Compositions of HFO-1234ZE(E), HFC-32, and HFC-152A, and a system for using said compositions

Abstract

An environmentally friendly refrigerant blend utilizing refrigerants including E-1,3,3,3-tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC-32), and 1,1-difluoroethane (HFC-152a). The blend has improved efficiency, low GWP, low toxicity, and low flammability for use in hybrid, mild hybrid, plug-in hybrid, or fully electric vehicles for thermal management (heat transfer from one part of the vehicle to another) of passenger compartments providing air conditioning (A / C) or heating to the passenger cabin.

Description

【Technical Field】 【0001】 (Cross - Reference to Related Applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 469,887, filed May 31, 2023, the entire disclosure of which is incorporated herein by reference. 【0002】 (Field of the Invention) The present invention relates to compositions comprising HFO - 1234zeE, HFC - 32, and HFC - 152a and their use. 【Background Art】 【0003】 The automotive industry is undergoing a transformation in its architecture platform from obtaining propulsion using an internal combustion engine (ICE) to obtaining propulsion using an electric motor. This transformation of the platform may significantly limit the size of the internal combustion engine (ICE) in hybrid and plug - in hybrid vehicles or completely eliminate the ICE in pure electric vehicles. Some vehicles still maintain an ICE and are known as hybrid electric vehicles (HEV), plug - in hybrid electric vehicles (PHEV), or mild hybrid electric vehicles (MHEV). Vehicles that are fully electric and do not have an ICE, including battery electric vehicles (BEV), are called electric vehicles (EV). All HEV, PHEV, MHEV, and EV use at least one electric motor. This electric motor provides the vehicle with some form of propulsion that is normally provided by an internal combustion engine (ICE) found in gasoline / diesel vehicles. 【0004】 In electric vehicles, the ICE (Internal Combustion Engine) is typically reduced in size (HEV, PHEV, or MHEV) or eliminated (EV) to reduce vehicle weight and thereby increase the number of electric drive cycles. The primary function of the ICE is to provide propulsion for the vehicle, but it also provides heat to the passenger compartment as a secondary function. Heating is usually required when ambient conditions are below 10°C. In non-electric vehicles, there is excess heat from the ICE that can be captured and used to heat the passenger compartment. It should be noted that the ICE may take some time (several minutes) to heat up and generate heat. Therefore, in electric vehicles, the reduction in size or elimination of the ICE creates a demand for effective alternative heating for the passenger compartment. In current EVs without an ICE, positive temperature coefficient (PTC) heaters are currently used. Using heat pumps for cooling and heating can replace PTC heaters in conjunction with the air conditioning system, enabling more efficient cooling and heating. 【0005】 Due to environmental pressures, hydrofluorocarbons, or HFCs, such as R-134a, are being phased out of automotive air conditioning systems to favor low-GWP refrigerants with a global warming potential (GWP) of less than 150. While the hydrofluoroolefin HFO-1234yf meets the low-GWP requirement (GWP = 4 per papadimitaurus, GWP < 1 per AR5), it has a lower refrigeration capacity compared to R-134a and cannot fully meet the heating requirements at low temperatures (-10°C). Another option for automotive heat pumps is refrigerant blends commonly used in fixed-refrigerant applications. Examples of compositions containing HFO-1234ze are disclosed in International Publication 2007 / 126414, which is incorporated herein by reference. 【0006】 Similarly, heating and cooling systems for stationary residential and commercial structures are also suffering from a shortage of suitable low-GWP refrigerants to replace the older, high-GWP refrigerants currently in use. [Prior art documents] [Patent Documents] 【0007】 [Patent Document 1] U.S. Patent Provisional Application No. 63 / 469,887 [Patent Document 2] International Publication No. 2007 / 126414 [Overview of the project] [Problems that the invention aims to solve] 【0008】 Therefore, in this field of technology, there is a need for new refrigerants that meet evolving regulations and provide heat transfer and refrigeration properties that meet or exceed the effectiveness of conventional refrigerants. There is a need for low-GWP heat pump type fluids to meet the growing need for thermal management that can provide both cooling and heating in hybrid, mild hybrid, plug-in hybrid, and electric vehicles, electrified mass transit, and residential and commercial structures. Furthermore, there is a need for a refrigerant that can be used in place of HFO-1234yf in ICE vehicles, particularly during maintenance. 【0009】 This invention solves specific problems associated with conventional refrigerants and provides compositions that meet evolving regulatory requirements. [Means for solving the problem] 【0010】 The present invention relates to environmentally friendly refrigerant blend compositions for use in hybrid, mild hybrid, plug-in hybrid, or fully electric vehicles for complete vehicle thermal management (heat transfer from one part of a vehicle to another), with small temperature gradients, low GWP (GWP ≤ 100), low toxicity (Class A according to ANSI / ASHRAE standard 34 or ISO standard 817), and low flammability (Class 2 or Class 2L according to ASHRAE 34 or ISO 817). The thermal management system can operate to cool and / or heat power electronics, batteries, and motors, and to provide air conditioning (A / C) and / or heating to the passenger compartment. These refrigerants can also be used in mass transit applications that benefit from heat pump systems enabling both heating and cooling of batteries and motors, and heating and cooling of passenger compartment areas. Mass transit applications may include, but are not limited to, transport vehicles such as ambulances, buses, shuttles, and trains. 【0011】 In one aspect of the present invention, the composition comprises a refrigerant blend of HFO-1234zeE, HFC-32, and HFC-152a. 【0012】 The inventors have discovered a refrigerant blend that provides at least 10% higher volumetric capacity than HFO-1234yf alone, has a COP greater than or equal to that of HFO-1234yf alone, has a mean temperature gradient of less than 6K, is non-toxic, and can be classified as Class 2 or 2L flammable by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers). 【0013】 The present invention includes the following aspects and embodiments. In one embodiment, compositions useful as refrigerants and heat transfer fluids are disclosed herein. The compositions disclosed herein include E-1,3,3,3-tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC-32), and 1,1-difluoroethane (HFC-152a). 【0014】 According to any of the embodiments described above, compositions comprising a refrigerant blend containing about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a are also disclosed herein. In this range, the GWP < 150, and it is classified as Class 2L (low flammability) by ASHRAE. 【0015】 According to any of the embodiments described above, compositions comprising a refrigerant blend essentially consisting of about 63–93 weight percent of HFO-1234zeE, about 6–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a are also disclosed herein. In this range, the GWP < 150, and it is classified as Class 2L (low flammability) by ASHRAE. 【0016】 According to any of the embodiments described above, compositions comprising a refrigerant blend essentially consisting of about 63–93 weight percent of HFO-1234zeE, about 6–17 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a are also disclosed herein. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, and the mean temperature gradient is 6K or less. 【0017】 According to any of the embodiments described above, compositions comprising a refrigerant blend essentially consisting of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a are also disclosed herein. In this range, the GWP < 150, it is classified as Class 2L (low flammability) by ASHRAE, and also provides a 10% higher capacity than HFO-1234yf alone. 【0018】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a is also disclosed herein. Within this range, the GWP is < 150, it is classified as class 2L (low flammability) by ASHRAE, and it also provides a capacity 15% higher than that of HFO-1234yf alone. 【0019】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a is also disclosed herein. Within this range, the GWP is < 150, it is classified as class 2L (low flammability) by ASHRAE, and it also provides a capacity 20% higher than that of HFO-1234yf alone. 【0020】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a is also disclosed herein. Within this range, the GWP is < 150, it is classified as class 2L (low flammability) by ASHRAE, it provides a capacity 10% higher than that of HFO-1234yf, and it exhibits an average temperature gradient of less than 6K. 【0021】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a is also disclosed herein. Within this range, the GWP is < 150, it is classified as class 2L (low flammability) by ASHRAE, it provides a capacity 15% higher than that of HFO-1234yf, and it exhibits an average temperature gradient of less than 6K. 【0022】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a is also disclosed herein. 【0023】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a is also disclosed herein. In this range, GWP < 150, it is classified as Class 2L (low flammability) by ASHRAE, and shows an average temperature gradient of less than 5K. 【0024】 According to any of the foregoing embodiments, a composition comprising a refrigerant blend consisting essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a is also disclosed herein. In this range, GWP < 150, it is classified as Class 2L (low flammability) by ASHRAE, and shows an average temperature gradient of less than 4K. 【0025】 According to any of the foregoing embodiments, a composition in which the refrigerant blend provides an average temperature gradient of from about 0.1K to less than about 6K is also disclosed herein. 【0026】 According to any of the foregoing embodiments, a composition in which the refrigerant blend provides an average temperature gradient of from about 0.1K to less than about 5K is also disclosed herein. 【0027】 According to any of the foregoing embodiments, a composition in which the refrigerant blend provides an average temperature gradient of from about 0.1K to less than about 4K is also disclosed herein. 【0028】 According to any of the foregoing embodiments, a composition in which the refrigerant blend has a GWP of about 150 or less is also disclosed herein. 【0029】 According to any of the embodiments described above, compositions in which the refrigerant blend has a GWP of about 120 or less are also disclosed herein. 【0030】 According to any of the embodiments described above, a composition further comprising at least one additional compound, wherein the additional compound is: a) At least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropine, HCC-1140, HFC-1234yf, HFO-1234ze(Z), HFO-1225yeE, HFO-1225yeZ, HFO-1225zc, HFC-134a, HFO-1243zf, and HCFO-1131; or b) At least one compound selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-143a, HCFC-22, HCC-40, HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, HCC-160, HCFO-1130a, HCFC-141b, HFO-1132a, HFC-143a, HCFO-1122, and HCFC-142b; or c) A combination of a) and b) is selected, Compositions are also disclosed in which the total amount of additional compounds is greater than zero and less than 1 weight percent. 【0031】 According to any of the embodiments described above, compositions comprising at least one of HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, or HCC-160, or a combination thereof, are also disclosed herein. 【0032】 According to any of the embodiments described above, compositions comprising additional compounds, HFC-143a, HFC-161, and HCFC-151a, are also disclosed herein. 【0033】 According to any of the embodiments described above, compositions comprising additional compounds including HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a are also disclosed herein. 【0034】 According to any of the embodiments described above, compositions comprising additional compounds, including HFO-1243zf, HCC-40, and HFC-161, are also disclosed herein. 【0035】 According to any of the embodiments described above, compositions in which the refrigerant blend has a combustion rate of 10 cm / s or less when measured according to the ISO 817 vertical tube method are also disclosed herein. 【0036】 According to any of the embodiments described above, compositions in which the refrigerant blend is classified as 2 L in terms of flammability as defined in ANSI / ASHRAE standard 34 are also disclosed herein. 【0037】 According to any of the embodiments described above, compositions in which the refrigerant blend has an LFL of less than 10 volume percent when measured according to ASTM-E681 are also disclosed herein. 【0038】 According to any of the embodiments described above, compositions further comprising a lubricant are also disclosed herein. 【0039】 According to any of the embodiments described above, compositions in which the lubricant is selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether are also disclosed herein. 