space. Heat transfer systems can be mobile or stationary.

[0034] Examples of heat transfer systems include any type of refrigeration and air conditioning system, including but not limited to stationary heat transfer systems, air conditioners, refrigerators, chillers, heat pumps, flooded evaporator heat pumps, direct expansion cooler heat pumps, coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, portable refrigeration units, portable heat transfer systems, portable heat pumps (including heat pumps for comfort cooling and heating of passenger compartments in automobiles), portable air conditioning units (for cooling of passenger compartments in automobiles), dehumidifiers, and combinations thereof. The focus of this application is on air conditioning systems and heat pump systems.

[0035] Volumetric capacity is the amount of heat absorbed or discharged divided by the theoretical compressor displacement. The heat removed or absorbed is the refrigerant mass flow rate multiplied by the enthalpy difference across the heat exchanger. 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 enthalpy difference across the heat exchanger. A higher volumetric capacity allows for the use of a smaller compressor under the same heat load. Here, cooling capacity refers to volumetric capacity in cooling mode, while heating capacity refers to volumetric capacity in heating mode.

[0036] The coefficient of performance (COP) is the heat absorbed or released divided by the energy input required to operate the cycle (approximately the compressor power). COP is specific to the operating mode of a heat pump, so COP is used for heating or COP is used for cooling. COP is directly related to the energy efficiency ratio (EER).

[0037] Subcooling refers to the temperature of a liquid dropping below its saturation point at a given pressure. The saturation point of a liquid is the temperature at which vapor completely condenses into a liquid. By cooling the liquid below its saturation temperature (or bubble point), the net cooling effect can be increased. Subcooling thus improves the cooling capacity and energy efficiency of a system. Subcooling is the amount of cooling to below the saturation temperature (in degrees Celsius).

[0038] Superheating refers to the temperature of vapor rising above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. At a given pressure, superheating continues to heat the vapor to a higher temperature. By heating the vapor above its saturation temperature (or dew point), the net refrigeration effect can be increased. Therefore, when superheating occurs in the evaporator, the system's refrigeration capacity and energy efficiency can be improved. Superheating in the suction line does not increase the net refrigeration effect and reduces efficiency and capacity. Superheat is the amount of heat generated above the saturation temperature (in degrees Celsius).

[0039] Temperature glide (sometimes simply called "glide") is the absolute value of the difference between the onset and termination temperatures of a refrigerant phase change process within the condenser of a refrigerant system, excluding any subcooling or superheating. For the evaporator, glide is the temperature difference between the dew point and the evaporator inlet. Glide can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to temperature glide in air conditioning or heat pump systems, it is common to provide an average temperature glide, which is the average of the temperature glide in the evaporator and the temperature glide in the condenser. Glide applies to blended refrigerants, i.e., refrigerants composed of at least two components.

[0040] Net cooling efficiency is the amount of heat absorbed by each kilogram of refrigerant in the evaporator to produce usable cooling.

[0041] Mass flow rate is the amount (in kilograms) of refrigerant that circulates through a refrigeration system, heat pump system, or air conditioning system within a given time period.

[0042] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition used in any heat transfer system) that provides hydrodynamic lubrication to the compressor to help prevent parts from seizing.

[0043] The Global Warming Potential (GWP) is an indicator used to estimate the relative contribution of atmospheric emissions of a specific greenhouse gas to global warming compared to the emission of one kilogram of carbon dioxide. GWPs can be calculated over different time periods, showing the impact on the atmospheric lifetime of a given gas. GWPs over a 100-year time period are typically used as a reference value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In this paper, the GWP values ​​are those reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4). The GWP estimate for HFO-1252zc is 1.

[0044] Ozone depletion potential (ODP) refers to the amount of ozone loss caused by a substance. ODP is the ratio of the effect of a chemical on ozone to the effect of a similar mass of CFC-11 (trichlorofluoromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs ranging from 0.01 to 1.0. The hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein have zero ODP because they do not contain chlorine, bromine, or iodine compounds known to cause ozone decomposition and depletion. HFO-1252zc has zero ozone depletion potential.

[0045] 1,1-Difluoropropylene (HFO-1252zc or R-1252zc) can be prepared by hydrogenating 3,3,3-trifluoropropylene (HFO-1243zf) on a carbon-supported palladium catalyst to form 1,1,1-trifluoropropane (HFC-263fb), followed by dehydrofluorination of HFC-263fb on a chromium catalyst or by pyrolysis at high temperature (see Agent's File No. FL2084 filed with this document and incorporated herein by reference).

[0046] E-1,3,3,3-Tetrafluoropropylene (HFO-1234zeE or R-1234zeE) is commercially available from Honeywell (Charlotte, North Carolina, USA). Difluoromethane (HFC-32 or R-32), 1,1,2,2-tetrafluoroethane (HFC-134 or R-134), 1,1,1,2-tetrafluoroethane (HFC-134a, R-134a), and carbon dioxide (CO2) are commercially available from various sources worldwide.

[0047] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus.

[0048] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0049] The transitional phrase "consistently composed of..." is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that the additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel characteristics of the invention protected by the claims. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...". Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain trace amounts (e.g., less than about 0.5% by weight in total) of impurities and / or byproducts (e.g., refrigerant components from the preparation of the refrigerant components or regenerated from other systems) that do not materially affect the novel and essential characteristics of the refrigerant mixture.

[0050] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless specific paragraphs are cited. In case of any conflict, this specification and its included definitions shall prevail. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0052] Refrigerant Composition

[0053] In one embodiment, the composition comprises, consists of, or is substantially composed of at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, or HFC-32. These compositions provide low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP). Furthermore, many of the compositions disclosed in this invention provide capacities within 20% of the capacity of R-454C.

[0054] In another embodiment, the composition comprises, consists of, or is substantially composed of the following:

[0055] HFO-1252zc, HFO-1234zeE, HFC-32 and HFC-134; or

[0056] HFO-1252zc, HFO-1234zeE, HFC-32 and CO2; or

[0057] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134 and CO2; or

[0058] HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or

[0059] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and HFC-134a; or

[0060] HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134a and CO2.

[0061] All percentages should be understood as weight percentages relative to the percentages of the components in the composition.

[0062] In the embodiments, the composition comprises, consists of, or is substantially composed of: about 1%-30% HFO-1252zc, about 48%-82% HFO-1234zeE, about 15%-22% HFC-32, and about 1%-4% HFC-134; or about 0.2%-98.5% HFO-1252zc, about 0.2%-98.5% HFO-1234zeE, about 0.2%-26.0% HFC-134, and about 0.2%-43.8% HFC-32; or about 0.2%-98.5% HFO-1252zc, about 0.2%-98.5% HFO-1252zc, and about 0.2%-98.5% HFC-134. HFO-1234ze(E), approximately 0.2%-12.9% HFC-134 and approximately 0.2%-20.9% HFC-32; or approximately 19.9%-84.6% HFO-1252zc, approximately 0.2%-58.7% HFO-1234ze(E), approximately 0.2%-3.0% HFC-134 and approximately 14.9%-20.9% HFC-32; or approximately 19.9%-22.9% HFO-1252zc, approximately 55.7%-58.7% HFO-1234ze(E), approximately 0.5% HFC-134 and approximately 20.9% HFC-32; or approximately 22.9% HFO-1252zc, approximately 55.7% HFO-1234ze(E), approximately 0.5% HFC-134, and approximately 20.9% HFC-32; or approximately 19.9% ​​HFO-1252zc, approximately 58.7% HFO-1234ze(E), approximately 0.5% HFC-134, and approximately 20.9% HFC-32; or 1.0%-21.0% HFO-1252zc, 64.0%-92.0% HFO-1234ze(E), 1.0%-11.0% HFC-134, and 1.0%-9.0% HFC-32; or 15.0%-2 1.0% HFO-1252zc, 63.0%-76.0% HFO-1234zeE, 1.0%-8.0% HFC-134 and 7.0%-9.0% HFC-32, or 15.0%-19.0% HFO-1252zc, 68.0%-72.0% HFO-1234ze(E), 3.0%-7.0% HFC-134 and 6.0%-10.0% HFC-32; or approximately 17.0% HFO-1252zc, approximately 70.0% HFO-1234ze(E), approximately 5.0% HFC-134 and approximately 8.0% HFC-32.

[0063] In another embodiment, the composition comprises, consists of, or substantially comprises: about 13%-30% HFO-1252zc, about 54%-72% HFO-1234zeE, about 8%-14% HFC-32, and about 1%-4% CO2; or about 13%-about 30% HFO-1252zc, about 54%-about 72% HFO-1234zeE, and about 8%-about 14% HFC-32. 2 and approximately 1%–4% CO2; or approximately 0.2%–98.5% HFO-1252zc, approximately 0.2%–98.5% HFO-1234ze(E), approximately 0.2%–44.0% HFC-32 and approximately 0.2%–8.0% CO2; or approximately 0.2%–98.5% HFO-1252zc, approximately 0.2%–98.5% HFO-1234ze(E), approximately 0.2%–22.0% H FC-32 and approximately 0.2%-3.0% CO2; or approximately 27.9%-84.6% HFO-1252zc, approximately 0.2%-51.7% HFO-1234ze(E), approximately 11.0%-22.0% HFC-32 and approximately 0.2%-2.0% CO2; or approximately 27.9%-64.7% HFO-1252zc, approximately 12.9%-51.7% HFO-1234ze(E), approximately 1 5.0%-22.0% HFC-32 and about 0.5%-1.0% CO2; or about 64.0% HFO-1252zc, about 13.0% HFO-1234ze(E), about 22.0% HFC-32 and about 1.0% CO2; or about 27.9% HFO-1252zc, about 51.7% HFO-1234ze(E), about 19.9% ​​HFC-32 and about 0.5% CO2.

[0064] In another embodiment, the composition comprises, consists of, or substantially comprises: about 5%-30% HFO-1252zc, about 46%-77% HFO-1234zeE, about 5%-22% HFC-32, about 1%-10% HFC-134, and about 1%-4% CO2; or about 1%-21% HFO-1252zc, about 42%-82% HFO-1234zeE, about 11%-22% HFC-32, about 1%-6% HFC-134, and about 1%-3% CO2; or about 0.2%-98.5% HFO-1252zc, about 0.2%-98.5% HFO-1234zeE, and about 1%-3% CO2. E), approximately 0.2%-26.0% HFC-134, approximately 0.2%-43.8% HFC-32, and approximately 0.2%-3.0% CO2; or approximately 0.2%-98.5% HFO-1252zc, approximately 0.2%-98.5% HFO-1234ze(E), approximately 0.2%-12.9% HFC-134, approximately 0.2%-20.9% HFC-32, and approximately 0.2%-3.0% CO2; or approximately 24.9%-84.6% HFO-1252zc, approximately 0.2%-53.7% HFO-1234ze(E), approximately 0.2%-6.0% HFC-134, and approximately 11.0%-20.9% HFC- 32 and approximately 0.2%-2.0% CO2; or approximately 24.9%-63.7% HFO-1252zc, approximately 13.9%-53.7% HFO-1234ze(E), approximately 0.2%-5.0% HFC-134, approximately 13.0%-20.9% HFC-32 and approximately 0.2%-2.0% CO2; or approximately 6.0%-20.0% HFO-1252zc, approximately 55.0%-73.0% HFO-1234zeE, approximately 11.0%-22.0% HFC-32 and approximately 1.0%-2.0% CO2; or approximately 5%-30% HFO-1252zc and approximately 46%-77% HFO-1234ze E, approximately 5%-22% HFC-32, approximately 1%-10% HFC-134 and approximately 1%-4% CO2; or approximately 1%-21% HFO-1252zc, approximately 42%-82% HFO-1234zeE, approximately 11%-22% HFC-32, approximately 1%-6% HFC-134 and approximately 1%-3% CO2; or approximately 63.7% HFO-1252zc, approximately 13.9% HFO-1234ze(E), approximately 0.5% HFC-134, approximately 20.9% HFC-32 and approximately 1.0% CO2; or approximately 24.9% HFO-1252zc, approximately 53.7% HFO-1234ze(E), approximately 0.It contains 2% HFC-134, approximately 20.9% HFC-32, and approximately 0.2% CO2.

