HFO-1234YF, HFO-1132E, AND HYDROCARBON COMPOSITIONS AND SYSTEMS FOR USING SAME - Patent application

Abstract

An environmentally friendly refrigerant blend utilizing a refrigerant comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene, at least one hydrocarbon selected from the group consisting of propane, cyclopropane, propylene, isobutane, and n-butane, and optionally 1,1-difluoroethane (HFC-152a). The blend has low GWP, low toxicity, and low flammability along with low temperature gradients for use in hybrid, mild hybrid, plug-in hybrid, or all-electric vehicles for passenger compartment thermal management (heat transfer from one part of the vehicle to another) to provide air conditioning (A / C) or heating to the passenger compartment.

Description

[Technical field]

[0001] The present invention is directed to compositions comprising HFO-1234yf, HFO-1132E, and at least one hydrocarbon, and their use as refrigerants in air conditioning and heat pump systems. [Background technology]

[0002] The automotive industry is undergoing an architecture platform refresh from using an internal combustion engine (ICE) for propulsion to using electric motors for propulsion. This platform refresh may significantly limit the size of the internal combustion engine (ICE) in hybrid, plug-in hybrid vehicles, or may eliminate the ICE entirely in pure electric vehicles. Some vehicles still retain an ICE and are known as hybrid electric vehicles (HEVs) or plug-in hybrid electric vehicles (PHEVs) or mild hybrid electric vehicles (MHEVs). Vehicles that are fully electric and do not have an ICE, including battery electric vehicles (BEVs), are called fully electric vehicles (EVs). All HEVs, PHEVs, MHEVs, and EVs use at least one electric motor. This electric motor provides some form of propulsion to the vehicle that is typically provided by the internal combustion engine (ICE) found in gasoline / diesel vehicles.

[0003] In electric vehicles, the ICE is usually reduced in size (HEV, PHEV, or MHEV) or eliminated (EV) to reduce the vehicle weight and thereby increase the electric drive cycles. The primary function of the ICE is to provide propulsion for the vehicle, but 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, which can be captured and used to heat the passenger compartment. It should be noted that the ICE can take some time (several minutes) to heat up and generate heat, but it works well down to temperatures as low as -30°C. Therefore, in electric vehicles, the reduction in size or elimination of the ICE creates a demand for an effective alternative heating of the passenger compartment. In current EVs that do not have an ICE, positive temperature coefficient (PTC) heaters are currently used. Using a heat pump for cooling and heating can replace the PTC heater along with the air conditioning system, allowing for more efficient cooling and heating.

[0004] Due to environmental pressures, the hydrofluorocarbon, or HFC, R-134a, is being phased out in mobile air conditioning in favor of low GWP refrigerants with a global warming potential (GWP) of less than 150. The hydrofluoroolefin, HFO-1234yf, meets the low GWP requirements (GWP=4 per Papadimitriou, GWP<1 per AR5), but has a lower refrigeration capacity compared to R-134a and cannot fully meet heating requirements at low (-10°C) to very low (-30°C) ambient temperatures in current system designs. Another option for automotive heat pumps is a refrigerant blend commonly used in stationary refrigerant applications. Examples of compositions containing HFO-1234yf are disclosed in WO 2007 / 126414, the disclosure of which is incorporated herein by reference.

[0005] Thus, a need exists 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 transportation, and residential and commercial structures. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2007 / 126414 Summary of the Invention [Problem to be solved by the invention]

[0007] Similarly, stationary residential and commercial structural heating and cooling also suffers from a lack of suitable low GWP refrigerants to replace the older high GWP refrigerants currently in use. [Means for solving the problem]

[0008] The present invention relates to compositions of environmentally friendly refrigerant blends with low GWP (GWP 100 or less), low toxicity (Class A per ANSI / ASHRAE Standard 34 or ISO Standard 817), and low flammability (Class 2 or Class 2L per ASHRAE 34 or ISO 817) with small temperature gradients for use in hybrid, mild hybrid, plug-in hybrid, or fully electric vehicles for full vehicle thermal management (transfer of heat from one part of the vehicle to another). The thermal management system can operate to cool and / or heat the power electronics, battery, motor, and provide air conditioning (A / C) and / or heating to the passenger compartment. These refrigerants can also be used in mass transit mobile applications that benefit from heat pump type systems that allow both heating and cooling of the battery, motor, and passenger compartment areas. Mass transit vehicle applications can include, but are not limited to, transportation vehicles such as ambulances, buses, shuttles, and trains.