【0040】 According to any of the embodiments described above, the polyol ester lubricant is also disclosed herein by reacting a carboxylic acid with a polyol containing a neopentyl skeleton selected from the group consisting of neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mixtures thereof. 【0041】 According to any of the embodiments described above, compositions in which the carboxylic acid has 2 to 18 carbon atoms are also disclosed herein. 【0042】 According to any of the embodiments described above, the lubricant is 10 at 20°C. 10 Compositions having a volume resistivity greater than Ω·m are also disclosed herein. 【0043】 According to any of the embodiments described above, a composition of the lubricant having a surface tension of about 0.02 N / m to 0.04 N / m at 20°C is also disclosed herein. 【0044】 According to any of the embodiments described above, compositions of the lubricant having a kinematic viscosity of about 20 cSt to about 500 cSt at 40°C are also disclosed herein. 【0045】 According to any of the embodiments described above, a composition of the lubricant having a dielectric breakdown voltage of at least 25 kV is also disclosed herein. 【0046】 According to any of the embodiments described above, compositions in which the lubricant has a hydroxyl value of up to 0.1 mg KOH / g are also disclosed herein. 【0047】 According to any of the embodiments described above, compositions further comprising 0.1 to 200 ppm by weight of water are also disclosed herein. 【0048】 According to any of the embodiments described above, compositions further comprising about 10 volume ppm to about 0.35 volume percent of oxygen are also disclosed herein. 【0049】 According to any of the embodiments described above, compositions further comprising about 100 volume ppm to about 1.5 volume percent of air are also disclosed herein. 【0050】 According to any of the embodiments described above, compositions further comprising a stabilizer are also disclosed herein. 【0051】 According to any of the embodiments described above, compositions in which the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones are also disclosed herein. 【0052】 According to any of the embodiments described above, compositions in which the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene are also disclosed herein. 【0053】 According to any of the embodiments described above, compositions are disclosed herein in which the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant. 【0054】 According to any of the embodiments described above, compositions further comprising at least one tracer are also disclosed herein. 【0055】 According to any of the embodiments described above, compositions in which the at least one tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight are also disclosed herein. 【0056】 According to any of the embodiments described above, compositions are also disclosed herein in which the at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof. 【0057】 According to any of the embodiments described above, the at least one tracer is HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC-338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, Compositions selected from the group consisting of 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 are also disclosed herein. 【0058】 According to any of the embodiments described above, compositions that do not contain or substantially contain Group A fluorinated substances are also disclosed herein. 【0059】 According to any of the embodiments described above, compositions in which the decomposition products of the composition do not contain or substantially contain Group A fluorinated substances are also disclosed herein. 【0060】 In another embodiment, a refrigerant storage container containing a composition according to any of the embodiments described above is disclosed herein, wherein the refrigerant comprises a gas phase and a liquid phase. 【0061】 In another embodiment, a system for heating and cooling the passenger compartment of an electric vehicle is also disclosed herein, comprising an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle, wherein a refrigerant composition of any of the above embodiments is circulated through each of the evaporator, compressor, condenser, and expansion device. 【0062】 According to any of the embodiments described above, cooling and heating systems are also disclosed herein, wherein the average temperature gradient is less than 6.0K, less than 5.0K, or less than 4.0K. 【0063】 According to any of the embodiments described above, a cooling and heating system that does not include a PTC heater is also disclosed herein. 【0064】 According to any of the embodiments described above, cooling and heating systems that are not reversible cooling loops are also disclosed herein. 【0065】 According to any of the embodiments described above, a cooling and heating system further comprising a reheater operably connected between the compressor and the condenser is also disclosed herein. 【0066】 In another embodiment, a method for replacing HFO-1234yf in a heating and cooling system contained within an electric vehicle is also disclosed herein, which includes providing one of the aforementioned compositions to the heating and cooling system as a heat transfer fluid. 【0067】 In another embodiment, a method is disclosed for replacing HFO-1234yf in a cooling system contained in an internal combustion engine or a hybrid vehicle, the method comprising adding one of the aforementioned compositions to the cooling system as a heat transfer fluid. 【0068】 According to any of the embodiments described above, a method for replacing HFO-1234yf is also disclosed herein, wherein the refrigerant blend produces a volumetric capacity at least 10% higher than HFO-1234yf alone when operated under the same set of conditions. Alternatively, the refrigerant blend may provide a capacity at least 15% higher than HFO-1234yf alone, or the refrigerant blend may provide a capacity at least 20% higher than 1234yf alone. 【0069】 According to any of the embodiments described above, a method for replacing HFO-1234yf is also disclosed herein, wherein the refrigerant blend produces a COP greater than that of HFO-1234yf alone when operated under the same conditions. The refrigerant blend may provide a COP 5%, 6%, or even 7% higher than that of 1234yf alone. 【0070】 In another embodiment, a method for servicing an electric vehicle's heating and cooling system is also disclosed herein, which includes the steps of removing all used refrigerant from the system and filling the system with one of the aforementioned compositions. 【0071】 In another embodiment, the use of any of the aforementioned compositions as a heat transfer fluid in a system for heating and cooling passenger compartments of a hybrid or electric vehicle is disclosed herein. 【0072】 Various aspects and embodiments of the present invention can be used individually or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description of preferred embodiments illustrating the principles of the present invention, as an example. [Brief explanation of the drawing] 【0073】 [Figure 1] This figure shows a reversible cooling or heating loop system according to an embodiment. [Figure 2] This figure shows a reversible cooling or heating loop system according to an embodiment. [Figure 3]This figure shows a cooling or heating loop system according to an embodiment. [Figure 4] This figure shows a reversible cooling or heating loop system according to an embodiment. [Figure 5] This figure shows a reversible cooling or heating loop system according to an embodiment. [Figure 6] This figure shows a cooling or heating system according to an embodiment. [Figure 7] This figure shows a cooling or heating system according to an embodiment. [Figure 8] This figure shows a cooling or heating system according to an embodiment. [Figure 9] This figure shows a cooling or heating system according to an embodiment. [Modes for carrying out the invention] 【0074】 definition As used herein, the terms heat transfer composition or heat transfer fluid mean a composition used to transfer heat from a heat source to a heat sink. 【0075】 A heat source is defined as any space, place, object, or body to which it is desirable to add, transfer, move, or remove heat. An example of a heat source in this embodiment is the passenger compartment of a vehicle that requires air conditioning. 【0076】 A heat sink is defined as any space, place, object, or body that can absorb heat. An example of a heat sink in this embodiment is a passenger compartment in a vehicle that requires heating. 【0077】 A heat transfer system is a system (or device) used to produce a heating or cooling effect at a specific location. In this invention, a heat transfer system means a heating or cooling system that provides heating or cooling to the passenger compartment of an automobile. This system may also be called a heat pump system, and may be a reversible heating system or a reversible cooling system, or simply a heating and cooling system. 【0078】 The heat transfer fluid comprises at least one refrigerant and at least one component selected from the group consisting of lubricants, stabilizers, tracers, UV dyes, and flame suppressants. 【0079】 Volumetric capacity is the amount of heat absorbed or released divided by the theoretical compressor displacement. The heat removed or absorbed is the enthalpy difference between the heat exchangers multiplied by the refrigerant mass flow rate. The theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., the compressor suction density). More simply, volumetric capacity is the suction density multiplied by the heat exchanger enthalpy difference. A higher volumetric capacity allows for the use of a smaller compressor for the same heat load. In this specification, cooling capacity refers to volumetric capacity in cooling mode, and heating capacity refers to volumetric capacity in heating mode. 【0080】 The coefficient of performance (COP) is calculated by dividing the amount of heat absorbed or released by the energy input required for the cycle to operate (approximated by the compressor's capacity). COP is specific to the operating mode of a heat pump and therefore can be either the COP for heating or the COP for cooling. COP is directly related to the energy efficiency ratio (EER). 【0081】 Supercooling refers to lowering the temperature of a liquid to below its saturation point at a given pressure. The saturation point is the temperature at which vapor completely condenses into liquid. By cooling a liquid to a temperature below its saturation temperature (or boiling point), the net refrigeration effect can be increased. Thus, supercooling improves the refrigeration capacity and energy efficiency of a system. The amount of supercooling is the amount of cooling below the saturation temperature (degrees). 【0082】 Superheating refers to raising the temperature of a vapor above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. Superheating continues to heat the vapor to a higher temperature at a given pressure. By heating the vapor to a temperature above the saturation temperature (or dew point temperature), the net refrigeration effect can be increased. Thus, when superheating occurs in an evaporator, it improves the refrigeration capacity and energy efficiency of the system. Superheating in a suction line does not add a net refrigeration effect and may reduce efficiency and capacity. The amount of superheating is the amount of heating above the saturation temperature (degrees). 【0083】 A temperature gradient (sometimes simply referred to as "gradient") is the absolute difference between the start and end temperatures of the phase change process by the refrigerant in the condenser of a refrigerant system, excluding any supercooling or superheating. In the case of an evaporator, the gradient is the temperature difference between the dew point and the evaporator inlet. The gradient can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to the temperature gradient of an air conditioning system or heat pump system, it is common to provide the mean temperature gradient, which is the average value of the temperature gradient in the evaporator and the temperature gradient in the condenser. The gradient is applicable to blended refrigerants, i.e., refrigerants composed of at least two components. 【0084】 In this specification, a small gradient is defined as an average gradient (e.g., a gradient in the range of greater than 0 to about less than 2.0K) over the operating range of the object under heating and cooling conditions, more preferably a small gradient is less than 3K over the operating range of the object, more preferably less than 2.5K over the operating range of the object, or most preferably less than 2.0K over the operating range of the object. 【0085】 E-1,3,3,3-tetrafluoropropene (HFO-1234zeE or R-1234zeE) is commercially available from Honeywell (Charlotte, North Carolina, USA). 1,1-difluoroethane (HFC-152a or R-152a) is commercially available from Chemors® (Wilmington, DE, USA). Difluoromethane (HFC-32 or R-32) is commercially available from various suppliers worldwide. 【0086】 As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing the elements listed is not necessarily limited to those elements alone, but may include other elements not expressly listed, or other elements inherent in such composition, process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist). 