[0065] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 1%-21% HFO-1252zc, about 57%-82% HFO-1234zeE, about 16%-22% HFC-32, and about 1%-3% HFC-134a; or about 0.1%-21.0% HFO-1252zc, about 58.0%-80.0% HFO-1234zeE, about 16.0%-20.0% HFC-32, and about 1.0%-3.0% HFC-134a.

[0066] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 1.0%-96.0% HFO-1252zc, about 1.0%-96.0% HFO-1234ze(E), about 1.0%-40.0% HFC-32, about 1.0%-24.0% HFC-134, and about 1.0%-21.0% HFC-134a; or about 1.0%-96.0% HFO-1252zc, about 1.0%-96.0% HFO-1234ze(E), about 1.0%-18.0% HFC-32, about 1.0%-11.0% HFC-134, and about 1.0%-10.0% HFO-1252zc, about 1.0%-96.0% HFO-1234ze(E), about 1.0%-18.0% HFC-32, about 1.0%-11.0% HFC-134, and about 1.0%-10.0% HFO-1234ze(E). HFC-134a; or approximately 36.0%-82.0% HFO-1252zc, approximately 1.0%-44.0% HFO-1234ze(E), approximately 15.0%-18.0% HFC-32, approximately 1.0%-3.0% HFC-134, approximately 1.0%-2.0% HFC-134a; or approximately 36.0%-63.0% HFO-1252zc, approximately 17.0%-44.0% HFO-1234ze(E), approximately 16.0%-18.0% HFC-32, approximately 1.0%-2.0% HFC-134 and approximately 1.0%-2.0% HFC-134a; or approximately 63.0% HFO-125 2zc, approximately 17.0% HFO-1234ze(E), approximately 1.0% HFC-134, approximately 1.0% HFC-134a, and approximately 18.0% HFC-32; or approximately 53.0% HFO-1252zc, approximately 28.0% HFO-1234ze(E), approximately 16.0% HFC-32, approximately 2.0% HFC-134, and approximately 1.0% HFC-134a; or approximately 1.0%-96.0% HFO-1252zc, approximately 1.0%-96.0% HFO-1234ze(E), approximately 1.0%-40.0% HFC-32, approximately 1.0%-25.0% HFC-134, and approximately 1.0% HFC-32. -21.0% HFC-134a; or approximately 1.0%-96.0% HFO-1252zc, approximately 1.0%-96.0% HFO-1234ze(E), approximately 1.0%-18.0% HFC-32, approximately 1.0%-11.0% HFC-134 and approximately 1.0%-10.0% HFC-134a; or approximately 45.0%-81.0% HFO-1252zc, approximately 1.0%-35.0% HFO-1234zeE, approximately 16.0%-18.0% HFC-32, approximately 1.0%-2.0% HFC-134 and approximately 1.0%-2.0% HFC-134a; or approximately 45.0%-63.0% HFO-1252zc, approximately 17.0%-35.0% HFO-1234zeE, approximately 17.0%-18.0% HFC-32, approximately 1.0%-1.0% HFC-134, and approximately 1.0%-1.0% HFC-134a; or approximately 63.0% HFO-1252zc, approximately 17.0% HFO-1234zeE, approximately 18.0% HFC-32, approximately 1.0% HFC-134, and approximately 1.0% HFC-134a; or approximately 54.0% HFO-1252zc, approximately 27.0% HFO-1234zeE, approximately 17.0% HFC-32, approximately 1.0% HFC-134, and approximately 1.0% HFC-134a.

[0067] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-40.0% HFC-32; 2.0%-22.0% HFC-134a and 2.0%-78.0% CO2; or about 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-18.0% HFC-32, 2.0%-10.0% HFC-134a and 2.0%-78.0% CO2; or about 34 .... 84.0% HFO-1252zc, 2.0%-46.0% HFO-1234ze(E), 10.0%-18.0% HFC-32, 2.0%-6.0% HFC-134a, and 2.0%-2.0% CO2; or approximately 34.0%-62.0% HFO-1252zc, 16.0%-46.0% HFO-1234ze(E), 12.0%-18.0% HFC-32, 2.0%-4.0% HFC-134a, and 2.0%-2.0% CO2; or approximately 62.0% HFO-1252zc, 16.0% HFO-1234ze(E), and 18.0% HF C-32, 2.0% HFC-134a and 2.0% CO2; or approximately 46.0% HFO-1252zc, 38.0% HFO-1234ze(E), 12.0% HFC-32, 2.0% HFC-134a and 2.0% CO2; or approximately 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-40.0% HFC-32 and 2.0%-22.0% HFC-134a and 2.0%-92.0% CO2; or approximately 28.0%-82.0% HFO-1252zc and 2.0%-40.0% HFO -1234ze(E), 4.0%-28.0% HFC-32, 2.0%-20.0% HFC-134a and 2.0%-4.0% CO2; or approximately 28.0%-66.0% HFO-1252zc, 2.0%-40.0% HFO-1234ze(E), 4.0%-28.0% HFC-32, 2.0%-20.0% HFC-134a and 2.0%-4.0% CO2; or approximately 52.0% HFO-1252zc, 14.0% HFO-1234ze(E), 26.0% HFC-32, 6.0% HFC-134a and 2.0% CO2; or approximately 58.0% HFO-1252zc, 26.0% HFO-1234ze(E), 12.0% HFC-32, 2.0% HFC-134a, and 2.0% CO2.

[0068] The compositions disclosed herein provide a GWP of less than or equal to 300, less than or equal to 150, or less than or equal to 149, a COP comparable to or improved upon R-454C, and a cooling capacity comparable to or within 20% of R-454C. Additionally, the compositions provide an acceptable average temperature glide and reasonable compressor discharge temperature. Furthermore, the flammability of the compositions as defined above is estimated to be Class 1, Class 2, or Class 2L according to ASHRAE classification.

[0069] Flammability is a term used to refer to the ability of a composition to ignite and / or spread a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (“LFL”) is the minimum concentration of a heat transfer composition in air that, under the test conditions specified in ASTM E681, can propagate a flame through a homogeneous mixture of the composition and air. The upper flammability limit (“UFL”) is the maximum concentration of a heat transfer composition in air that, under the same test conditions, can propagate a flame through a homogeneous mixture of the composition and air.

[0070] In order for a refrigerant to be classified as low flammability (2L class) by ANSI / ASHRAE, it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa); 2) have a flame propagation rate >0.0062 lb / ft. 3 (0.10kg / m 3 1) LFL; 2) Heat of combustion <8169 Btu / lb (19,000 kJ / kg); and 3) Maximum combustion rate ≤3.9 in / s (10 cm / s) when tested in dry air at 73.4°F (23.0°C) and 14.7 psia (101.3 kPa).

[0071] 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); 2) have a flame propagation rate >0.0062 lb / ft. 3 (0.10kg / m 3 ) LFL; and 3) having a heat of combustion of <8169 Btu / lb (19,000 kJ / kg).

[0072] ASHRAE Standard 34 provides a method for calculating the heat of combustion of refrigerant blends using an equilibrium stoichiometric equation based on the complete combustion of one mole of refrigerant with enough oxygen for a stoichiometric reaction.

[0073] HFO-1252zc can be combined with at least one of HFC-134, HFC-134a, and / or CO2, and HFC-32 and HFO-1234zeE, providing an estimated flammability rating of Class 1, Class 2, or 2L as defined by ANSI / ASHRAE Standard 34 and ISO 817. Class 2 and 2L flammability ratings are manageable in refrigeration systems. Specific applications may have different flammability requirements.

[0074] Compositions disclosed herein containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof, are estimated to be classified as flammable in the 2L class.

[0075] Any of the above embodiments involving compositions comprising or substantially comprising at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, HFC-32, or compositions thereof may further comprise at least one additional compound from the list in Table A.

[0076] Table A

[0077]

[0078]

[0079] In one embodiment, any one of the compositions of the above embodiments further comprises at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFC-134a, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye. In another embodiment, any one of the compositions of the above embodiments further comprises at least one additional compound containing HFO-1234yf. In another embodiment, any one of the compositions of the above embodiments further comprises at least one additional compound containing HFO-1243zf. In another embodiment, any one of the compositions of the above embodiments further comprises at least one additional compound containing HFO-263fb.

[0080] Some of the compounds identified in Table 1 that are present in the compositions of the present invention may exist as different configurational isomers or stereoisomers. The present invention is intended to include all isomers of a single configuration, a single stereoisomer, or any combination or mixture thereof. For example, 1,2-difluoroethane (HFO-1132) is intended to represent any combination or mixture of cis-isomer (Z), trans-isomer (E), or any ratio of two isomers. A single isomer or multiple isomers of the same compound may be used in any proportion.

[0081] The amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 ppm and less than 5,000 ppm, and specifically may be in the range of greater than zero to about 1,000 ppm, about 5 ppm to about 500 ppm and about 1 ppm to about 100 ppm.

[0082] In one embodiment, the amount of the additional compound present in any of the aforementioned refrigerant compositions may be greater than 0% by weight and less than 1% by weight, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight of the refrigerant composition.

[0083] Compositions containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof, will behave more consistently and stably in the presence of only a small amount of water. Therefore, in embodiments, the composition of any of the above embodiments contains less than 100 ppm (by weight) of water, preferably less than 20 ppm (by weight), and even more preferably less than 10 ppm (by weight).

[0084] Furthermore, compositions containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof, will exhibit more consistent and stable behavior in the presence of only trace amounts of oxygen or air. Therefore, in another embodiment, the composition of any of the above embodiments further contains less than about 5% by volume of non-adsorbable gas (NAG), preferably less than 3% by volume, and more preferably less than 1.5% by volume. Moreover, due to the presence of air or NAG, the compositions protected by the claims of this invention will contain less than 1% by volume of oxygen, preferably less than 0.5% by volume, and more preferably less than 0.3% by volume.

[0085] In another embodiment, the composition of any of the above embodiments further comprises a stabilizer. Such stabilizer compounds are intended to be present in small amounts and to prevent decomposition during use or storage of the composition due to the presence of water, air, NAG, or oxygen in the system. Due to the presence of double bonds, HFO-type refrigerants may experience thermal instability and decomposition under extreme use, handling, or storage conditions. Therefore, the addition of a stabilizer to HFO-type refrigerants can be advantageous. Stabilizers may particularly include nitromethane, ascorbic acid, terephthalic acid, azoles such as toluenetriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, 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 WO2019213004, WO2020222864 and WO2020222865; the disclosure of which is incorporated herein by reference.

[0086] If the composition does contain a stabilizer, it may contain any amount of any of the stabilizers listed above, from 0.001 wt% to 1 wt%, preferably from about 0.001 wt% to about 0.5 wt%, more preferably from about 0.001 wt% to about 0.3 wt%.

[0087] In embodiments, the compositions of the above embodiments contain a tracer compound or a tracer. The tracer may include 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 parts (ppm) to about 1000 ppm by weight based on 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.

[0088] Tracers can be present in predetermined amounts to allow the detection of any dilution, contamination, or other alterations to the composition. The presence of certain compounds in the composition can indicate the method or process by which one of the components was produced. Tracers can also be added to the composition in specific amounts to identify the composition's origin. In this way, the detection of patent infringement can be achieved. Tracers can be refrigerant compounds, but are present in the composition at levels unlikely to affect the performance of the refrigerant component.

[0089] The tracer compound can be a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochloroolefin, a chlorofluorocarbon, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, or a combination thereof. Examples of tracer compounds include, but are not limited to, 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-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), and HFC-245fa (1,1,1,3,3-pentafluoropropane). Propane), 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 (trichlorofluoromethane), CFC-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-1,1,2,2-tetrafluoroethane), 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 (ethylene fluoride), HCFO-1130 (1,2-dichloroethylene), HCFO-1130a (1,1-dichloroethylene), HCFO-1131 (1-chloro-2-fluoroethane), HCFO-1122 (2-chloro-1,1-difluoroethylene), HFO-1123 (1,1,2-trifluoroethylene), HFO-1234ye (1,2,3,3-tetrafluoropropylene), 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.

[0090] In another embodiment, the composition of any of the above embodiments further comprises at least one lubricant. The lubricant may be selected from polyol esters, polyvinyl ethers, and polyalkylene glycols. The lubricant may also include those commonly referred to as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include alkanes (i.e., saturated hydrocarbons with straight and branched carbon chains), cycloalkanes (i.e., saturated hydrocarbons with cyclic or cyclic structures, which may be alkanes), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention also include those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryl compounds (i.e., straight and branched alkylalkylbenzenes), synthetic alkanes and cycloalkanes, organosilicones, and polyalphaolefins. A representative conventional lubricant of the present invention is commercially available BVM 100 N (an alkane mineral oil sold by BVA Oils), available from Crompton Co. under the trademark Suniso. ® 3GS and Suniso ® 5GS commercially available cycloalkane mineral oil, can be branded as Sontex ® 372LT is a cycloalkanes mineral oil purchased from Pennzoil, and can be marketed under the trademark Calumet. ® RO-30 is a cycloalkanes mineral oil obtained from Calumet Lubricants, and can be marketed under the brand name Zerol. ® 75. Zerol ® 150 and Zerol ® 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0091] The lubricants of this invention also include lubricants designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of this invention under the operating conditions of compression refrigeration and air conditioning equipment. Lubricants include, but are not limited to, polyol esters (POEs) such as Castrol. ®100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow Chemical, Midland, Mich., and polyvinyl ethers (PVEs) such as PVE-FVC68D.

[0092] In one specific embodiment, the composition of any of the above embodiments is combined with a PAG lubricant, a PVE lubricant, or a POE lubricant for use in an air conditioning system or a heat pump system. The lubricant may be present in an amount less than 80% by weight of the total composition. The lubricant may also be present in an amount less than 60% by weight of the total composition. In other embodiments, the amount of lubricant may be between about 0.1% by weight and 50% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 20% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 5% by weight of the total composition. If lubricant compatibility is an issue, the system may optionally include an oil separator for more reliable operation.

[0093] In another embodiment, the composition of any of the above embodiments is used to introduce a lubricant into an air conditioning system or heat pump system, and alternatively other additives, such as a) an acid scavenger, b) a performance enhancer, and c) a flame retardant. In a preferred embodiment, the composition of the present invention comprises an acid scavenger. Examples of acid scavengers that may be included in the compositions of the present invention 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 Application Publication No. WO 2020 / 222864, the disclosures of which are incorporated herein by reference in their entirety. In some embodiments, the acid scavenger may comprise one or more epoxides, one or more amines and / or one or more hindered amines, such as, for example, but not limited to, epoxide. The acid scavenger (e.g., an activated aromatic compound, a siloxane, or both) may be present at any concentration resulting in a relatively low total acid value, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. Preferably, the acid scavenger is present at a concentration greater than about 0.0050% by weight, more preferably greater than about 0.05% by weight, and even more preferably greater than about 0.1% by weight (e.g., greater than about 0.5% by weight) based on the total weight of the refrigerant composition. Based on the total weight of the refrigerant composition, the acid scavenger is preferably present at a concentration 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 greater than about 2% by weight (e.g., less than about 1.8% by weight).

[0094] Preferred additives include those described in U.S. Patent Nos. 5,152,926 and 4,755,316, which are incorporated herein by reference. In particular, preferred extreme pressure additives comprise mixtures of: (A) toluenetriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphorohydrin (e.g., ZELEC 3337), or (iii) zinc dialkyl dithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-thiadiazole derivative (e.g., Curvan 826) or mixtures thereof. Additional examples of additives that may be used are given in U.S. Patent No. 5,976,399 (Schnur, 5:12-6:51, which is hereby incorporated by reference).

[0095] Acid value was measured in mg KOH / g according to ASTM D664-01. Total halide concentration, fluoride ion concentration, and total organic acid concentration were measured by ion chromatography. The chemical stability of the refrigerant system was measured according to ASHRAE 97:2007 (RA2017), "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The viscosity of the lubricant was tested at 40°C according to ASTM D-7042.

[0096] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) proposed 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 Serial No. 11 / 575,256, published as U.S. Publication 2007 / 0290164) and Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Publication 2006 / 0116310). All of the foregoing applications are expressly incorporated herein by reference.

[0097] Preferred flame retardants include those described and incorporated herein by reference in patent application CA 2557873 A1, entitled "Refrigerant compositions containing fluorine substituted olefins", and fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox described and incorporated herein by reference in patent application WO2009018117A1, entitled "Refrigerant compositions comprising fluoroolefins and uses thereof". ® Lubricant.

[0098] In one implementation, as used herein, “Group A fluorinated substances” includes any substance that satisfies the following condition: (i) contains at least one fully fluorinated methyl (–CF3) or methylene (–CF2–) carbon atom (without any H / Cl / Br / I attached thereto); as well as (ii) Complies with the persistence standards in soil / sediments and water as specified in Annex XIII (Section 1.1.1) of the EU REACH Regulation. https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html Visited on May 2, 2023 This standard is referenced in Annex XV Restriction Report dated March 22, 2023, and its disclosure is incorporated herein by reference. https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414- 8823-b49b9fd43aea, accessed May 2, 2023 In one implementation, Group A fluorinated substances include, but are not limited to, trifluoroacetic acid (TFA).

[0099] As used in this article, "Group A fluorides" includes Henry's Law constant. < 250Pa*m 3 Any substance containing at least one fully fluorinated methyl (–CF3) or methylene (–CF2–) carbon atom (without any H / Cl / Br / I bonded to it). In one embodiment, Group A fluorinated substances include, but are not limited to, TFA.

[0100] Therefore, according to some embodiments, the composition of any of the above embodiments is free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase "free from" regarding the presence of Group A fluorinated substances in the compositions of the invention means that, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing a gaseous or liquid sample), and / or ion chromatography (by analyzing a water sample after bubbling a hot fluid through water), the amount of such substance in the composition is sufficiently low to be undetectable, including but not limited to 0%. Such methods are well known to those skilled in the art. In some embodiments, as used herein, the phrase "substantially free" regarding the presence of Group A fluorinated substances in the compositions of the invention means, when measured by gas chromatography (GC), such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high performance liquid chromatography (HPLC) or high performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0% by weight and < 5% by weight, or >0% by weight and < 4% by weight, or >0% by weight and < 3% by weight, or >0% by weight and < 2% by weight, or >0% by weight and < 1% by weight, and all values ​​and ranges therebetween. TFA analytical standards can be used for gas chromatography or ion chromatography and are available from sources such as Sigma Aldrich.

[0101] Furthermore, in some embodiments, the degradation products of the composition of any of the above embodiments are free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase "free from" regarding the formation of Group A fluorinated substances by the compositions of the present invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation 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 with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. In one embodiment, as used herein, the phrase "substantially free from" regarding the formation of Group A fluorinated substances by the compositions of the present invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is >0% and < 5%, or >0% and < 4%, or >0% and < 3%, or >0% and < 2%, or >0% and < 1%, and all values ​​and ranges in between. Methods and Systems

[0102] Compositions comprising or substantially comprising at least one of HFC-134, HFC-134a or CO2 and HFO-1252zc, HFO-1234zeE, HFC-32 may be used in many methods and systems for providing air conditioning and heating.

[0103] In one embodiment, a cooling method is provided, comprising evaporating near a subject to be cooled a composition comprising at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, HFC-32, or a composition thereof or substantially thereof, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0104] In one embodiment, the air conditioner can be a residential, commercial, or industrial air conditioning system. These air conditioners can include, but are not limited to, window-type, ducted, ductless, enclosed-terminal systems, and those located outside the building but connected to it, such as rooftop systems. Due to the high critical temperatures of blends containing at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, or HFC-32, the method of the present invention may be particularly useful in regions with high ambient temperatures.

[0105] In another embodiment, a heating method is provided, comprising evaporating a composition comprising at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, or HFC-32, and then condensing the composition near the body to be heated, wherein the heating is provided by a heat pump.

[0106] In one embodiment, the heat pump is a residential, light commercial, or industrial heat pump system. These heat pumps may include, but are not limited to, residential heat pumps providing comfortable air conditioning and heating, hot water heat pumps for heating air (via a secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high-temperature heat pumps. Due to the high critical temperature of blends containing at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, or HFC-32, it is possible to heat water to temperatures higher than propane or R-454C or R-410A.

[0107] In another embodiment, the method for refrigeration is particularly useful in areas where the ambient temperature may exceed 35°C.

[0108] In geographical areas with high ambient temperatures, where air conditioning becomes essential, 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. Therefore, these refrigerants perform poorly in extremely hot environments. During operation at high ambient temperatures, the energy efficiency of the refrigerant typically decreases as the condensing temperature approaches its critical temperature. In hot climates, R-22 remains the refrigerant of choice for many air conditioning and refrigeration applications because it is non-flammable and has a higher critical temperature, thus providing higher cooling capacity and higher energy efficiency in hot climates compared to R-410A or R-32. However, R-22 is an ozone-depleting substance under the Montreal Protocol, which aims to reduce ozone depletion. Therefore, legislation has been passed mandating the phase-out of R-22 in the air conditioning and refrigeration sectors. There is a focus on finding refrigerants with the lowest possible direct GWP and good performance in hot (or high ambient) temperature regions.