【0087】 The transitional phrase "consisting of" excludes any unspecified elements, processes, or components. In patent claims, such a phrase closes the claim to materials other than those listed, with the exception of impurities normally associated with the materials. If the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the preamble, it limits the elements to those specified in that clause only, and does not exclude other elements from the claim as a whole. 【0088】 The transitional phrase "consisting essentially of" is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements substantially influence the fundamental and novel features of the claimed invention, particularly the mode of action for achieving any of the desired results of the processes of the invention. The term "consisting essentially of" has an intermediate meaning between "including" and "consisting of." 【0089】 If applicants define an invention or part thereof using open-ended terms such as "including," it should be readily understood that (unless otherwise specified) such descriptions should also be interpreted as including inventions that use the terms "essentially consisting of" or "consisting of," such as compositions that are essentially or consist of. 【0090】 Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning. 【0091】 Refrigerant blend The global warming potential (GWP) is an index used to estimate the relative contribution to global warming caused by one kilogram of atmospheric emissions of a particular greenhouse gas compared to one kilogram of carbon dioxide emissions. GWP can be calculated for various time periods and reflects the atmospheric lifetime impact of a given gas. A GWP for a 100-year period is the commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. The Intergovernmental Panel on Climate Change (IPCC) provides scrutinized values ​​of refrigerant GWPs in its official assessment reports (ARs). The Fourth Assessment Report is designated as AR4, and the Fifth Assessment Report as AR5. The GWP values ​​reported herein for the refrigerant blends refer to the AR5 values ​​of the compounds listed herein. 【0092】 The ozone depletion potential (ODP) is a numerical value that indicates the amount of ozone depletion caused by a substance. ODP is the ratio of the effect of a chemical substance on ozone to the effect of a similar mass of R-11 or trichlorofluoromethane. R-11 is a type of chlorofluorocarbon (CFC) that contains chlorine, which is a cause of ozone depletion. Furthermore, the ODP of CFC-11 is defined as 1.0. Other CFCs and hydrofluorochlorocarbons (HCFCs) have ODPs in the range of 0.01 to 1.0. Hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein have an ODP of zero because they do not contain chlorine, bromine, or iodine, which are known to contribute to ozone decomposition and depletion. 【0093】 The composition comprises a refrigerant blend essentially consisting of E-1,3,3,3-tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC-32), and 1,1-difluoroethane (HFC-152a). Preferred amounts of HFO-1234zeE in the refrigerant blend include, but are not limited to, amounts of about 63 to 93 weight percent, about 68 to 93 weight percent, about 71 to 93 weight percent, about 63 to 86 weight percent, about 63 to 84 weight percent, about 63 to 82 weight percent, about 63 to 80 weight percent, about 63 to 76 weight percent, or about 63 to 69 weight percent, based on the total refrigerant blend composition. Suitable amounts of HFC-32 in the refrigerant blend include, but are not limited to, amounts of about 6% to 21% by weight, or about 6% to 17% by weight, about 6% to 12% by weight, about 6% to 9% by weight, about 11% to 21% by weight, or about 11% to 17% by weight, or about 14% to 17% by weight, or about 16% to 17% by weight, based on the total refrigerant blend composition. Suitable amounts of HFC-152a in the refrigerant blend include, but are not limited to, amounts of 1% to about 20% by weight, or about 7% to about 20% by weight, or about 10% to about 20% by weight, or about 15% to about 20% by weight, based on the total refrigerant blend composition. 【0094】 In one embodiment, the composition comprises a refrigerant blend containing about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63 to 86 weight percent of HFO-1234zeE, about 11 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63 to 84 weight percent of HFO-1234zeE, about 14 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. 【0095】 In another embodiment, the composition includes a refrigerant blend comprising a refrigerant blend essentially consisting of about 63–93 weight percent HFO-1234zeE, about 6–17 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, and the mean temperature gradient is less than 6K. 【0096】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–86 weight percent HFO-1234zeE, about 11–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, and also providing a 10% higher capacity than HFO-1234yf alone. 【0097】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–84 weight percent HFO-1234zeE, about 14–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, and also providing a 15% higher capacity than HFO-1234yf alone. 【0098】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–82 weight percent HFO-1234zeE, about 16–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, and also providing a 20% higher capacity than HFO-1234yf alone. 【0099】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–80 weight percent HFO-1234zeE, about 11–17 weight percent HFC-32, and about 7–20 weight percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, providing 10% higher capacity than HFO-1234yf, and exhibiting an average temperature gradient of less than 6K. 【0100】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–76 wt percent HFO-1234zeE, about 14–17 wt percent HFC-32, and about 10–20 wt percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE, providing a 15% higher capacity than HFO-1234yf, and exhibiting an average temperature gradient of less than 6K. 【0101】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a. 【0102】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 68–93 wt percent HFO-1234zeE, about 6–12 wt percent HFC-32, and about 1–20 wt percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE and exhibiting an average temperature gradient of less than 5K. 【0103】 In another embodiment, the composition comprises a refrigerant blend essentially consisting of about 71–93 wt percent HFO-1234zeE, about 6–9 wt percent HFC-32, and about 1–20 wt percent HFC-152a. In this range, the GWP < 150, classifying it as Class 2L (low flammability) by ASHRAE and exhibiting an average temperature gradient of less than 4K. 【0104】 The refrigerant blend has zero ODP and low GWP, or GWP ≤ 150, preferably GWP ≤ 120, or more preferably GWP ≤ 100 (according to the AR5 value). Table 1 below is a summary table showing refrigerants and GWPs from the Fifth Assessment Report conducted by the Intergovernmental Panel on Climate Change (IPCC). 【0105】 In the case of refrigerant blends, the GWP can be calculated as a weighted average of the individual GWP values ​​of the components in the blend, taking into account the mass (e.g., wt%) of each component in the blend. Table 1 provides the GWP values ​​for each component of the refrigerant blend of the present invention, along with two examples of GWP values ​​for refrigerant blends. 【0106】 [Table 1] 【0107】 The refrigerant blends described herein operate in heat exchangers, i.e., evaporators and / or condensers with low temperature gradients. Therefore, fractional distillation of the composition is limited in operation that provides efficient and consistent performance for cooling and heating. 【0108】 In some embodiments, the refrigerant blend provides an average temperature gradient of less than 6 K over the target operating range, more preferably a small gradient of less than 5 K over the target operating range, and most preferably less than 4.0 K over the target operating range (e.g., a gradient in the range of greater than 0 to about less than 4.0 K). This effect is observed when any of the aforementioned refrigerant blends are used in a heat pump. 【0109】 In some embodiments, compositions comprising, essentially, or consisting of HFO-1234ze(E), HFC-152a, and HFC-32 and their degradation products according to the present invention are preferably free from or substantially free from Group A fluorinated substances. 【0110】 In one embodiment, as used herein, “Group A fluorinated substance” includes a substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to H / Cl / Br / I) and (ii) meets the criteria for persistence in soil / sediments and water. The criteria are set forth in Annex XIII (Section 1.1.1) of the European Union's REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed May 2, 2023), which is referenced in the Regulatory Report Annex XV dated March 22, 2023, and whose disclosures are incorporated into this document by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed May 2, 2023). In one embodiment, the Group A fluorinated substance is, but is not limited to, trifluoroacetic acid (TFA). 【0111】 In another embodiment, as used herein, “Group A fluorinated substance” has a Henry’s Law constant of 250 Pa * m 3 The substance comprises any substance that is less than or equal to / mol and contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to H / Cl / Br / I). In one embodiment, the Group A fluorinated substance is, but is not limited to, TFA. 【0112】 Accordingly, according to some embodiments, the compositions of the present invention contain HFO-1234ze(E), HFC-152a, and HFC-32, and do not contain or substantially contain group A fluorinated substances such as TFA. In one embodiment, the term “does not contain” as used herein with respect to the presence of group A fluorinated substances in the composition means that the amount of such substances in the composition is so low that it is undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. In one embodiment, the phrase "substantially absent" as used herein with respect to the presence of Group A fluorinated substances in the composition means that the amount of such substances in the composition is greater than 0% by weight and less than 15% by weight, greater than 0% by weight and less than 10% by weight, greater than 0% by weight and less than 5% by weight, greater than 0% by weight and less than 4% by weight, greater than 0% by weight and less than 3% by weight, greater than 0% by weight and less than 2% by weight, greater than 0% by weight and less than 1% by weight, and all values ​​and ranges in between, when measured by gas chromatography (GC) techniques, e.g., gas chromatography (GC) with a flame ionization detector or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectroscopy (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectroscopy (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectroscopy (HPLC-MS) techniques. TFA analytical standards can be used with either gas chromatography or ion chromatography and are available, for example, from Sigma Aldrich. 【0113】 Furthermore, in some embodiments, the decomposition products of such compositions of the present invention, including HFO-1234ze(E), HFC-152a, and HFC-32, do not contain or substantially contain group A fluorinated substances such as TFA. In one embodiment, the term “does not contain” as used herein with respect to the formation of group A fluorinated substances by the composition means that the theoretical molar yield of such substances in the air, soil / sediment and water environmental compartments generated during the tropospheric decomposition of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques, e.g., GC or GC / MS methods using flame ionization detectors or electron capture detectors, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. In one embodiment, the phrase “substantially free” as used herein with respect to the formation of Group A fluorinated substances by the Composition means that the theoretical molar yield of such substances in the air, soil / sediment, and water environmental compartments generated during the tropospheric decomposition of the Composition is greater than 0% and 5% or less, greater than 0% and 4% or less, greater than 0% and 3% or less, greater than 0% and 2% or less, greater than 0% and 1% or less, and all values ​​and ranges in between, when measured by GC techniques, e.g., GC or GC / MS methods using a flame ionization detector or electron capture detector, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. 【0114】 Refrigerant additives The composition of the present invention, which includes a refrigerant blend, may further include a lubricant and can be used as a heat transfer fluid. The composition of the present invention, which includes a refrigerant blend and a lubricant, may contain additives such as stabilizers, leak detection materials (e.g., UV dyes), tracers, and other beneficial additives. 【0115】 The lubricant selected for this composition preferably has sufficient solubility in the refrigerant blend to ensure that the lubricant can be reliably returned from the evaporator to the condenser. Furthermore, the miscibility should not be so great as to reduce the effective viscosity of the lubricant for lubricating the compressor. In a preferred embodiment, the lubricant and refrigerant blend are miscible over a wide temperature range. For use in mobile air conditioning and heating, miscibility over a temperature range of about -40°C to about +40°C is desirable. 【0116】 Examples of lubricants of the present invention include polyalkylene glycol lubricants (PAG), polyol ester lubricants (POE), polyvinyl ether lubricants (PVE), as well as poly-α-olefins (PAO), alkylbenzenes, mineral oils, fluorinated polyethers, and even silicone lubricants. 