[0109] In methods for generating cooling, the subject to be cooled can be defined as any space, location, object, or subject for which cooling is desired. Examples include open or enclosed spaces requiring cooling, such as residences, such as apartments or apartment buildings, university dormitories, townhouses or other attached houses, or single-family homes; or the subject to be cooled can be any other building, such as office buildings, supermarkets, college or university classrooms or administration buildings.

[0110] In another embodiment, a method for generating air conditioning at high ambient temperatures is provided. The method comprises evaporating a composition containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or a composition thereof or substantially composed thereof, and then condensing said composition. This method is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0111] In another embodiment, a method is provided for replacing HCFC-22 in a high-ambient-temperature air conditioning device, comprising supplying the device with a composition comprising at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof. This method of replacing HCFC-22 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0112] Similarly, in some industrial air conditioning applications, heat must be released in high ambient temperatures. HCFC-124 has been used as a working fluid in such applications. HCFC-124, as an ozone-depleting substance, is also controlled under the Montreal Protocol, and more environmentally sustainable alternatives are needed. Therefore, a method for replacing HCFC-124 in industrial air conditioning equipment is provided, comprising supplying said equipment with at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or a composition substantially composed of or composed of these. This method of replacing HCFC-124 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0113] In another embodiment, the cooling method and the method for replacing HCFC-22 or HCFC-124 can be used in systems operating at ambient temperatures of 40°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 45°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 50°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 55°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 60°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 35°C and 50°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 35°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 40°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 45°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 50°C and 60°C.

[0114] In another embodiment, a system for cooling or heating is provided, comprising a composition containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, and optionally a lubricant. The system includes an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle.

[0115] Air conditioning or heat pump systems can be residential, light commercial, or industrial. Various such systems have been described previously in this article.

[0116] In another implementation, the air conditioning or heat pump system is a secondary loop system.

[0117] It has been found that compositions containing at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof, will exhibit some temperature slip in the heat exchanger. Therefore, the system will operate more efficiently if the heat exchanger operates in counter-current mode or a cross-flow mode with a counter-current tendency. A counter-current tendency means that the closer the heat exchanger is to a counter-current mode, the more efficient the heat transfer. Therefore, heat exchangers, particularly evaporators, in air conditioning or heat pump systems are designed to provide some aspects of this counter-current tendency. Thus, this document provides air conditioning or heat pump systems comprising one or more heat exchangers (evaporators, condensers, or both) operating in counter-current mode or a cross-flow mode with a counter-current tendency.

[0118] In addition, the compositions of the present invention can be used in systems having heat exchangers that operate in a cross-flow mode.

[0119] In another embodiment, this document provides an air conditioning or heat pump system comprising a composition comprising at least one of HFC-134, HFC-134a, or CO2 and HFO-1252zc, HFO-1234zeE, HFC-32, or substantially thereof, wherein the system comprises one or more heat exchangers (evaporator, condenser, or both) operating in a counter-current mode, a cross-current mode, or a cross-current mode with a counter-current tendency.

[0120] In another embodiment, a method for replacing R-454C, propane, or R-410A in an air conditioning or heat pump system is also disclosed herein, the method comprising providing any one of the aforementioned compositions.

[0121] In another embodiment, the use of any of the foregoing compositions in an air conditioning or heat pump system is also disclosed herein.

[0122] The following examples are provided to illustrate certain aspects of the invention and should not limit the scope of the appended claims. Example Example 1

[0123] Under the residential air conditioning conditions shown below, the composition of the present invention, protected by claims and containing HFO-1252zc, HFO-1234zeE, HFC-134, and HFC-32, is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The calculation results are provided in Tables 1A and 1B.

[0124]

[0125] Data shows that the composition containing HFO-1252zc, HFO-1234zeE, HFC-134 and HFC-32 provides a higher COP (a measure of energy efficiency) than R-454C, and a CAP (cooling capacity) within 20% of R-454C.

[0126] In summary, for the cooling mode, the composition ranges of 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), 0.2% to 26.0% HFC-134, and 0.2% to 43.8% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 9.9K, a cooling capacity range with a deviation of -48.1% to 22.3% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of -2.4% to 5.4% from the cooling COP of R-454C evaluated under the same setting conditions.

[0127] Similarly, but less generally, for cooling modes, the composition ranges of 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), 0.2% to 12.9% HFC-134, and 0.2% to 20.9% HFC-32 will have a GWP of less than 150, a maximum average slip of approximately 9.6K, an ASHRAE flammability rating of 3, 2L, and 2, a cooling capacity range with a deviation of -48.1% to -2.2% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of 1.5% to 5.0% from the cooling COP of R-454C evaluated under the same setting conditions.

[0128] For the cooling mode, the preferred blend composition range of 19.9% ​​to 84.6% R-1252ZC, 0.2% to 58.7% HFO-1234ZE(E), 0.2% to 3.0% HFC-134, and 14.9% to 20.9% HFC-32 will have a GWP of <150, a maximum average heat exchanger slip of 9.4 K, and an ASHRAE flammability rating of 2, 3, and 2 L, with minimum and maximum cooling capacities of -10.0% and -2.2% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 1.5% and 2.5% respectively compared to R-454C evaluated under the same setting conditions.

[0129] For the cooling mode, blends ranging from 19.9% ​​to 22.9% R-1252ZC, 55.7% to 58.7% HFO-1234ZE(E), 0.5% to 0.5% HFC-134, and 20.9% to 20.9% HFC-32, or even more preferred blend compositions, will have a GWP of <150, a maximum average heat exchanger slip of 9.4 K, an ASHRAE flammability rating of 2 L, and minimum and maximum cooling capacities of -9.9% and -9.2% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 2.4% and 2.5% respectively compared to R-454C evaluated under the same setting conditions.

[0130] Even more preferred is a maximum cooling capacity composition of 22.9 wt% R-1252ZC, 55.7 wt% HFO-1234ZE(E), 0.5 wt% HFC-134, and 20.9 wt% HFC-32, which is -9.2% of R-454C, wherein the COP for cooling under the same cycling conditions is 2.4% lower than that of R-454C, the maximum average heat exchanger slip is 9.3 K, and its ASHRAE flammability rating is 2 L.

[0131] Even more preferred is a composition of 19.9 wt% R-1252ZC, 58.7 wt% HFO-1234ZE(E), 0.5 wt% HFC-134, and 20.9 wt% HFC-32, which has a maximum cooling COP efficiency of 2.5% compared to R-454C, wherein the CAP for cooling under the same cycling conditions is -9.9% compared to R-454C, the maximum average heat exchanger slip is 9.4 K, and its ASHRAE flammability rating is 2 L.

[0132]

[0133]

[0134]

[0135] In summary, for the cooling mode, the composition range of 1.0% to 21.0% R-1252ZC, 64.0% to 92.0% HFO-1234ZE(E), 1.0% to 11.0% HFC-134, and 1.0% to 9.0% HFC-32 will have a GWP of <150, an ASHRAE flammability rating of 2L, a mean temperature glide of no more than 6.5, a cooling capacity of 40.0% to 48.9% of the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP of 108.6% to 109.3% of the cooling COP of R-454C evaluated under the same setting conditions.

[0136] Similarly, but less generally, for cooling modes, the composition range of 15.0% to 21.0% HFO-1252zc, 63.0% to 76.0% HFO-1252zeE, 1.0% to 8.0% HFC-134, and 7.0% to 9.0% HFC-32 will have a GWP of <150, an ASHRAE flammability rating of 2L, a mean temperature glide of no more than 6.5, a cooling capacity of 49.1% to 53.0% of the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP of 108.6% to 108.7% of the cooling COP of R-454C evaluated under the same setting conditions. Example 2

[0137] Under the residential heat pump conditions shown below, the claimed composition of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, and CO2 is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The calculation results are provided in Tables 2A and 2B.

[0138]

[0139] Data shows that compositions containing HFO-1252zc, HFO-1234zeE, HFC-32 and CO2 offer higher COP (a measure of energy efficiency) than R-454C, and CAP (cooling capacity) within 20% of R-454C or even within 15% in some cases.

[0140] In summary, for heating modes, the composition ranges of 0.2% to 8.0% carbon dioxide, 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), and 0.2% to 44.0% HFC-32 will have a GWP of less than 298, a maximum average slip of approximately 10.0 K, a heating capacity range with a deviation of -50.7% to 50.3% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of -3.6% to 2.3% from the heating COP of R-454C evaluated under the same setting conditions. Table 2 lists example compositions with ASHRAE flammability ratings of 2L, 2, and 3 in the GWP < 298 range.

[0141] Similarly, but less generally, for heating modes, the composition ranges of 0.2% to 3.0% carbon dioxide, 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), and 0.2% to 22.0% HFC-32 will have a GWP of less than 149, a maximum average slip of about 10.0 K, an ASHRAE flammability rating of 2, 3, and 2 L, a heating capacity range with a deviation of -50.7% to 2.0% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of 0.1% to 2.3% from the heating COP of R-454C evaluated under the same setting conditions.

[0142] For the heating mode, a preferred blend composition range of 0.2% to 2.0% carbon dioxide, 27.9% to 84.6% R-1252ZC, 0.2% to 51.7% HFO-1234ZE(E), and 11.0% to 22.0% HFC-32 will have a GWP of <149, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2 and 3, and minimum and maximum heating capacities of -10.0% and 2.0% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 0.6% and 1.3% respectively compared to R-454C evaluated under the same setting conditions.

[0143] For the heating mode, blends with compositions ranging from 0.5% to 1.0% carbon dioxide, 27.9% to 64.7% R-1252ZC, 12.9% to 51.7% HFO-1234ZE(E), and 15.0% to 22.0% HFC-32, or even more preferred blend compositions, will have a GWP of <149, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2, and minimum and maximum heating capacities of -10.0% and 1.5% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 0.6% and 1.2% respectively compared to R-454C evaluated under the same setting conditions.

[0144] Even more preferred is a maximum heating capacity composition of 1.0 wt% carbon dioxide, 64.0 wt% R-1252ZC, 13.0 wt% HFO-1234ZE(E) and 22.0 wt% HFC-32, which is 1.5% higher than that of R-454C, wherein the COP for heating under the same cycling conditions is 0.6% higher than that of R-454C, the maximum average heat exchanger slip is 9.2 K, and its ASHRAE flammability rating is 2.

[0145] Even more preferred is a composition of 0.5 wt% carbon dioxide, 27.9 wt% R-1252ZC, 51.7 wt% HFO-1234ZE(E), and 19.9 wt% HFC-32, which has a maximum heating COP of 1.2% compared to R-454C, wherein the CAP for heating under the same cycle conditions is -9.5% compared to R-454C, the maximum average heat exchanger slip is 10.0 K, and its ASHRAE flammability rating is 2.

[0146]

[0147]

[0148]

[0149] Example 3

[0150] Under the residential heat pump conditions shown below, the claimed composition of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and CO2 is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The calculation results are provided in Tables 3A and 3B.

[0151]

[0152] Data shows that compositions containing HFO-1252zc, HFO-1234zeE, HFC-134, HFC-32 and CO2 provide a higher COP (a measure of energy efficiency) than R-454C, and a CAP (cooling capacity) within 20%, or 15%, or even 12% of R-454C in some cases.

[0153] In summary, for heating modes, the composition ranges of 0.2% to 3.0% carbon dioxide, 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), 0.2% to 26.0% HFC-134, and 0.2% to 43.8% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 10.0 K, a heating capacity range with a deviation of -51.3% to 33.3% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of -2.4% to 2.6% from the heating COP of R-454C evaluated under the same setting conditions. Table 3 lists example compositions with ASHRAE flammability ratings of 2, 2L, 3, and 1 in the GWP < 300 range.

[0154] Similarly, but less generally, for heating modes, the composition ranges of 0.2% to 3.0% carbon dioxide, 0.2% to 98.5% R-1252ZC, 0.2% to 98.5% HFO-1234ZE(E), 0.2% to 12.9% HFC-134, and 0.2% to 20.9% HFC-32 will have a GWP of less than 150, a maximum average slip of about 10.0 K, an ASHRAE flammability rating of 2, 3, and 2 L, a heating capacity range with a deviation of -51.3% to 0.5% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of 0.1% to 2.5% from the heating COP of R-454C evaluated under the same setting conditions.

[0155] For the heating mode, a preferred blend composition range of 0.2% to 2.0% carbon dioxide, 24.9% to 84.6% R-1252ZC, 0.2% to 53.7% HFO-1234ZE(E), 0.2% to 6.0% HFC-134, and 11.0% to 20.9% HFC-32 will have a GWP of <150, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2 and 3, and minimum and maximum heating capacities of -10.0% and 0.5% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 0.7% and 1.3% respectively compared to R-454C evaluated under the same setting conditions.

[0156] For the heating mode, blend compositions ranging from 0.2% to 2.0% carbon dioxide, 24.9% to 63.7% R-1252ZC, 13.9% to 53.7% HFO-1234ZE(E), 0.2% to 5.0% HFC-134, and 13.0% to 20.9% HFC-32, or even more preferred blend compositions, will have a GWP of <150, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2, and minimum and maximum heating capacities of -10.0% and -0.1% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 0.7% and 1.2% respectively compared to R-454C evaluated under the same setting conditions.

[0157] Even more preferred is a maximum heating capacity composition of 1.0 wt% carbon dioxide, 63.7 wt% R-1252ZC, 13.9 wt% HFO-1234ZE(E), 0.5 wt% HFC-134 and 20.9 wt% HFC-32, which is -0.1% of R-454C, wherein under the same cycling conditions, the COP for heating is 0.7% of R-454C, the maximum average heat exchanger slip is 9.2 K, and its ASHRAE flammability rating is 2.

[0158] Even more preferred is a composition of 0.2 wt% carbon dioxide, 24.9 wt% R-1252ZC, 53.7 wt% HFO-1234ZE(E), 0.2 wt% HFC-134, and 20.9 wt% HFC-32, which has a maximum heating COP of 1.2% compared to R-454C, wherein the CAP for heating under the same cycle conditions is -9.8% compared to R-454C, the maximum average heat exchanger slip is 9.9 K, and its ASHRAE flammability rating is 2.

[0159]

[0160]

[0161]

[0162] Example 4

[0163] Under the residential air conditioning conditions shown below, the claimed composition of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The calculation results are provided in Tables 4A and 4B.

[0164] condition :

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] Data shows that the compositions of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a provide a GWP of less than 150 and a reasonable compressor discharge temperature. Additionally, the compositions provide an average temperature glide of less than 10K, or less than 9K, or less than 8K. Furthermore, the compositions provide up to 20% of the capacity of R-454C, and their COP is at least 2%, or even 30% or more, higher than that of R-454C. Example 5

[0171] Under the residential air conditioning conditions shown below, the claimed composition of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and CO2 is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). Tables 5A and 5B provide the calculation results. condition :

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] Data shows that the composition of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and CO2 provides a GWP of less than 150 and a reasonable compressor discharge temperature. Additionally, the composition provides an average temperature glide of less than 10K, or less than 9K. Furthermore, the composition provides up to 20% of the capacity of R-454C, and its COP is at least 2%, or even 30% or more, higher than that of R-454C.

[0178] The capacity of the claimed compositions of the present invention may be lower than that of R-410A, but the increased COP (at least 7% higher, or even 8% higher than that of R-410A) may warrant a minor redesign to allow the use of the lower capacity refrigerant of the present invention in systems similar to R-410A systems. Example 6

[0179] Under residential heat pump conditions in the cooling and heating modes shown below, the composition of the present invention, protected by claims and containing HFO-1252zc, HFO-1234zeE, HFC-134, HFC-134a, and HFC-32, is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). Table 6a provides the calculation results for the cooling mode, while Table 6b provides the calculation results for the heating mode.

[0180]

[0181] In summary, for cooling modes, the composition ranges of 1.0% to 96.0% R-1252ZC, 1.0% to 96.0% HFO-1234ZE(E), 1.0% to 24.0% HFC-134, 1.0% to 21.0% HFC-134A, and 1.0% to 40.0% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 10.0 K, a cooling capacity range with a deviation of -47.2% to 20.1% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of -1.1% to 4.7% from the cooling COP of R-454C evaluated under the same setting conditions. Table 6a lists example compositions with ASHRAE flammability ratings of 2L, 2, 3, and 1 in the GWP < 300 range.

[0182] Similarly, but less generally, for cooling modes, the composition ranges of 1.0% to 96.0% R-1252ZC, 1.0% to 96.0% HFO-1234ZE(E), 1.0% to 11.0% HFC-134, 1.0% to 10.0% HFC-134A, and 1.0% to 18.0% HFC-32 will have a GWP of less than 150, a maximum average slip of approximately 9.6 K, an ASHRAE flammability rating of 2L, 2, and 3, a cooling capacity range with a deviation of -47.2% to -5.2% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of 1.7% to 4.4% from the cooling COP of R-454C evaluated under the same setting conditions.

[0183] For the cooling mode, the preferred blend composition range of 36.0% to 82.0% R-1252ZC, 1.0% to 44.0% HFO-1234ZE(E), 1.0% to 3.0% HFC-134, 1.0% to 2.0% HFC-134A, and 15.0% to 18.0% HFC-32 will have a GWP of <150, a maximum average heat exchanger slip of 8.2 K, and ASHRAE flammability ratings of 3 and 2, with minimum and maximum cooling capacities of -10.0% and -5.2% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 2.2% and 2.6% respectively compared to R-454C evaluated under the same setting conditions.

[0184] For the cooling mode, blends ranging from 36.0% to 63.0% R-1252ZC, 17.0% to 44.0% HFO-1234ZE(E), 1.0% to 2.0% HFC-134, 1.0% to 2.0% HFC-134A, and 16.0% to 18.0% HFC-32, or even more preferred blends, will have a GWP of <150, a maximum average heat exchanger slip of 8.2 K, an ASHRAE flammability rating of 2, and minimum and maximum cooling capacities of -10.0% and -6.0% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 2.2% and 2.4% respectively compared to R-454C evaluated under the same setting conditions.

[0185] Even more preferred is a maximum cooling capacity composition of 63.0 wt% R-1252ZC, 17.0 wt% HFO-1234ZE(E), 1.0 wt% HFC-134, 1.0 wt% HFC-134A and 18.0 wt% HFC-32, which is -6.0% compared to R-454C, wherein under the same cycling conditions, the COP for cooling is 2.2% compared to R-454C, the maximum average heat exchanger slip is 7.4 K, and its ASHRAE flammability rating is 2.

[0186] Even more preferred is a composition of 53.0 wt% R-1252ZC, 28.0 wt% HFO-1234ZE(E), 2.0 wt% HFC-134, 1.0 wt% HFC-134A and 16.0 wt% HFC-32, which has a maximum cooling COP efficiency of 2.4% compared to R-454C, wherein the CAP for cooling under the same cycle conditions is -9.9% compared to R-454C, the maximum average heat exchanger slip is 7.2 K, and its ASHRAE flammability rating is 2.

[0187] In summary, for heating modes, the composition ranges of 1.0% to 96.0% R-1252ZC, 1.0% to 96.0% HFO-1234ZE(E), 1.0% to 25.0% HFC-134, 1.0% to 21.0% HFC-134A, and 1.0% to 40.0% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 10.0 K, a heating capacity range with a deviation of -50.1% to 19.7% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of -1.3% to 2.8% from the heating COP of R-454C evaluated under the same setting conditions. Table 6b lists example compositions with ASHRAE flammability ratings of 2L, 3, 1, and 2 in the GWP < 300 range.

[0188] Similarly, but less generally, for heating modes, the composition ranges of 1.0% to 96.0% R-1252ZC, 1.0% to 96.0% HFO-1234ZE€, 1.0% to 11.0% HFC-134, 1.0% to 10.0% HFC-134A, and 1.0% to 18.0% HFC-32 will have a GWP of less than 150, a maximum average slip of about 10.0 K, an ASHRAE flammability rating of 2, 3, and 2 L, a heating capacity range with a deviation of -50.1% to -6.5% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of 1.1% to 2.7% from the heating COP of R-454C evaluated under the same setting conditions.

[0189] For the heating mode, the preferred blend composition range of 45.0% to 81.0% R-1252ZC, 1.0% to 35.0% HFO-1234ZE€, 1.0% to 2.0% HFC-134, 1.0% to 2.0% HFC-134A, and 16.0% to 18.0% HFC-32 will have a GWP of <150, a maximum average heat exchanger slip of 8.3 K, an ASHRAE flammability rating of 2 and 3, and minimum and maximum heating capacities of -10.0% and -6.5% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 1.1% and 1.2% respectively compared to R-454C evaluated under the same setting conditions.

[0190] For the heating mode, blends ranging from 45.0% to 63.0% R-1252ZC, 17.0% to 35.0% HFO-1234ZE€, 1.0% to 1.0% HFC-134, 1.0% to 1.0% HFC-134A, and 17.0% to 18.0% HFC-32, or even more preferred blend compositions, will have a GWP of <150, a maximum average heat exchanger slip of 8.3 K, an ASHRAE flammability rating of 2, and minimum and maximum heating capacities of -9.9% and -7.4% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of 1.1% and 1.1% respectively compared to R-454C evaluated under the same setting conditions.

[0191] Even more preferred is a composition of 63.0 wt% R-1252ZC, 17.0 wt% HFO-1234ZE€, 1.0 wt% HFC-134, 1.0 wt% HFC-134A and 18.0 wt% HFC-32, which has a maximum heating capacity that is -7.4% compared to R-454C, wherein the COP for heating under the same cycling conditions is 1.1% compared to R-454C, the maximum average heat exchanger slip is 7.8 K, and its ASHRAE flammability rating is 2.

[0192] Even more preferred is a composition with a maximum heating COP of 54.0 wt% R-1252ZC, 27.0 wt% HFO-1234ZE€, 1.0 wt% HFC-134, 1.0 wt% HFC-134A and 17.0 wt% HFC-32, which has a maximum heating COP of 1.1% compared to R-454C, wherein the CAP for heating under the same cycling conditions is -9.9% compared to R-454C, the maximum average heat exchanger slip is 7.8 K, and its ASHRAE flammability rating is 2.