【0117】 Preferred lubricants may be one or more polyalkylene glycol type lubricants (PAGs), one or more polyol ester type lubricants (POEs), one or more poly-α-olefin (PAOs), or one or more polyvinyl ether lubricants. In addition, the lubricant for combination with the refrigerant blend of the present invention may be a mixture of any of PAGs, POEs, and / or PVE lubricants. 【0118】 Polyalkylene glycol (PAG) oil may be a homopolymer or copolymer consisting of two or more oxypropylene groups. PAG oil may be end-protected, one end-protected, or both ends-protected. Examples of commercially available PAG oils include, but are not limited to, ND-8, Castrol PAG 46, Castrol PAG 100, Castrol PAG 150, Daphne Hermetic PAG PL, and Daphne Hermetic PAG PR. 【0119】 The PAG lubricant properties used in this invention are 10 at 20°C. 10It contains a volume resistivity greater than Ω·m, a surface tension of approximately 0.02 N / m to 0.04 N / m at 20°C, a kinematic viscosity of approximately 20 cSt to 500 cSt at 40°C, a dielectric breakdown voltage of at least 25 kV, and a hydroxyl value of up to 0.1 mg KOH / g. 【0120】 In one embodiment, the lubricant comprises PAG and is stable when exposed to the composition of the present invention having a total acid number (TAN) of less than about 1, greater than 0 and less than 1, greater than 0 and less than about 0.75, and optionally greater than 0 and less than 0.4, and a mg KOH / g number. In this embodiment, the lubricant comprises PAG and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PAG and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–80 weight percent HFO-1234zeE, about 11–17 weight percent HFC-32, and about 7–20 weight percent HFC-152a. In yet another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–76 weight percent HFO-1234zeE, about 14–17 weight percent HFC-32, and about 10–20 weight percent HFC-152a. In yet another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 63–69 weight percent HFO-1234zeE, about 16–17 weight percent HFC-32, and about 15–20 weight percent HFC-152a.In another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises PAG, and the refrigerant essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. And in a further embodiment, the refrigerant composition further comprises more than about 0 and less than 1 weight percent of additional compounds. 【0121】 A preferred lubricant may be one or more polyol ester type lubricants (POEs) or one or more polyvinyl ether lubricants. POE lubricants are typically formed by a chemical reaction (esterification) between a carboxylic acid or a mixture of carboxylic acids and an alcohol or a mixture of alcohols. 【0122】 In one embodiment, the polyol ester, as used herein, comprises an ester of a diol or polyol having about 3 to 20 hydroxyl groups and a carboxylic acid (or fatty acid) having about 1 to 24 carbon atoms, and is preferably used as a polyol. Esters that can be used as base oils are described in European Patent Application No. 2 727 980(A1), published pursuant to Section 153(4), which is incorporated herein by reference. Examples of diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. 【0123】 Examples of the polyols mentioned above include polyhydric alcohols, such as trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerin, polyglycerin (dimers to icomers of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol-glycerin condensates, adonitol, arabitol, xylitol, mannitol, etc.; polysaccharides, such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, melegitose; and their partial etherification products and methyl glucosides. Among these, hindered alcohols, such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), and tri(pentaerythritol), are preferred as polyols. 【0124】 The number of carbon atoms in a fatty acid is not particularly limited, but generally, fatty acids having 1 to 24 carbon atoms are used. Among fatty acids having 1 to 24 carbon atoms, from the viewpoint of lubrication properties, fatty acids having 3 or more carbon atoms are preferred, fatty acids having 4 or more carbon atoms are more preferred, fatty acids having 5 or more carbon atoms are even more preferred, and fatty acids having 10 or more carbon atoms are most preferred. In addition, from the viewpoint of compatibility with refrigerants, fatty acids having 18 or fewer carbon atoms are preferred, fatty acids having 12 or fewer carbon atoms are more preferred, and fatty acids having 9 or fewer carbon atoms are even more preferred. In one embodiment, the carboxylic acid has 2 to 18 carbon atoms. 【0125】 In addition, the fatty acid may be either a straight-chain fatty acid or a branched-chain fatty acid. From the viewpoint of lubrication properties, a straight-chain fatty acid is preferred, while from the viewpoint of hydrolysis stability, a branched-chain fatty acid is preferred. Furthermore, the fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. Specifically, examples of the above fatty acids include straight-chain or branched-chain fatty acids, such as pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanic acid, oleic acid, etc.; and so-called neoacids, in which a carboxylic acid group is bonded to a quaternary carbon atom. More specifically, preferred examples include valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n-decanoic acid), oleic acid (cis-9-octadecanoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid. Incidentally, polyol esters may be partial esters in which the hydroxyl groups of the polyol are not completely esterified; complete esters in which all hydroxyl groups are esterified; or mixtures of partial and complete esters, with complete esters sometimes being preferred. 【0126】 In polyol esters, from the viewpoint of superior hydrolysis stability, esters of hindered alcohols, such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), and tri(pentaerythritol), are more preferred, and esters of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, or pentaerythritol are even more preferred; from the viewpoint of particularly excellent compatibility with refrigerants and hydrolysis stability, pentaerythritol esters are most preferred. 【0127】 Preferred specific examples of polyol esters include: diesters of neopentyl glycol with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; triesters of trimethylolethane with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and trimethylolpropane with valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2- Examples include triesters of methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid with one or more fatty acids selected from these; triesters of trimethylolbutane with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and tetraesters of pentaerythritol with one or more fatty acids selected from valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid. Incidentally, esters with two or more fatty acids may also be mixtures of two or more esters of one fatty acid and a polyol, and esters of such mixed fatty acids and polyols. In particular, esters of mixed fatty acids and polyols are superior in low-temperature properties and compatibility with refrigerants. 【0128】 POE lubricants used in air conditioning applications for electric vehicles may have a kinematic viscosity of 20-500 cSt or 75-110 cSt, ideally about 80-100 cSt, most specifically 85-95 cSt (measured at 40°C according to ASTM D445). However, without intending to limit the present invention, it should be noted that other lubricant viscosities may be included depending on the requirements of the heat pump compressor in electric vehicles. Preferred features of automotive POE-type lubricants for use with the compositions of the present invention are listed below. 【0129】 [Table 2] 【0130】 In one embodiment, the lubricant comprises POE, which is stable upon exposure to the composition of the present invention, and the refrigerant composition has an amount of F ions less than about 500 ppm, optionally greater than 0 ppm to less than 500 ppm, greater than 0 ppm to less than 100 ppm, optionally greater than 0 ppm to less than 50 ppm. In one embodiment of this invention, the refrigerant is about 63 to 93 weight percent, or about 68 to 93 weight percent, or about 71 to 93 weight percent, or about 63 to 86 weight percent, or about 63 to 84 weight percent, or about 63 to 82 weight percent, or about 63 to 80 weight percent, or about 63 to 76 weight percent, or about 63 to 69 weight percent of HFO-1234zeE and about 6 to 21 weight percent, or about 6 to 17 weight percent, or about The refrigerant composition essentially consists of 6–12 weight percent, or about 6–9 weight percent, or about 11–21 weight percent, or about 11–17 weight percent, or about 14–17 weight percent, or about 16–17 weight percent of HFC-32, and about 1 weight percent to about 20 weight percent, or about 7 weight percent to 20 weight percent, or about 10 weight percent to 20 weight percent, or about 15 weight percent to 20 weight percent of HFC-152a. In further embodiments, the refrigerant composition further comprises more than zero and less than 1 weight percent of additional compounds. 【0131】 In one embodiment, the lubricant comprises POE and is stable when exposed to the composition of the present invention having a total acid number (TAN) of less than about 1, greater than 0 and less than 1, greater than 0 and less than about 0.75, and optionally greater than 0 and less than 0.4 mg KOH / g. In this embodiment, the lubricant comprises POE and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises POE and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–86 weight percent HFO-1234zeE, about 11–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–84 weight percent HFO-1234zeE, about 14–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In yet another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–82 weight percent HFO-1234zeE, about 16–21 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–80 weight percent HFO-1234zeE, about 11–17 weight percent HFC-32, and about 7–20 weight percent HFC-152a. In another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–76 weight percent HFO-1234zeE, about 14–17 weight percent HFC-32, and about 10–20 weight percent HFC-152a. In yet another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 63–69 weight percent HFO-1234zeE, about 16–17 weight percent HFC-32, and about 15–20 weight percent HFC-152a.In another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises POE, and the refrigerant essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. And in a further embodiment, the refrigerant composition further comprises more than about zero and less than 1 weight percent of additional compounds. 【0132】 In another embodiment, a PVE lubricant may be included as a lubricant in the composition of the present invention. Without intending to limit the scope of the present invention, examples of polyvinyl ether oils in embodiments of the present invention include those taught in the literature, such as those described in U.S. Patents No. 5,399,631 and No. 6,454,960. In another embodiment of the present invention, the polyvinyl ether oil is composed of structural units of the type shown by Formula 1: 【0133】 [ka] In the formula, R1, R2, R3, and R4 are independently selected from hydrogen and hydrocarbons, and the hydrocarbons may optionally contain one or more ether groups. In a preferred embodiment of the present invention, as shown in Formula 2, R1, R2, and R3 are each hydrogen. 【0134】 [ka] 【0135】 In another embodiment of the present invention, polyvinyl ether oil is composed of structural units of the type shown by formula 3: 【0136】 [ka] In the formula, R5 and R6 are independently selected from hydrogen and hydrocarbons, and m and n are integers. 【0137】 In one embodiment, the polyvinyl ether oil comprises a copolymer of the following two units. 【0138】 [ka] 【0139】 The properties of the lubricant (viscosity, solubility of the refrigerant, and miscibility with the refrigerant) can be adjusted by changing the m / n ratio and the sum of m+n. In another embodiment, the PVE lubricant is 50 to 95 weight percent of unit 1. 【0140】 In one embodiment, the lubricant comprises PVE and is stable when exposed to the composition of the present invention having a total acid number (TAN) of less than about 1, greater than 0 and less than 1, greater than 0 and less than about 0.75, and optionally greater than 0 and less than 0.4 mg KOH / g. In this embodiment, the lubricant comprises PVE and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PVE and the refrigerant essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a.In another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the lubricant comprises PVE, and the refrigerant essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. And in a further embodiment, the refrigerant composition further comprises more than about zero and less than 1 weight percent of additional compounds. 【0141】 With respect to POE lubricants, similar properties and characteristics may be required, particularly for use in automotive air conditioning and heating systems, since PVE lubricants are used in the compositions described herein. 【0142】 In a preferred embodiment, the lubricant is soluble in the refrigerant at temperatures in the range of about -40°C to about 80°C, more preferably in the range of about -30°C to about 40°C, and more specifically in the range of -25°C to 40°C. In another embodiment, high-temperature insolubility is undesirable because attempts to retain the lubricant within the compressor are not preferred. 