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] Example 7

[0201] Under residential heat pump conditions in the cooling and heating modes shown below, the composition of the present invention, protected by claims, containing HFO-1252zc, HFO-1234zeE, HFC-134a, HFC-32, and CO2, is compared with R-454C (ASHRAE designation of a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). Table 7a provides the calculated results for the cooling mode, while Table 7b provides the results for the heating mode.

[0202]

[0203] In summary, for cooling modes, the composition ranges of 2.0% to 78.0% carbon dioxide, 2.0% to 92.0% R-1252ZC, 2.0% to 92.0% HFO-1234ZE(E), 2.0% to 22.0% HFC-134A, and 2.0% to 40.0% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 10.0 K, a cooling capacity range with a deviation of -37.7% to 218.6% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of -35.0% to 3.2% from the cooling COP of R-454C evaluated under the same setting conditions. Table 7a lists example compositions with ASHRAE flammability ratings of 2, 1, 3, and 2 L in the GWP < 300 range.

[0204] Similarly, but less generally, for cooling modes, the composition ranges of 2.0% to 78.0% CO2, 2.0% to 92.0% R-1252ZC, 2.0% to 92.0% HFO-1234ZE(E), 2.0% to 10.0% HFC-134A, and 2.0% to 18.0% HFC-32 will have a GWP of less than 149, a maximum average slip of approximately 10.0 K, an ASHRAE flammability rating of 1, 3, 2 L, and 2, a cooling capacity range with a deviation of -37.7% to 213.4% from the cooling capacity of R-454C evaluated under the same setting conditions, and a cooling COP range with a deviation of -35.0% to 3.1% from the cooling COP of R-454C evaluated under the same setting conditions.

[0205] For the cooling mode, a preferred blend composition range of 2.0% to 2.0% CO2, 34.0% to 84.0% R-1252ZC, 2.0% to 46.0% HFO-1234ZE(E), 2.0% to 6.0% HFC-134A, and 10.0% to 18.0% HFC-32 will have a GWP of <149, a maximum average heat exchanger slip of 10.0 K, and ASHRAE flammability ratings of 2 and 3, with minimum and maximum cooling capacities of -10.0% and 1.3% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 1.5% and 2.3% respectively compared to R-454C evaluated under the same setting conditions.

[0206] For the cooling mode, blends ranging from 2.0% to 2.0% carbon dioxide, 34.0% to 62.0% R-1252ZC, 16.0% to 46.0% HFO-1234ZE(E), 2.0% to 4.0% HFC-134A, and 12.0% to 18.0% HFC-32 will have a GWP of <149, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2, and minimum and maximum cooling capacities of -9.9% and 0.6% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum cooling COP efficiencies of 1.5% and 2.1% respectively compared to R-454C evaluated under the same setting conditions.

[0207] Even more preferred is a maximum cooling capacity composition of 2.0 wt% carbon dioxide, 62.0 wt% R-1252ZC, 16.0 wt% HFO-1234ZE(E), 2.0 wt% HFC-134A and 18.0 wt% HFC-32, which is 0.6% greater than that of R-454C, wherein under the same cycling conditions, the COP for cooling is 1.5% greater than that of R-454C, the maximum average heat exchanger slip is 9.5 K, and its ASHRAE flammability rating is 2.

[0208] Even more preferred is the composition of 2.0 wt% carbon dioxide, 46.0 wt% R-1252ZC, 38.0 wt% HFO-1234ZE(E), 2.0 wt% HFC-134A and 12.0 wt% HFC-32, which has a maximum cooling COP efficiency of 2.1% compared to R-454C, wherein the CAP for cooling under the same cycle conditions is -9.9% compared to R-454C, the maximum average heat exchanger slip is 9.3 K, and its ASHRAE flammability rating is 2.

[0209] In summary, for heating modes, the composition ranges of 2.0% to 92.0% carbon dioxide, 2.0% to 92.0% R-1252ZC, 2.0% to 92.0% HFO-1234ZE(E), 2.0% to 22.0% HFC-134A, and 2.0% to 40.0% HFC-32 will have a GWP of less than 300, a maximum average slip of approximately 10.0 K, a heating capacity range with a deviation of -40.4% to 348.8% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of -22.6% to 1.4% from the heating COP of R-454C evaluated under the same setting conditions. Table 7b lists example compositions with ASHRAE flammability ratings of 2, 1, 2L, and 3 in the GWP < 300 range.

[0210] Similarly, but less generally, for heating modes, the composition ranges of 2.0% to 92.0% carbon dioxide, 2.0% to 92.0% R-1252ZC, 2.0% to 92.0% HFO-1234ZE(E), 2.0% to 22.0% HFC-134A, and 2.0% to 40.0% HFC-32 will have a GWP of less than 300, a maximum average slip of about 10.0 K, an ASHRAE flammability rating of 2, 1, 3, and 2 L, a heating capacity range with a deviation of -40.4% to 348.8% from the heating capacity of R-454C evaluated under the same setting conditions, and a heating COP range with a deviation of -22.6% to 1.4% from the heating COP of R-454C evaluated under the same setting conditions.

[0211] For the heating mode, the preferred blend composition range of 2.0% to 4.0% carbon dioxide, 28.0% to 82.0% R-1252ZC, 2.0% to 40.0% HFO-1234ZE(E), 2.0% to 20.0% HFC-134A, and 4.0% to 28.0% HFC-32 will have a GWP of <300, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2 and 3, and minimum and maximum heating capacities of -10.0% and 10.0% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of -0.4% and 0.9% respectively compared to R-454C evaluated under the same setting conditions.

[0212] For the heating mode, blends with compositions ranging from 2.0% to 4.0% carbon dioxide, 28.0% to 66.0% R-1252ZC, 2.0% to 40.0% HFO-1234ZE(E), 2.0% to 20.0% HFC-134A, and 4.0% to 28.0% HFC-32, or even more preferred blend compositions, will have a GWP of <300, a maximum average heat exchanger slip of 10.0 K, an ASHRAE flammability rating of 2, and minimum and maximum heating capacities of -10.0% and 10.0% respectively compared to R-454C evaluated under the same setting conditions, and minimum and maximum heating COP efficiencies of -0.4% and 0.8% respectively compared to R-454C evaluated under the same setting conditions.

[0213] Even more preferred is a composition of 2.0 wt% carbon dioxide, 52.0 wt% R-1252ZC, 14.0 wt% HFO-1234ZE(E), 6.0 wt% HFC-134A and 26.0 wt% HFC-32, which is 10.0% greater than that of R-454C, wherein the COP for heating under the same cycling conditions is -0.3% compared to R-454C, the maximum average heat exchanger slip is 9.3 K, and its ASHRAE flammability rating is 2.

[0214] Even more preferred is a composition of 2.0 wt% carbon dioxide, 58.0 wt% R-1252ZC, 26.0 wt% HFO-1234ZE(E), 2.0 wt% HFC-134A and 12.0 wt% HFC-32, which has a maximum heating COP efficiency of 0.8% compared to R-454C, wherein the CAP for heating under the same cycle conditions is -9.5% compared to R-454C, the maximum average heat exchanger slip is 9.5 K, and its ASHRAE flammability rating is 2.

[0215]

[0216]

[0217]

[0218] Example 8

[0219] Under the residential air conditioning conditions shown below, the composition of the present invention, protected by claims, containing HFO-1252zc, HFO-1234zeE, HFC-134, and HFC-32, is compared with R-410A (the ASHRAE designation of a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). Tables 8A and 8B provide the calculation results.

[0220]

[0221] In summary, for the cooling mode, the composition range of 1.0% to 21.0% R-1252zc, 64.0% to 92.0% HFO-1234ze(E), 1.0% to 11.0% HFC-134, and 1.0% to 9.0% HFC-32 will have a GWP of <150, an ASHRAE flammability rating of 2L, a mean temperature glide of no more than 6.5, a cooling capacity of 40.0% to 48.9% of the cooling capacity of R-410A evaluated under the same setting conditions, and a cooling COP of 108.6% to 109.3% of the cooling COP of R-410A evaluated under the same setting conditions.

[0222] Similarly, but less generally, for the cooling mode, the composition range of 15.0% to 21.0% HFO-1252zc, 63.0% to 76.0% HFO-1234zeE, 1.0% to 8.0% HFC-134, and 7.0% to 9.0% HFC-32 will have a GWP of <150, an ASHRAE flammability rating of 2L, a mean temperature glide of no more than 6.5, a cooling capacity of 49.1% to 53.0% of the cooling capacity of R-410A evaluated under the same setting conditions, and a cooling COP of 108.6% to 108.7% of the cooling COP of R-410A evaluated under the same setting conditions.

[0223]

[0224]

[0225]

[0226]

Claims

1. A composition comprising at least one of HFC-134, HFC-134a, or CO2, and HFO-1252zc, HFO-1234zeE, or HFC-32.

2. The composition according to claim 1, wherein the composition comprises: HFO-1252zc, HFO-1234zeE, HFC-32 and HFC-134; or HFO-1252zc, HFO-1234zeE, HFC-32 and CO2; or HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134 and CO2; or HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and HFC-134a; or HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134a and CO2.

3. The composition according to claim 1 or 2, wherein the composition comprises: 1%-30% HFO-1252zc, 48%-82% HFO-1234zeE, 15%-22% HFC-32, and 1%-4% HFC-134; or 0.2%-98.5% by weight of HFO-1252zc, 0.2%-98.5% by weight of HFO-1234zeE, 0.2%-26.0% by weight of HFC-134, and 0.2%-43.8% by weight of HFC-32; or 0.2%-98.5% HFO-1252zc, 0.2%-98.5% HFO-1234ze(E), 0.2%-12.9% HFC-134, and 0.2%-20.9% HFC-32; or 19.9%-84.6% HFO-1252zc, 0.2%-58.7% HFO-1234ze(E), 0.2%-3.0% HFC-134, and 14.9%-20.9% HFC-32; or 19.9%-22.9% HFO-1252zc, 55.7%-58.7% HFO-1234ze(E), approximately 0.5% HFC-134, and approximately 20.9% HFC-32; or Approximately 22.9% by weight of HFO-1252zc, approximately 55.7% by weight of HFO-1234ze(E), approximately 0.5% by weight of HFC-134, and approximately 20.9% by weight of HFC-32; or Approximately 19.9% ​​by weight of HFO-1252zc, approximately 58.7% by weight of HFO-1234ze(E), approximately 0.5% by weight of HFC-134, and approximately 20.9% by weight of HFC-32; or 1.0%-21.0% HFO-1252zc, 64.0%-92.0% HFO-1234ze(E), 1.0%-11.0% HFC-134, and 1.0%-9.0% HFC-32; or 15.0%-21.0% HFO-1252zc, 63.0%-76.0% HFO-1234zeE, 1.0%-8.0% HFC-134, and 7.0%-9.0% HFC-32; or 15.0%-19.0% HFO-1252zc, 68.0%-72.0% HFO-1234ze(E), 3.0%-7.0% HFC-134, and 6.0%-10.0% HFC-32; or Approximately 17.0% HFO-1252zc, approximately 70.0% HFO-1234ze(E), approximately 5.0% HFC-134, and approximately 8.0% HFC-32.

4. The composition according to claim 3, wherein the composition has an average temperature glide of not more than 9.9 K, or not more than 9.6 K, or not more than 9.4 K, or not more than 9.3 K, or not more than 6.5 K, or in the range of 6.0-6.5 K, or in the range of 5.1-6.1 K.

5. The composition according to claim 3 or claim 4, wherein the composition has a volumetric cooling capacity relative to R-454C within the following range: The volumetric cooling capacity of the R-454C is 51.9% to 122.3%; or The volumetric cooling capacity of the R-454C is 51.9% to 97.8%; or The volumetric cooling capacity of R-454C is 90.0% to 97.8%; or The volumetric cooling capacity of R-454C is 90.1% to 90.2%; or The volumetric cooling capacity of R-454C is 40.0% to 48.9%; or The volumetric cooling capacity of the R-454C is 49.1% to 53.0%; or The volumetric cooling capacity of R-454C is 47.3% to 45.2%; or The volumetric cooling capacity of the R-454C is 47.2% to 48.2%.

6. The composition according to any one of claims 3 to 5, wherein the composition has a cooling COP within the range of: The cooling COP of R-454C is 97.6% to 105.4%; or The cooling COP of R-454C is 101.5% to 105.0%; or The cooling COP of R-454C is 101.5% to 102.5%; or The cooling COP of R-454C is 102.4% to 102.5%; or The cooling COP of R-454C is 108.6% to 109.3%; or The cooling COP of R-454C is 108.6% to 108.7%; or The cooling COP of R-454C is 108.6% to 108.8%.

7. The composition according to any one of claims 3 to 6, wherein the composition has a GWP of less than 300 or less than 150 or less than 125 or in the range of 89-125 or in the range of 92-147.

8. The composition according to any one of claims 3 to 7, wherein the composition has an ASHRAE flammability rating of 2L, 2 or 1.

9. The composition according to claim 1 or 2, wherein the composition comprises: Approximately 13% to 30% by weight of HFO-1252zc, approximately 54% to 72% by weight of HFO-1234zeE, approximately 8% to 14% by weight of HFC-32, and approximately 1% to 4% by weight of CO2; or 0.2%-98.5% HFO-1252zc, 0.2%-98.5% HFO-1234ze(E), 0.2%-44.0% HFC-32, and 0.2%-8.0% CO2; or 0.2%-98.5% HFO-1252zc, 0.2%-98.5% HFO-1234ze(E), 0.2%-22.0% HFC-32, and 0.2%-3.0% CO2; or 27.9%-84.6% HFO-1252zc, 0.2%-51.7% HFO-1234ze(E), 11.0%-22.0% HFC-32, and 0.2%-2.0% CO2; or 27.9%-64.7% HFO-1252zc, 12.9%-51.7% HFO-1234ze(E), 15.0%-22.0% HFC-32, and 0.5%-1.0% CO2; or Approximately 64.0% by weight of HFO-1252zc, approximately 13.0% by weight of HFO-1234ze(E), approximately 22.0% by weight of HFC-32, and approximately 1.0% by weight of CO2; or Approximately 27.9% by weight of HFO-1252zc, approximately 51.7% by weight of HFO-1234ze(E), approximately 19.9% ​​by weight of HFC-32 and approximately 0.5% by weight of CO2.

10. The composition of claim 9, wherein the composition has a GWP of less than 298 or less than 149.

11. The composition according to claim 9 or claim 10, wherein the composition has an average temperature glide of not more than 10.0 K or not more than 9.2 K.

12. The composition according to any one of claims 9 to 11, wherein the composition exhibits a volumetric heating capacity relative to R-454C within the following range: The volumetric heating capacity of R-454C is 49.3% to 150.3%; or The volumetric heating capacity of R-454C is 49.3% to 102.0%; or The volumetric heating capacity of R-454C is 90.0% to 102.0%; or The volumetric heating capacity of R-454C is 90.0% to 101.5%; or The volumetric heating capacity of R-454C is approximately 101.5%; or The volumetric heating capacity of R-454C is approximately 101.2%.

13. The composition according to any one of claims 9 to 12, wherein the composition exhibits a heating COP relative to R-454C within the range of: The heating COP of R-454C is 96.4% to 102.3%; or The heating COP of R-454C is 100.1% to 102.3%; or The heating COP of R-454C is 100.6% to 101.3%; or The heating COP of R-454C is 100.6% to 101.2%; or The heating COP of R-454C is approximately 100.6%; or The heating COP of R-454C is approximately 99.5%.

14. The composition according to any one of claims 9 to 13, wherein the composition has an ASHRAE flammability rating of 2L or 2.

15. The composition according to claim 1 or 2, wherein the composition comprises: 0.2%-98.5% HFO-1252zc, 0.2%-98.5% HFO-1234ze(E), 0.2026.0% HFC-134, 0.2%-43.8% HFC-32, and 0.2%-3.0% CO2; or 0.2%-98.5% HFO-1252zc, 0.2%-98.5% HFO-1234ze(E), 0.2%-12.9% HFC-134, 0.2%-20.9% HFC-32, and 0.2%-3.0% CO2; or 24.9%-84.6% HFO-1252zc, 0.2%-53.7% HFO-1234ze(E), 0.2%-6.0% HFC-134, 11.0%-20.9% HFC-32, and 0.2%-2.0% CO2; or 24.9%-63.7% HFO-1252zc, 13.9%-53.7% HFO-1234ze(E), 0.2%-5.0% HFC-134, 13.0%-20.9% HFC-32, and 0.2%-2.0% CO2; or 6.0 wt%–20.0 wt% of HFO-1252zc, 55.0 wt%–73.0 wt% of HFO-1234zeE, 11.0 wt%–22.0 wt% of HFC-32, and 1.0 wt%–2.0 wt% of CO2; or 5%-30% by weight of HFO-1252zc, 46%-approx. 77% by weight of HFO-1234zeE, approximately 5%-approx. 22% by weight of HFC-32, approximately 1%-approx. 10% by weight of HFC-134, and approximately 1%-approx. 4% by weight of CO2; or 1%-21% HFO-1252zc, 42%-82% HFO-1234zeE, 11%-22% HFC-32, 1%-6% HFC-134, and 1%-3% CO2; or Approximately 63.7% by weight of HFO-1252zc, approximately 13.9% by weight of HFO-1234ze(E), approximately 0.5% by weight of HFC-134, approximately 20.9% by weight of HFC-32, and approximately 1.0% by weight of CO2; or Approximately 24.9% by weight of HFO-1252zc, approximately 53.7% by weight of HFO-1234ze(E), approximately 0.2% by weight of HFC-134, approximately 20.9% by weight of HFC-32 and approximately 0.2% by weight of CO2.

16. The composition of claim 15, wherein the composition has a GWP of less than 300 or less than 150.

17. The composition according to claim 15 or claim 16, wherein the composition has an average temperature glide of not more than 10.0 K, or not more than 9.9 K, or not more than 9.2 K.

18. The composition according to any one of claims 15 to 17, wherein the composition exhibits a volumetric heating capacity relative to R-454C within the following range: The volumetric heating capacity of R-454C is 48.7% to 133.3%; or The volumetric heating capacity of R-454C is 48.7% to 100.5%; or The volumetric heating capacity of R-454C is 90.0% to 100.5%; or The volumetric heating capacity of R-454C is 90.0% to 100.1%; or The volumetric heating capacity of R-454C is approximately 99.9%; or The volumetric heating capacity of R-454C is approximately 101.

2.

19. The composition according to any one of claims 15 to 18, wherein the composition exhibits a heating COP relative to R-454C within the range of: The heating COP of R-454C is 97.6% to 102.6%; or The heating COP of R-454C is 100.1% to 102.5%; or The heating COP of R-454C is 100.7% to 101.3%; or The heating COP of R-454C is 100.7% to 101.2%; or The heating COP of R-454C is approximately 100.7%; or The heating COP of R-454C is approximately 1.2%.

20. The composition according to any one of claims 15 to 19, wherein the composition has an ASHRAE flammability rating of 1, 2, or 2L.

21. The composition according to any one of claims 15 to 20, wherein the volumetric cooling capacity exhibited by the composition relative to R-454C is 85.57% to 80.07% of the cooling capacity of R-454C.

22. The composition according to any one of claims 15 to 21, wherein the composition exhibits a heating COP relative to R-454C of 53.69% to 57.38% of the heating COP of R-454C.

23. The composition according to claim 1 or claim 2, wherein the composition comprises: 1%-21% HFO-1252zc, 57%-82% HFO-1234zeE, 16%-22% HFC-32, and 1%-3% HFC-134a; or 0.1 wt%-21.0 wt% of HFO-1252zc, 58.0 wt%-80.0 wt% of HFO-1234zeE, 16.0 wt%-20.0 wt% of HFC-32 and 1.0 wt%-3.0 wt% of HFC-134a.

24. The composition of claim 23, wherein the composition has an average temperature glide of not more than 9.55 K, or not more than 8.94 K, or not more than 7.95 K.

25. The composition according to claim 23 or claim 24, wherein the volumetric cooling capacity of the composition relative to R-454C is in the range of 80.1% to 86.2% of the volumetric cooling capacity of R-454C.

26. The composition according to any one of claims 23 to 25, wherein the composition has a cooling COP relative to R-454C in the range of 102.92% to 103.61% of the cooling COP of R-454C.

27. The composition according to any one of claims 23 to 26, wherein the composition has a GWP of less than 300 or less than 150.

28. The composition according to claim 1 or 2, wherein the composition comprises: 1.0%-96.0% HFO-1252zc, 1.0%-96.0% HFO-1234ze(E), 1.0%-40.0% HFC-32, 1.0%-24.0% HFC-134, and 1.0%-21.0% HFC-134a; or 1.0%-96.0% HFO-1252zc, 1.0%-96.0% HFO-1234ze(E), 1.0%-18.0% HFC-32, 1.0%-11.0% HFC-134, 1.0%-10.0% HFC-134a; or 36.0%-82.0% HFO-1252zc, 1.0%-44.0% HFO-1234ze(E), 15.0%-18.0% HFC-32, 1.0%-3.0% HFC-134, 1.0%-2.0% HFC-134a; or 36.0%-63.0% HFO-1252zc, 17.0%-44.0% HFO-1234ze(E), 16.0%-18.0% HFC-32, 1.0%-2.0% HFC-134, 1.0%-2.0% HFC-134a; or 63.0 wt% HFO-1252zc, 17.0 wt% HFO-1234ze(E), 1.0 wt% HFC-134, 1.0 wt% HFC-134a and 18.0 wt% HFC-32; or 53.0 wt% HFO-1252ZC, 28.0 wt% HFO-1234ze(E), 16.0 wt% HFC-32, 2.0 wt% HFC-134, 1.0 wt% HFC-134a; or 1.0%-96.0% HFO-1252zc, 1.0%-96.0% HFO-1234ze(E), 1.0%-40.0% HFC-32, 1.0%-25.0% HFC-134, and 1.0%-21.0% HFC-134a; or 1.0%-96.0% HFO-1252zc, 1.0%-96.0% HFO-1234ze(E), 1.0%-18.0% HFC-32, 1.0%-11.0% HFC-134, and 1.0%-10.0% HFC-134a; or 45.0%-81.0% HFO-1252zc, 1.0%-35.0% HFO-1234zeE, 16.0%-18.0% HFC-32, 1.0%-2.0% HFC-134, 1.0%-2.0% HFC-134a; or 45.0%-63.0% HFO-1252zc, 17.0%-35.0% HFO-1234zeE, 17.0%-18.0% HFC-32, 1.0%-1.0% HFC-134 and 1.0%-1.0% HFC-134a; or 63.0 wt% HFO-1252zc, 17.0 wt% HFO-1234zeE, 18.0 wt% HFC-32, 1.0 wt% HFC-134, 1.0 wt% HFC-134a; or 54.0 wt% HFO-1252zc, 27.0 wt% HFO-1234zeE, 17.0 wt% HFC-32, 1.0 wt% HFC-134 and 1.0 wt% HFC-134a.