【0143】 The amount of lubricant can range from approximately 1% to 20% by weight, 1% to 7% by weight, and in some cases, 1% to 3% by weight. 【0144】 To suppress the hydrolysis of lubricating oil, it is necessary to control the moisture concentration in the heating / cooling systems of electric vehicles. Therefore, the lubricant in this embodiment needs to have a low moisture content, typically less than 100 ppm by weight. 【0145】 In a preferred embodiment, the lubricant comprises a POE lubricant that is soluble in the refrigerant blend of the vehicle heat pump system at temperatures ranging from about -35°C to about 100°C, more preferably from about -35°C to about 50°C, and more specifically from -30°C to 40°C. In another preferred embodiment, the POE lubricant is soluble at temperatures above about 70°C, more preferably above about 80°C, and most preferably at temperatures between 90°C and 95°C. 【0146】 Of particular note is that at 20℃, 10 10 PAG, POE, PAO, and PVE lubricants having a volume resistivity greater than Ω·m; a surface tension of approximately 0.02 N / m to 0.04 N / m at 20°C; a kinematic viscosity of approximately 20 cSt to 500 cSt, or approximately 50 cSt to 200 cSt, or approximately 75 cSt to 100 cSt at 40°C; a dielectric breakdown voltage of at least 25 kV; and a hydroxyl value of up to 0.1 mg KOH / g. 【0147】 HFO-type refrigerants are thermally unstable due to the presence of double bonds and can decompose under extreme use, handling, or storage conditions. Therefore, adding stabilizers to HFO-type refrigerants can be beneficial. In particular, examples of stabilizers include nitromethane, ascorbic acid, terephthalic acid; azoles such as toltriazole or benzotriazole; phenolic compounds such as tocopherol; hydroquinone, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol; epoxides such as n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, and butylphenyl glycidyl ether (sometimes fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides); cyclic monoterpenes; terpenes such as d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, or β-pinene; phosphates, phosphates, phosphonates, thiols, and lactones. Examples of suitable stabilizers are disclosed in International Publication Nos. 2019213004, 2020222864, and 2020222865, which are incorporated herein by reference. 【0148】 The blend may or may not contain stabilizers, depending on the requirements of the system in which it is used. If the refrigerant blend contains stabilizers, it may contain any amount between 0.001% and 1% by weight, preferably about 0.01% to about 0.5% by weight, more preferably about 0.01% to about 0.3% by weight, of any of the stabilizers listed above, most often preferably d-limonene. 【0149】 In some embodiments, the compositions disclosed herein may contain a tracer compound or a tracer. The tracer may contain two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million (ppm) to about 1000 ppm, based on the weight of the total composition. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm. 【0150】 A predetermined amount of tracer may be present in the composition of the present invention to enable the detection of any dilution, contamination, or other change of the composition. The presence of a particular compound in the composition may indicate by what method or process one of the components was produced. A specified amount of tracer may be added to the composition to identify the source of the composition. In this way, detection of patent infringement can be achieved. The tracer may be a refrigerant compound, but it is present in the composition at a level that is unlikely to affect the performance of the refrigerant component of the composition. 【0151】 The tracer compound may be a hydrofluorocarbon, hydrofluoroolefin, hydrochlorocarbon, hydrochloroolefin, hydrochlorofluorocarbon, hydrochlorofluoroolefin, hydrochlorocarbon, hydrochloroolefin, chlorofluorocarbon, chlorofluoroolefin, hydrocarbon, perfluorocarbon, perfluoroolefin, or a combination thereof. Examples of tracer compounds include HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2 -Fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1-trifluoro-2-methylpropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane), CFC-12 (dichlorodiph HCFC-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 (chloromethyl HFO-1141 (fluoroethene), HCFO-1130 (1,2-dichloroethene), HCFO-1130a (1,1-dichloroethene), HCFO-1131 (1-chloro-2-fluoroethene), HCFO-1122 (2-chloro-1,1-difluoroethene), HFO-1123 (1,1,2-trifluoroethene), HFO-1234ye (1,2,3,3-tetrafluoroethene) Examples include, but are not limited to, trafluoropropene, 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. In embodiments, any range of the compositions of the present disclosure may further include additional compounds. In one embodiment, the refrigerant blend may include, essentially consist of, or consist of HFO-1234zeE, HFC-32, and HFC-152a, in addition to an optional additional compound. In one embodiment, the composition comprises the refrigerant blend and the additional compound, the refrigerant blend essentially consisting of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the composition comprises the refrigerant blend and the additional compound, the refrigerant blend isIn another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend comprising a In another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In yet another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 63–69 weight percent HFO-1234zeE, about 16–17 weight percent HFC-32, and about 15–20 weight percent HFC-152a. In another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 68–93 weight percent HFO-1234zeE, about 6–12 weight percent HFC-32, and about 1–20 weight percent HFC-152a. In another embodiment, the composition comprises a refrigerant blend and additional compounds, the refrigerant blend essentially consisting of about 71–93 weight percent HFO-1234zeE, about 6–9 weight percent HFC-32,and essentially consist of about 1 to 20 weight percent of HFC-152a. In any of the above embodiments, additional compounds are present in amounts greater than about 0 and less than 1 weight percent. 【0152】 In another embodiment, the composition comprises at least one additional compound, a) At least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropine, HCC-1140, HFC-1234yf, HFO-1234ze(Z), HFO-1225yeE, HFO-1225yeZ, HFO-1225zc, HFC-134a, HFO-1243zf, and HCFO-1131; or b) At least one compound selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-143a, HCFC-22, HCC-40, HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, HCC-160, HCFO-1130a, HCFC-141b, HFO-1132a, HFC-143a, HCFO-1122, and HCFC-142b; or c) A combination of a) and b) is selected, The compound further comprises a compound whose total amount is greater than zero and less than 1 weight percent. 【0153】 In another embodiment, the composition comprises a refrigerant blend within any range of the above components and further comprises additional compounds including at least one of HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, or HCC-160, or a combination thereof. 【0154】 In another embodiment, the composition comprises a refrigerant blend within any range of the above components and further comprises additional compounds including at least one of HFC-143a, HFC-161, and HCFC-151a, or a combination thereof. 【0155】 In another embodiment, the composition comprises a refrigerant blend from any range of the above components and further comprises additional compounds comprising at least one of HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a, or a combination thereof. 【0156】 In another embodiment, the composition comprises a refrigerant blend from any range of the above components and further comprises additional compounds comprising at least one of HFO-1243zf, HCC-40, and HFC-161, or a combination thereof. 【0157】 Flammability of refrigerant blends Flammability is a term used to describe the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (LFL) is the lowest concentration of the heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the test conditions described in ASTM (American Society of Testing and Material) E681. The upper flammability limit (UFL) is the highest concentration of the heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the same test conditions. 【0158】 To be classified as non-flammable (Class 1, no flame propagation) according to ANSI / ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers) Standard 34 or ISO 817:2014(en)Refrigerants-Designation and Safety Classification, the refrigerant must meet the requirements of ASTM E681 when formulated in both the liquid and vapor phases, and must be non-flammable in both the liquid and vapor phases obtained in leak scenarios as defined by ANSI / ASHRAE Standard 34:2019 or ISO 817:2014(en)Refrigerants-Designation and Safety Classification. 【0159】 For a refrigerant blend to be classified as low-flammability (Class 2L) by ANSI / ASHRAE, the worst-case formulation (WCF) and worst-case fractionation for flammability (WCFF) must be determined based on manufacturing tolerances and vapor leakage behavior. To be classified as Class 2L, low-flammability, the WCF and WCFF must exhibit flame propagation of 0.0062 lb / ft when tested at 140°F (60°C) and 14.7 psia (101.3 kPa). 3 (0.10 kg / m 3 ) It must have an LFL of 2) and a maximum combustion rate of 3.9 in. / s (10 cm / s) or less when tested at 73.4°F (23.0°C) and 14.7 psia (101.3 kPa). In addition, the nominal refrigerant blend must have a heat of combustion of less than 8169 Btu / lb (19,000 kJ / kg). 【0160】 ASHRAE Standard 34 provides a methodology for calculating the heat of combustion of a refrigerant blend using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with sufficient oxygen for a stoichiometric reaction. 【0161】 When HFO-1234zeE, HFC-32, and HFC-152a components are blended in specific ratios, the resulting blend has flammability of Class 2 or Class 2L as defined by ANSI / ASHRAE standard 34 and ISO 817. Class 2 and Class 2L flammability can be controlled in automotive heating / cooling systems. 【0162】 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 in particular may be in the range of about 5 to about 1,000 ppm, about 5 to about 500 ppm, and about 1 to about 100 ppm. 【0163】 In one embodiment, the amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 to less than 1% by weight of the refrigerant composition, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight. 【0164】 Another embodiment of the present invention relates to storing any of the aforementioned compositions in a gas phase and / or liquid phase in a sealed container. The water concentration in the gas phase and / or liquid phase in the sealed container is in the range of about 0.1 to 200 ppm by weight. The oxygen concentration in the gas phase and / or liquid phase in the sealed container is in the range of about 10 ppm by volume to about 0.35 percent by volume at about 25°C. The air concentration in the gas phase and / or liquid phase in the sealed container is in the range of about 100 ppm by volume to about 1.5 percent by volume. 【0165】 Containers for storing the aforementioned compositions can be constructed of any suitable material and design that can seal the compositions while maintaining the gas and liquid phases. Examples of suitable containers include pressure vessels such as tanks, filling cylinders, and secondary filling cylinders. Containers can be constructed from any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, especially low-alloy steel, stainless steel, and possibly aluminum alloys. 【0166】 The compositions of the present invention can be prepared by any convenient method for combining desired amounts of individual components. A preferred method is to weigh out the desired amounts of components and then combine them in a suitable tank. Stirring may be used if desired. In another embodiment, any of the aforementioned refrigerant compositions can be prepared by blending HFO-1234zeE, HFC-32, and HFC-152a, and optionally at least one additional compound. 【0167】 In further embodiments, the composition may be prepared from recycled or regenerated refrigerants. One or more of the components can be recycled or regenerated by removing contaminants such as lubricants or residues that may contain particulate matter from air, water, or system components. Means for removing contaminants can vary widely but may include distillation, decantation, filtration, and / or drying using molecular sieves or other absorbents. The recycled or regenerated components may then be combined with the other components as described above. 【0168】 System and Method Embodiments of the present invention provide a system for heating and cooling the passenger compartment of an electric vehicle. The system comprises an evaporator, a compressor, a condenser, and an expansion unit, each operably connected to perform a vapor compression cycle, and the system contains one of the aforementioned compositions comprising a refrigerant blend essentially consisting of HFO-1234zeE, HFC-32, and HFC-152a. The mean temperature gradient in the system of the present invention is 6.0K or less, preferably 5.0K or less, or more preferably 4.0K or less. The system is preferably a heat pump. Due to the superior performance of the heat pump system in both heating and cooling the passenger compartment of an electric vehicle, the system may no longer require a heater with a positive temperature coefficient (PTC). 