29. The composition of claim 28, wherein the composition has a GWP of less than 300 or less than 150.

30. The composition of claim 28 or claim 29, wherein the composition exhibits an average temperature glide of no more than 10.0 K, or no more than 9.6 K, or no more than 8.3 K, or no more than 8.2 K, or no more than 7.8 K, or no more than 7.4 K, or no more than 7.2 K.

31. The composition according to any one of claims 28 to 30, wherein the composition exhibits a volumetric cooling capacity relative to R-454C within the following range: The volumetric cooling capacity of R-454C is 52.8% to 79.9.1%; or The volumetric cooling capacity of R-454C is 52.8% to 94.8%; or The volumetric cooling capacity of R-454C is 90.0% to 94.8.2%; or The volumetric cooling capacity of R-454C is 90.0% to 94.0%; or The volumetric cooling capacity of the R-454C is approximately 94.0%; or The volumetric cooling capacity of the R-454C is approximately 90.1%.

32. The composition according to any one of claims 28 to 31, wherein the composition exhibits a cooling COP relative to R-454C within the range of: The cooling COP of R-454C is 98.9% to 104.7%; or The cooling COP of R-454C is 101.7% to 104.4%; or The cooling COP of R-454C is 102.2% to 102.6%; or The cooling COP of R-454C is 102.2% to 102.4%; or The cooling COP of the R-454C is approximately 102.2%; or The cooling COP of the R-454C is approximately 102.4%.

33. The composition according to any one of claims 28 to 32, wherein the composition exhibits a volumetric heating capacity relative to R-454C within the following range: The volumetric heating capacity of R-454C is 49.9% to 80.3%; or The volumetric heating capacity of R-454C is 49.9% to 93.5%; or The volumetric heating capacity of R-454C is 90.0% to 93.5%; or The volumetric heating capacity of R-454C is 90.1% to 92.6%; or The volumetric heating capacity of R-454C is approximately 92.6%; or The volumetric heating capacity of R-454C is approximately 90.1%.

34. The composition according to any one of claims 28 to 33, wherein the composition exhibits a heating COP relative to R-454C within the range of: The heating COP of R-454C is 98.7% to 102.8%; or The heating COP of R-454C is 101.1% to 102.7%; or The heating COP of R-454C is 101.1% to 101.2%; or The heating COP of R-454C is approximately 101.1%; or...

35. The composition according to any one of claims 28 to 34, wherein the composition has an ASHRAE flammability rating of 1, 2, or 2L.

36. The composition according to claim 1 or 2, wherein the composition comprises: 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-40.0% HFC-32; 2.0%-22.0% HFC-134a and 2.0%-78.0% CO2; or 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-18.0% HFC-32, 2.0%-10.0% HFC-134a, and 2.0%-78.0% CO2; or 34.0%-84.0% HFO-1252zc, 2.0%-46.0% HFO-1234ze(E), 10.0%-18.0% HFC-32, 2.0%-6.0% HFC-134a, and 2.0%-2.0% CO2; or 34.0%-62.0% HFO-1252zc, 16.0%-46.0% HFO-1234ze(E), 12.0%-18.0% HFC-32, 2.0%-4.0% HFC-134a, and 2.0%-2.0% CO2; or 62.0 wt% HFO-1252zc, 16.0 wt% HFO-1234ze(E), 18.0 wt% HFC-32, 2.0 wt% HFC-134a and 2.0 wt% CO2; or 46.0 wt% HFO-1252zc, 38.0 wt% HFO-1234ze(E), 12.0 wt% HFC-32, 2.0 wt% HFC-134a and 2.0 wt% CO2; or 2.0%-92.0% HFO-1252zc, 2.0%-92.0% HFO-1234ze(E), 2.0%-40.0% HFC-32, 2.0%-22.0% HFC-134a, and 2.0%-92.0% CO2; or 28.0%-82.0% HFO-1252zc, 2.0%-40.0% HFO-1234ze(E), 4.0%-28.0% HFC-32, 2.0%-20.0% HFC-134a, and 2.0%-4.0% CO2; or 28.0%-66.0% HFO-1252zc, 2.0%-40.0% HFO-1234ze(E), 4.0%-28.0% HFC-32, 2.0%-20.0% HFC-134a, and 2.0%-4.0% CO2; or 52.0 wt% HFO-1252zc, 14.0 wt% HFO-1234ze(E), 26.0 wt% HFC-32, 6.0 wt% HFC-134a and 2.0 wt% CO2; or 58.0 wt% HFO-1252zc, 26.0 wt% HFO-1234ze(E), 12.0 wt% HFC-32, 2.0 wt% HFC-134a and 2.0 wt% CO2.

37. The composition of claim 36, wherein the composition exhibits an AGW of less than 300 or less than 149.

38. The composition according to claim 36 or claim 37, wherein the composition exhibits a volumetric cooling capacity relative to R-454C within the following range: The volumetric cooling capacity of the R-454C is 62.3% to 218.6%; or The volumetric cooling capacity of the R-454C is 62.3% to 213.4%; or The volumetric cooling capacity of R-454C is 90.0% to 101.3%; or The volumetric cooling capacity of R-454C is 90.1% to 100.6%; or The volumetric cooling capacity of the R-454C is approximately 100.6%; or The volumetric cooling capacity of the R-454C is approximately 90.1%.

39. The composition according to any one of claims 36 to 38, wherein the composition exhibits a cooling COP relative to R-454C within the range of: The cooling COP of R-454C is 65.0% to 103.2%; or The cooling COP of R-454C is 65.0% to 103.1%; or The cooling COP of R-454C is 101.5% to 102.3%; or The cooling COP of R-454C is 101.5% to 102.1%; or The cooling COP of the R-454C is approximately 101.5%; or The cooling COP of the R-454C is approximately 2.1%.

40. The composition according to any one of claims 36 to 39, wherein the composition exhibits a volumetric heating capacity relative to R-454C within the following range: The volumetric heating capacity of R-454C is 59.6% to 348.8%; or The volumetric heating capacity of R-454C is 90.0% to 110.0%; or The volumetric heating capacity of R-454C is approximately 110.0%; or The volumetric heating capacity of R-454C is approximately 90.5%.

41. The composition according to any one of claims 36 to 40, wherein the composition exhibits a heating COP relative to R-454C within the range of: The heating COP of R-454C is 77.4% to 101.4%; or The heating COP of R-454C is 77.4% to 101.4%; or The heating COP of R-454C is 99.6% to 100.9%; or The heating COP of R-454C is 99.6% to 100.8%; or The heating COP of R-454C is approximately 99.7%; or The heating COP of R-454C is approximately 100.8%; or...

42. The composition according to any one of claims 36 to 41, wherein the composition exhibits an average temperature glide of not more than 10.0 K, or not more than 9.5 K, or not more than 9.3 K.

43. The composition according to any one of claims 36 to 42, wherein the composition has an ASHRAE flammability rating of 1, 2, or 2L.

44. The composition according to any one of claims 1 to 43, wherein the composition further comprises at least one additional compound selected from the group consisting of: HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-134a, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, H FO-374, n-butane, propadiene, 2-butene, cyclobutene, 2-methylpropene, 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 / Zt-BuO-CF=CH-CH3.

45. The composition according to any one of claims 1 to 44, wherein the composition further comprises at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO-1252yf, HFO-1252zf and HFO-1252ye.

46. ​​The composition according to any one of claims 1 to 45, wherein the composition further comprises 0.1 ppm to 200 ppm of water by weight; about 10 ppm to about 0.35% by volume of oxygen by volume; and / or about 100 ppm to about 1.5% by volume of air or NAG.

47. The composition according to any one of claims 1 to 46, wherein the composition comprises a stabilizer.

48. The composition of claim 47, wherein the stabilizer is selected from the group consisting of: nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

49. The composition according to any one of claims 47 or 49, wherein the stabilizer is selected from toluenetriazole, benzotriazole, tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxide, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

50. The composition according to any one of claims 47 to 49, wherein the stabilizer is present in an amount of about 0.001% by weight to 1.0% by weight based on the weight of the refrigerant.

51. The composition according to any one of claims 1 to 50, wherein the composition further comprises a lubricant.

52. The composition of claim 51, wherein the lubricant is at least one selected from the group consisting of: polyalkylene glycols, polyol esters, poly-α-olefins, and polyethylene ethers.

53. The composition according to claim 51 or 52, wherein the lubricant is a polyol ester or a polyethylene ether.

54. The composition according to any one of claims 51 to 53, wherein the lubricant has at least one property selected from the group consisting of: greater than 10 at 20°C 10 Volume resistivity in Ω-m; surface tension from about 0.02 N / m to about 0.04 N / m at 20 °C; kinematic viscosity from about 20 cSt to about 500 cSt at 40 °C; breakdown voltage of at least 25 kV; and hydroxyl value of at most 0.1 mg KOH / g.

55. The composition according to any one of claims 1 to 54, wherein the composition comprises at least one tracer.

56. The composition of claim 55, wherein the tracer is present in an amount from about 1.0 ppm to about 1000 ppm by weight.

57. The composition according to any one of claims 55 or 56, 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.

58. The composition according to any one of claims 55 to 57, wherein the 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.

59. The composition according to any one of claims 1 to 58, wherein the composition is free from or substantially free from Group A fluorinated substances, and wherein the degradation products of the composition are free from or substantially free from Group A fluorinated substances.

60. A method for cooling, the method comprising evaporating a composition according to any one of claims 1 to 59 near a body to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

61. A method for heating, the method comprising evaporating a composition according to any one of claims 1 to 50, and then condensing the composition near a body to be heated, wherein the heating is provided by a heat pump.

62. A system for cooling or heating, said system comprising the composition according to any one of claims 1 to 50.

63. The system of claim 62, the system comprising an evaporator, a compressor, a condenser and an expander, each operatively connected to perform a vapor compression cycle.

64. The system according to claim 62 or 63, wherein the air conditioner or heat pump is a residential, light commercial or industrial air conditioner or heat pump.

65. The system according to any one of claims 62 to 64, wherein the system is a secondary loop system.

66. A method of replacing R-454C, propane, or R-410A in an air conditioning system or heat pump system, the method comprising providing the system with a composition according to any one of claims 1 to 50 in place of R-454C, propane, or R-410A.

67. Use of the composition according to any one of claims 1 to 50 as a refrigerant in an air conditioning system or a heat pump system.

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