【0169】 Refrigerant blends can be used in various heating and cooling systems. In some embodiments, a reversing valve is used, and the same loop is used for both cooling and heating. In other embodiments, an air-side bypass or a redesign of the refrigerant valve / system can achieve the same effect as a reversible cycle without a reversing valve. 【0170】 In the embodiment shown in Figure 1, the refrigeration system 100 having a refrigeration loop 110 comprises a first heat exchanger 120, a pressure regulator 130, a second heat exchanger 140, a compressor 150, and a four-way valve 160. The first and second heat exchangers are of the air / refrigerant type. The refrigerant in the loop 110 and the airflow generated by the fan pass through the first heat exchanger 120. 【0171】 In cooling mode, the refrigerant, which has been started to move by the compressor 150, passes through the valve 160, then through the heat exchanger 120 which acts as a condenser, i.e., transfers thermal energy to the outside, then through the pressure regulator 130, and then through the heat exchanger 140 which acts as an evaporator, cooling the airflow that is intended to be blown into the interior of the vehicle. 【0172】 In heat pump mode, the direction of the refrigerant flow is reversed using valve 160. Heat exchanger 140 functions as a condenser, and heat exchanger 120 functions as an evaporator. Heat exchanger 140 can then be used to heat the airflow directed towards the passenger compartment of the vehicle. 【0173】 The additional heat transfer loops are connected to the heat pump system and allow heat to be absorbed or released in the heat exchangers 120 and / or 140, thereby transferring heat away from the motor or battery, and thus have the function of providing thermal management for those compartments of the vehicle as well as cooling and heating for the passenger compartment. 【0174】 In the embodiment shown in Figure 2, the refrigeration system 300 having a refrigeration loop 310 comprises a first heat exchanger 320, a pressure regulator 330, a second heat exchanger 340, a compressor 350, and a four-way valve 360. The first heat exchanger 320 and the second heat exchanger 340 are of the air / refrigerant type. The operation of the heat exchangers 320 and 340 is the same as in the first embodiment shown in Figure 1. Two fluid / liquid heat exchangers 370 and 380 are installed in both the refrigeration loop circuit 310 and the engine cooling circuit or secondary glycol-water circuit. Installing fluid / liquid heat exchangers without passing an intermediate gaseous fluid (e.g., air) contributes to improved heat exchange compared to air / fluid heat exchangers. 【0175】 In one embodiment, a system for heating and cooling the passenger compartment of an electric vehicle further comprises a reheater operably connected between a compressor and a condenser to reduce humidity in the passenger compartment during the cooling mode. 【0176】 In the embodiment shown in Figure 3, the refrigeration system 400 having a refrigeration loop 410 comprises a first heat exchanger (condenser) 420, a pressure regulator 430, a second heat exchanger (evaporator) 440, a compressor 450, a three-way valve 460, and a third heat exchanger (for reheating) 470. In cooling mode, at least a portion of the discharge flow from the compressor 450 is directed through the three-way valve 460 to the third heat exchanger 470. The outlet flow from the third heat exchanger 470 is discharged into the inlet of the first heat exchanger 420. The refrigerant is condensed by the first heat exchanger 420 using an external fan 480 and ambient air as a heat sink. The existing saturated or supercooled liquid expands in the pressure regulator 430, and the resulting low-pressure saturated mixture of refrigerant liquid and vapor enters the second heat exchanger 440. By using a second fan 490 located outside the cooling loop, the refrigerant evaporates within the second heat exchanger 440. The air passing through the second heat exchanger 440 is cooled to below the air dew point temperature. This partially condenses the moisture in the air, thereby lowering the absolute humidity of the air. The air then passes through a third heat exchanger 470, which transfers heat to the air, causing the air temperature to rise above the dew point and the relative humidity of the air to decrease, and the air is then supplied to the passenger compartment. This process of cooling to a temperature below the dew point temperature to remove moisture and then reheating to a temperature above the dew point temperature enables cooling and relative humidity control of the vehicle's passenger compartment. In heating mode, a three-way valve 460 is adjusted to obstruct the flow of refrigerant to the first heat exchanger 420, and heating of all vehicle compartments is achieved using the third heat exchanger 470 in the heat pump configuration shown in Figure 1. 【0177】 In the embodiment shown in Figure 4, an air conditioning (AC) and heat pump (HP) system 500 can provide heating, cooling, or both within the vehicle passenger compartment or for other vehicle loads. The system 500 includes an AC circuit 510 and an HP circuit 520. In the air conditioning-only mode, the HP control valve 530 upstream of the heat pump condenser 540 is closed, allowing refrigerant to flow from the compressor 550 into the air-cooled AC condenser 560, through the AC expansion valve 570 to the AC evaporator 580, providing cooling to the passenger compartment. The refrigerant then returns from the AC evaporator 580 to the compressor 550. In the heat pump-only mode, the AC control valve 535 upstream of the AC condenser 560 is closed, allowing refrigerant to flow from the compressor 550 into the HP condenser 540, providing heating to the passenger compartment. The refrigerant then flows from the HP condenser 540 through the HP expansion valve 575 to the HP evaporator 585. A separate humidity control mode can be achieved by sending a portion of the compressor discharge gas to the AC circuit 510 and the remainder to the HP circuit 520. 【0178】 In the embodiment shown in Figure 5, a system 600 can be realized for heating, cooling, or both for the vehicle passenger compartment or other vehicle loads. The system 600 includes an AC circuit 610 and a water-cooled / HP circuit 620. In AC-only mode, the water loop control valve 630 upstream of the water-cooled condenser 640 is closed, allowing refrigerant to flow from the compressor 650 into the AC condenser 660, through the AC expansion valve 670 to the AC evaporator 680, and provide cooling to the passenger compartment. In HP-only mode, the AC control valve 635 upstream of the AC condenser 660 is closed, allowing refrigerant to flow from the compressor 650 into the water-cooled condenser 640. A heat transfer fluid (e.g., water or another heat transfer fluid) receives the heat generated in the water-cooled condenser 640 and transfers it to the passenger compartment heater core 690, supplying heat to the passenger compartment. The heat transfer fluid can return from the passenger compartment heater core 690 to the water-cooled condenser 640. The refrigerant flows from the water-cooled condenser 640 through the HP expansion valve 675 to the HP evaporator 685, which cools a heat transfer fluid that can be used to cool other components of the vehicle, and then returns to the compressor 650. In some embodiments, there are one or more water / heat transfer fluid loops that can be used to heat and / or cool various other components of the vehicle. A separate humidity control mode can be achieved by sending a portion of the compressor discharge gas to the AC circuit 610 and the remainder to the water-cooled / HP circuit 620. 【0179】 In the embodiments shown in Figures 6 to 9, the same components are present in the system, but only some of those components are used depending on the operating mode. 【0180】 In one embodiment, in a heating mode where specific conditions exist that both the vehicle's passenger compartment and other vehicle components require heat, the refrigerant circuit 700 operates as shown in Figure 6. Starting from the compressor 750, the discharged refrigerant vapor takes two paths. One path passes through the passenger compartment condenser 740. The passenger compartment condenser 740 is typically a finned-tube or microchannel type refrigerant-air heat exchanger and may be single-pass or multi-pass. A first fan 745 in the vehicle ventilation piping guides a flow of either 100% outside air or a mixture of outside air and return air from the vehicle's passenger compartment across this passenger compartment condenser 740, where the refrigerant heats the air as it condenses. In this mode, a physical bypass 735 in the vehicle ventilation piping prevents any air from passing over the passenger compartment evaporator 730. The second path of the refrigerant leaving the compressor passes through a valve 770 and enters a liquid / heat transfer fluid heat exchanger 720, which allows heat to be transferred from the warm refrigerant to the vehicle's heat transfer fluid loop (not shown). Next, this vehicle heat transfer loop can be used to manage other vehicle heat loads. The heat transfer fluid in the heat transfer fluid loop may be water or a water / glycol solution. Next, the condensed refrigerant exiting the exchanger 720 merges with the liquid refrigerant outlet of the condenser 740, and the merged flow flows through the expansion device 775, which reduces the pressure of the liquid refrigerant and creates a liquid-vapor mixture. This liquid-vapor mixture then flows through the outdoor heat exchanger 780 (i.e., the evaporator in this configuration). The outdoor heat exchanger 780 is typically a finned tube or microchannel type refrigerant-air heat exchanger and may be single-pass or multi-pass. A second fan 785 guides an airflow across the outdoor heat exchanger 780, allowing the liquid-vapor refrigerant mixture to completely evaporate before it absorbs heat from the ambient air and returns to the compressor 750. 【0181】 In another embodiment, in a heating mode where specific conditions exist requiring only passenger compartment heating, the refrigerant circuit 800 operates as shown in Figure 7. Starting from the compressor 850, the discharge vapor first flows through the passenger compartment condenser 840. A first fan 845 in the vehicle ventilation piping guides a flow of either 100% outside air or a mixture of outside air and return air from the vehicle's passenger compartment across this passenger compartment condenser 840, and the refrigerant exchanges heat between the condenser 840 and the air. In this mode, a physical bypass 835 in the vehicle ventilation piping prevents any air from flowing beyond the passenger compartment evaporator 830. The refrigerant condenses in the passenger compartment condenser 840 and flows to the expansion device 875, which reduces the pressure of the liquid refrigerant and creates a liquid-vapor mixture. This liquid-vapor mixture flows through the outdoor heat exchanger 880 (i.e., the evaporator in this configuration). The second fan 885 will guide an airflow across the outdoor heat exchanger 880, allowing the liquid-vapor refrigerant mixture to completely evaporate before it absorbs heat from the ambient air and returns to the compressor 850. 【0182】 In another embodiment, in a cooling mode where certain conditions exist requiring cooling of both the vehicle passenger compartment and vehicle components, the refrigerant circuit 900 operates as shown in Figure 8. Starting from the compressor 950, the discharged refrigerant vapor first flows through the passenger compartment condenser 940, but in this mode, there is no heat transfer as a physical bypass 945 in the vehicle ventilation piping prevents any air from flowing beyond the passenger compartment condenser 940. The vaporized refrigerant passes through the passenger compartment condenser 940 and flows through valve 975 into the outdoor heat exchanger 980. In this mode, the first fan 985 induces a flow across the heat exchanger, causing the high-temperature refrigerant vapor to exchange heat and condense into a liquid, so the outdoor heat exchanger 980 functions as a condenser. Some of this liquid refrigerant leaves the outdoor heat exchanger 980 and enters the internal heat exchanger 990. The liquid refrigerant is supercooled in the internal heat exchanger 990 and then flows into the expansion device 910 and the passenger compartment evaporator 930. This air-refrigerant cabin evaporator 930 is a finned-tube or microchannel heat exchanger and may be single-pass or multi-pass. A second fan (or cabin ventilator fan) 935 guides a flow of either 100% outside air or a mixture of outside air and return air from the cabin across the coils of the cabin evaporator 930, where heat is exchanged between the air and the refrigerant. The refrigerant evaporates and returns to the internal heat exchanger 990, where it is further superheated before finally re-entering the compressor 950. The remaining portion of the refrigerant that leaves the condenser 980 flows through the expansion valve 915 into the liquid / heat transfer fluid heat exchanger 920, where heat from vehicle components is transferred to the refrigerant via a heat transfer fluid loop (not shown). This vehicle heat transfer loop can then be used to manage other vehicle heat loads. The refrigerant evaporates within the heat exchanger 920 and merges with the refrigerant that leaves the internal heat exchanger 990 at the intake of the compressor 950. 【0183】 In another embodiment, in a cooling mode where specific conditions exist requiring only vehicle passenger compartment cooling, the refrigerant circuit 1000 operates as shown in Figure 9. Starting from the compressor 1050, the discharged refrigerant vapor first flows through the passenger compartment condenser 1040, and in this mode, there is no heat transfer as a physical bypass 1045 in the vehicle ventilation piping prevents any air from flowing beyond the passenger compartment condenser 1040. The vaporized refrigerant passes through the passenger compartment condenser 1040 and flows through the valve 1075 into the outdoor heat exchanger 1080. In this mode, the first fan 1085 induces a flow across the heat exchanger 1080, and the high-temperature refrigerant vapor exchanges heat and condenses into a liquid, so the outdoor heat exchanger 1080 functions as a condenser. This liquid refrigerant leaves the outdoor heat exchanger 1080 and enters the internal heat exchanger 1090. The liquid refrigerant is supercooled in the internal heat exchanger 1090 and then flows into the expansion device 1010 and the cabin evaporator 1030. A second fan (or cabin ventilator fan) 1035 directs a flow of either 100% outside air or a mixture of outside air and return air from the cabin across the cabin evaporator 1030, where heat is exchanged between the air and the refrigerant. The refrigerant evaporates and returns to the internal heat exchanger 1090, where it is further superheated before finally returning to the compressor 1050. 【0184】 For use in hybrid, mild hybrid, plug-in hybrid, or fully electric vehicles for thermal management (heat transfer from one part of the vehicle to another) of passenger compartments providing air conditioning (A / C) or heating to the passenger compartment, the refrigerant blends of the present disclosure, comprising HFO-1234zeE, HFC-32, and HFC-152a, have low GWP, low toxicity, and low flammability with small temperature gradients. In addition, the refrigerant blends provide improved performance under the same conditions compared to HFO-1234yf, and in particular, provide higher capacity than HFO-1234yf alone, and more than 20% higher than HFO-1234yf alone, and a higher COP than HFO-1234yf alone when operating under the same conditions. The COP is preferably at least 5% higher than HFO-1234yf alone, more preferably at least 6% higher than HFO-1234yf alone, and most preferably at least 7% higher than HFO-1234yf alone, when operating under the same conditions. 【0185】 In another embodiment, a method for replacing HFO-1234yf in a heating and cooling system contained within an electric vehicle is also disclosed herein, comprising providing one of the aforementioned compositions as a heat transfer fluid to the heating and cooling system. The composition for replacing HFO-1234yf comprises a refrigerant blend essentially consisting of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63 to 86 weight percent of HFO-1234zeE, about 11 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a.In another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. According to any of the embodiments described above, the refrigerant blend produces a volumetric heating capacity that is at least 10%, 15%, or 20% higher than that of HFO-1234yf alone when operating under the same conditions. In the method of substituting HFO-1234yf, the average temperature gradient with the substitute composition is less than 6.0K, preferably less than 5.0K, or more preferably less than 4.0K. 【0186】 In another embodiment, a method is disclosed for replacing HFO-1234yf in a cooling system contained within an internal combustion engine or hybrid vehicle, comprising adding one of the aforementioned compositions to the cooling system as a heat transfer fluid. The replacement can be performed during vehicle maintenance due to refrigerant leakage or performance degradation, or during the initial filling of a system designed to use HFO-1234yf. A composition for replacing HFO-1234yf comprises a refrigerant blend essentially consisting of about 63–93 weight percent of HFO-1234zeE, about 6–17 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a.In another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. According to any of the embodiments described above, the refrigerant blend produces a volumetric heating capacity that is at least 10%, 15%, or 20% higher than that of HFO-1234yf alone when operating under the same conditions. In this method of substituting HFO-1234yf, the mean temperature gradient with the substitute composition is less than 6.0K, preferably less than 5.0K, or more preferably less than 4.0K. 【0187】 In one embodiment, a method for servicing the heating and cooling systems of an electric vehicle is provided. This method includes removing all spent refrigerant from the system and refilling the system with a composition comprising a refrigerant blend essentially consisting of HFO-1234zeE, HFC-32, and HFC-152a. The spent refrigerant may be any of the aforementioned compositions, or it may be a composition that has changed from any of the aforementioned compositions due to some fractionation of the low-boiling-point components of the refrigerant blend and preferential leakage. Due to fractionation that can occur while operating a refrigerant with a temperature gradient, leakage of refrigerant may change the composition of the remainder in the heating and cooling system. This change in composition makes it difficult to determine the composition of the remainder in the system. Therefore, if the system performance is degraded, it is necessary to remove all refrigerant present in the heating and cooling system and refill the system with a fresh refrigerant blend having an optimized refrigerant blend composition. Furthermore, since many of the compositions listed in Table 3 exhibit performance quite similar to pure HFO-1234yf, compositions containing HFO-1234zeE, HFC-32, and HFC-152a can be used to replenish the heat transfer fluid in existing vehicles that require additional refrigerant. Alternatively, the compositions may also be useful when a complete refill of the refrigerant is required to completely replace HFO-1234yf during maintenance. 【0188】 In one embodiment, the use of any of the aforementioned compositions, comprising a refrigerant blend essentially consisting of HFO-1234zeE, HFC-32, and HFC-152a, is provided as a heat transfer fluid in a system for heating and cooling passenger compartments of an electric vehicle. 【0189】 In other embodiments, including compositions intended to replace conventional high-GWP refrigerants in refrigeration, air conditioning, and heat pump applications, it is desirable that the refrigerant composition exhibits lower GWP and similar or improved refrigerant properties compared to conventional refrigerants. 【0190】 In some embodiments, the compositions disclosed herein may be used in stationary systems such as refrigeration, air conditioning, and heat pump systems. The compositions of the present invention can function as a substitute for conventional refrigerants having much higher GWP, particularly R-404A, R-410A, R-407A, R-407C, or R-407F. Stationary systems may include refrigerated cases in supermarkets, frozen cases in supermarkets, cooling systems providing air conditioning to large buildings such as apartments, office buildings, hospitals, and / or school buildings, residential air conditioning systems, residential heat pumps for heating or cooling air, or for heating water or other heat transfer fluids, or residential refrigerators or freezers. The cooling system mentioned may be a centrifugal, screw, or scroll system, as defined by the compressor used. Furthermore, the cooling system may operate with a direct expansion heat exchanger or a full-liquid evaporator heat exchanger. 【0191】 In one embodiment, a stationary refrigeration, air conditioning, or heat pump system is disclosed herein that contains a refrigerant essentially comprising about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially comprises about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially comprises about 63 to 86 weight percent of HFO-1234zeE, about 11 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. 【0192】 In another embodiment, a method for replacing a first refrigerant selected from R-22, R-404A, R-507A, R-507B, R-410A, R-407A, R-407C, or R-407F is disclosed herein, comprising removing at least a portion of the first refrigerant and filling with a second refrigerant consisting of about 63–93 weight percent of HFO-1234zeE, about 6–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend consists of about 63–93 weight percent of HFO-1234zeE, about 6–17 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a.In another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. 【0193】 In another embodiment, a method for replacing a first refrigerant selected from R-513A, R-448A, R-448B, R-449A, R-452A, R-454A, R-454B, R-454C, R-466A, R-1234yf, or R-1234ze is disclosed herein, comprising removing at least a portion of the first refrigerant and filling with a second refrigerant consisting of about 63–93 weight percent of HFO-1234zeE, about 6–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend consists of about 63–93 weight percent of HFO-1234zeE, about 6–17 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–86 weight percent of HFO-1234zeE, about 11–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–84 weight percent of HFO-1234zeE, about 14–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–82 weight percent of HFO-1234zeE, about 16–21 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–80 weight percent of HFO-1234zeE, about 11–17 weight percent of HFC-32, and about 7–20 weight percent of HFC-152a. In another embodiment, the refrigerant blend essentially consists of about 63–76 weight percent of HFO-1234zeE, about 14–17 weight percent of HFC-32, and about 10–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 63–69 weight percent of HFO-1234zeE, about 16–17 weight percent of HFC-32, and about 15–20 weight percent of HFC-152a.In another embodiment, the refrigerant blend essentially consists of about 68–93 weight percent of HFO-1234zeE, about 6–12 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. In yet another embodiment, the refrigerant blend essentially consists of about 71–93 weight percent of HFO-1234zeE, about 6–9 weight percent of HFC-32, and about 1–20 weight percent of HFC-152a. 【0194】 This use of the composition of the present invention has been described in detail in the preceding description and will be demonstrated in the following examples. The following examples are provided to illustrate specific aspects of the present invention and will not limit the scope of the appended claims. [Examples] 【0195】 (Example 1) Using a thermodynamic modeling program, the predicted performance of blends containing HFO-1234zeE, HFC-152a, and HFC-32 was modeled compared to HFO-1234yf alone. Fourteen sets of different conditions specified by the Society of Automotive Engineers (SAE) were modeled for characterizing refrigerant performance in automotive heat pump systems. Component properties were obtained from NIST REFPROP version 10. 【0196】 The conditions used are as described below in this specification and in Table 2. Evaporator overheating = 10K Suction line overheating = 0K Supercooling=5K Entropy efficiency of compressors, etc. = 70% Compressor volumetric efficiency = 95% 【0197】 [Table 3] * PTC = positive coefficient heater, positive coefficient heater 【0198】 Thermodynamic Modeling Comparison of Heat Pump Systems: HFO-1234zeE / HFC-152a / HFC-32 vs. HFO-1234yf. The results shown in Table 3 are the average temperature gradient, volumetric capacity, and COP for SAE points 1-13 (see Table 2 above). The capacity and COP are percentages higher than the corresponding values ​​for the refrigerant blends compared to HFO-1234yf alone. 【0199】 [Table 4-1] 【0200】 [Table 4-2] 【0201】 [Table 4-3] 【0202】 The data above demonstrates that refrigerant blends containing HFO-1234zeE, HFC-32, and HFC-152a often provide higher volumetric capacity, lower average temperature gradients (often below 6K), and significantly higher COP (up to 7% higher) than HFO-1234yf alone. The improved performance of the blends of the present invention indicates that new fluids can be easily used to provide sufficient cooling and heat to the passenger compartments of electric or hybrid vehicles. 【0203】 Furthermore, since many of the compositions listed in Table 3 exhibit performance quite similar to pure HFO-1234yf, compositions containing HFO-1234zeE, HFC-32, and HFC-152a can be used to replenish the heat transfer fluid in existing vehicles that require additional refrigerant. Alternatively, the compositions may also be useful when a complete refill of the refrigerant is required to completely replace HFO-1234yf during maintenance. 【0204】 While the present invention has been described with reference to preferred embodiments, those skilled in the art will understand that various modifications can be made without departing from the scope of the invention, and that equivalents can be used in place of certain elements. Furthermore, many modifications can be made without departing from the essential scope of the invention to adapt specific situations or materials to the teachings of the invention. Therefore, the present invention is not limited to the specific embodiments disclosed as the best mode intended for carrying out the invention, but is intended to include all embodiments included within the scope of the appended claims.

Claims

[Claim 1] A composition comprising a refrigerant blend containing HFO-1234zeE, HFC-32, and HFC-152a. [Claim 2] The composition according to claim 1, wherein the refrigerant blend essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 3] The composition according to claim 1 or 2, wherein the refrigerant blend essentially consists of about 63 to 93 weight percent of HFO-1234zeE, about 6 to 17 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 4] The composition according to claim 1 or 2, wherein the refrigerant blend essentially consists of about 63 to 86 weight percent of HFO-1234zeE, about 11 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 5] The composition according to claim 1, 2, or 4, wherein the refrigerant blend essentially consists of about 63 to 84 weight percent of HFO-1234zeE, about 14 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 6] The composition according to any one of claims 1, 2, 4, or 5, wherein the refrigerant blend essentially consists of about 63 to 82 weight percent of HFO-1234zeE, about 16 to 21 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 7] The composition according to any one of claims 1, 2, or 4, wherein the refrigerant blend essentially consists of about 63 to 80 weight percent of HFO-1234zeE, about 11 to 17 weight percent of HFC-32, and about 7 to 20 weight percent of HFC-152a. [Claim 8] The composition according to any one of claims 1, 2, 3, 4, 5, or 7, wherein the refrigerant blend essentially consists of about 63 to 76 weight percent of HFO-1234zeE, about 14 to 17 weight percent of HFC-32, and about 10 to 20 weight percent of HFC-152a. [Claim 9] The composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein the refrigerant blend essentially consists of about 63 to 69 weight percent of HFO-1234zeE, about 16 to 17 weight percent of HFC-32, and about 15 to 20 weight percent of HFC-152a. [Claim 10] The composition according to any one of claims 1, 2, or 3, wherein the refrigerant blend essentially consists of about 68 to 93 weight percent of HFO-1234zeE, about 6 to 12 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 11] The composition according to claim 1, 2, 3, or 10, wherein the refrigerant blend essentially consists of about 71 to 93 weight percent of HFO-1234zeE, about 6 to 9 weight percent of HFC-32, and about 1 to 20 weight percent of HFC-152a. [Claim 12] The composition according to any one of claims 1 to 11, wherein the refrigerant blend provides an average temperature gradient of about 0.1 K to less than 6 K. [Claim 13] The composition according to any one of claims 1 to 12, wherein the refrigerant blend provides an average temperature gradient of about 0.1 K to less than about 5 K. [Claim 14] The composition according to any one of claims 1 to 13, wherein the refrigerant blend provides an average temperature gradient of about 0.1 K to less than 4 K. [Claim 15] The composition according to any one of claims 1 to 14, wherein the refrigerant blend has a GWP of about 150 or less. [Claim 16] The composition according to any one of claims 1 to 15, wherein the refrigerant blend has a GWP of about 120 or less. [Claim 17] It further comprises at least one additional compound, wherein the additional compound is: a. At least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropyne, HCC-1140, HFC-1234yf, HFO-1234ze(Z), HFO-1225yeE, HFO-1225yeZ, HFO-1225zc, HFC-134a, HFO-1243zf, and HCFO-1131; or b. At least one compound selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-143a, HCFC-22, HCC-40, HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, HCC-160, HCFO-1130a, HCFC-141b, HFO-1132a, HFC-143a, HCFO-1122, and HCFC-142b; or c. A combination of a) and b); selected from the above, The composition according to any one of claims 1 to 16, wherein the total amount of the additional compound is greater than zero and less than 1 weight percent. [Claim 18] The composition according to claim 17, wherein the additional compound comprises at least one of HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, or HCC-160, or a combination thereof. [Claim 19] The composition according to claim 17, wherein the additional compound comprises HFC-143a, HFC-161, and HCFC-151a. [Claim 20] The composition according to claim 17, wherein the additional compound comprises HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a. [Claim 21] The composition according to any one of claims 17 or 20, wherein the additional compound comprises HFO-1243zf, HCC-40, and HFC-161. [Claim 22] The composition according to any one of claims 1 to 21, wherein the refrigerant blend has a combustion rate of 10 cm / s or less when measured according to the ISO 817 vertical tube method. [Claim 23] The composition according to any one of claims 1 to 22, wherein the refrigerant blend is classified as 2 L in terms of flammability as defined in ANSI / ASHRAE standard 34. [Claim 24] The composition according to any one of claims 1 to 23, wherein the refrigerant blend has an LFL of less than 10 volume percent when measured according to ASTM-E681. [Claim 25] The composition according to any one of claims 1 to 24, further comprising a lubricant. [Claim 26] The composition according to claim 25, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-α-olefin, and polyvinyl ether. [Claim 27] The composition according to claim 26, wherein the polyol ester lubricant is obtained by reacting a carboxylic acid with a polyol containing a neopentyl skeleton selected from the group consisting of neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mixtures thereof. [Claim 28] The composition according to claim 27, wherein the carboxylic acid has 2 to 18 carbon atoms. [Claim 29] The aforementioned lubricant is 10 at 20°C １０ The composition according to any one of claims 25 to 28, having a volume resistivity greater than Ω·m. [Claim 30] The composition according to any one of claims 25 to 29, wherein the lubricant has a surface tension of about 0.02 N / m to 0.04 N / m at 20°C. [Claim 31] The composition according to any one of claims 25 to 30, wherein the lubricant has a kinematic viscosity of about 20 cSt to about 500 cSt at 40°C. [Claim 32] The composition according to any one of claims 25 to 31, wherein the lubricant has a dielectric breakdown voltage of at least 25 kV. [Claim 33] The composition according to any one of claims 25 to 32, wherein the lubricant has a hydroxy value of up to 0.1 mg KOH / g. [Claim 34] The composition according to any one of claims 1 to 33, further comprising 0.1 to 200 ppm by weight of water. [Claim 35] The composition according to any one of claims 1 to 34, further comprising about 10 volume ppm to about 0.35 volume percent of oxygen. [Claim 36] The composition according to any one of claims 1 to 35, further comprising about 100 volume ppm to about 1.5 volume percent of air. [Claim 37] The composition according to any one of claims 1 to 36, further comprising a stabilizer. [Claim 38] The composition according to claim 37, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azole, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones. [Claim 39] The composition according to any one of claims 37 or 38, wherein the stabilizer is selected from toltriaazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene. [Claim 40] The composition according to any one of claims 37 to 39, wherein the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant. [Claim 41] The composition according to any one of claims 1 to 40, further comprising at least one tracer. [Claim 42] The composition according to claim 41, wherein the at least one tracer is present in an amount of about 1.0 ppm by weight to about 1000 ppm by weight. [Claim 43] The composition according to any one of claims 40 or 41, 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. [Claim 44] The at least one tracer is HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC -272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, C FC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCF C-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO -1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf A composition according to any one of claims 41 to 43, selected from the group consisting of HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof. [Claim 45] A refrigerant storage container comprising the refrigerant according to any one of claims 34, 35, or 36, wherein the refrigerant comprises a gas phase and a liquid phase. [Claim 46] A system for heating and cooling the passenger compartment of an electric vehicle, comprising an evaporator, a compressor, a condenser, and an expansion device, each operably connected to perform a vapor compression cycle, comprising the composition according to any one of claims 1 to 44. [Claim 47] The system according to claim 46, wherein the average temperature gradient is less than 6.0 K, preferably less than 5.0 K, and more preferably less than 4.0 K. [Claim 48] The system according to any one of claims 46 or 47, wherein the system does not include a PTC heater. [Claim 49] The system according to any one of claims 46, 47, or 48, further comprising a reheater operably connected between the compressor and the condenser. [Claim 50] A method for replacing HFO-1234yf in a heating and cooling system installed in an electric vehicle, comprising providing a composition according to any one of claims 1 to 44 as a heat transfer fluid. [Claim 51] The method according to claim 49, wherein the refrigerant produces a volumetric heating capacity at least 20% higher than HFO-1234yf alone when operating under the same conditions. [Claim 52] The method according to claim 50 or 51, wherein the refrigerant, when operated under the same conditions, produces a COP higher than that of HFO-1234yf alone. [Claim 53] A method for replacing HFO-1234yf in a cooling system provided in an internal combustion engine vehicle or a hybrid vehicle, comprising including the composition according to any one of claims 1 to 44 as a heat transfer fluid in the cooling system. [Claim 53] Use of the composition according to any one of claims 1 to 44 as a heat transfer fluid in a system for heating and cooling passenger compartments of a hybrid or electric vehicle. [Claim 54] The composition according to any one of claims 1 to 44, wherein the composition does not contain or substantially contains a group A fluorinated substance, and the decomposition product of the composition does not contain or substantially contains a group A fluorinated substance.

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