[0009] In one embodiment of the invention, the composition comprises a refrigerant blend containing HFO-1234yf, HFO1132E, and at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane. In another embodiment of the invention, the composition further comprises HFC-152a.

[0010] The compositions of the present invention exhibit low temperature gradients over the operating conditions of the vehicle's thermal management system. It is preferable to have fluids with low or no temperature gradients due to the manner in which automotive vehicles are repaired or maintained. Currently, during the vehicle A / C repair or maintenance process, the refrigerant is handled through specific automotive maintenance machines that recover the refrigerant, recycle the refrigerant to some intermittent quality level to remove all contaminants, and then recharge the vehicle with the refrigerant after the repair or maintenance is completed. These machines are called R / R / R machines because they recover, recycle, and recharge the refrigerant. This on-site recovery, recycling, and recharge of the refrigerant during vehicle maintenance or repair is possible because a single compound refrigerant, currently HFO-1234yf, is used. Current automotive maintenance machines typically cannot handle refrigerant blends that may fractionate during use and in some cases cause the lowest boiling point components to leak preferentially. Thus, the refrigerant removed from the system during maintenance may not have the same ratio of components as the original blend that was charged. Because refrigerants are handled "on-site" at vehicle repair shops, there is no opportunity to reconstitute blended refrigerants to the original composition concentration as refrigerant recyclers do. Refrigerants with higher temperature gradients may sometimes require "reconstitution" to the original formulation or loss of cycle performance may occur. Thus, there is a need for refrigerants with lower temperature gradients for automotive applications. Because heat pump fluids are handled in the same manner as air conditioning fluids, this requirement of low temperature gradients also applies to heat pump type fluids if they are handled and / or maintained in the same manner as conventional air conditioning fluids. In addition, current heat exchangers are designed based on the use of single compound refrigerants. In order to maintain the overall system performance of current systems utilizing single component fluids, new refrigerants with significant temperature gradients may require a complete redesign of heat exchangers and other system components.

[0011] While HFO-1234yf can be used as an air conditioning refrigerant, it is limited in its ability to function as a heat pump type fluid, i.e., provide the required capacity in both cooling and heating modes. Thus, the refrigerants described herein uniquely provide improved capacity over HFO-1234yf in the heating operating range and / or extend the heating range capability over HFO-1234yf down to an evaporator temperature of -30°C, provide similar or improved efficiency (COP), have low GWP, low to mild flammability, while also uniquely exhibiting low temperature glide. Thus, these refrigerants are most useful in electric vehicle applications, particularly HEVs, PHEVs, MHEVs, EVs, and mass transit vehicles that require these properties beyond the lower heating range. It should be noted that the heat pump fluid must perform well in the air conditioning cycle, i.e., at refrigerant average condensing temperatures of 40°C or less, and desirably provide similar or greater capacity compared to HFO-1234yf. Thus, the refrigerant blends described herein perform particularly well over the temperature range of -30°C to +40°C and can provide both heating and cooling depending on which cycle the heat pump system requires.

[0012] The inventors have discovered a refrigerant blend that provides at least 20% higher volumetric capacity than HFO-1234yf alone, has a COP equal to or greater than the COP of HFO-1234yf alone, has an average temperature gradient of less than 4K, is non-toxic, and can be classified by ASHRAE as Class 2 or 2L flammable.

[0013] The present invention includes the following aspects and embodiments. In one embodiment, disclosed herein are compositions useful as refrigerants and heat transfer fluids. The compositions disclosed herein include 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2-difluoroethylene (HFO-1132E), at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and optionally 1,1-difluoroethane (HFC-152a).

[0014] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant blend comprising 51 to 90 weight percent HFO-1234yf, 3 to 25 weight percent HFO-1132E, about 1 to 4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and 0 to about 20 weight percent HFC-152a.

[0015] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant blend comprising 77 to 90 weight percent HFO-1234yf, 6 to 19 weight percent HFO-1132E, and about 1 to 4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane.

[0016] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 58-90 weight percent HFO-1234yf, about 3-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propane.

[0017] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 58-89 weight percent HFO-1234yf, about 6-18 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent propane.

[0018] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 84-89 weight percent HFO-1234yf, about 8-13 weight percent HFO-1132E, and about 1-4 weight percent propane.

[0019] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 61-90 weight percent HFO-1234yf, about 4-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane.

[0020] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 61-89 weight percent HFO-1234yf, about 5-15 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane.

[0021] Also disclosed herein is a composition, according to any of the foregoing embodiments, wherein the refrigerant blend consists essentially of about 84-90 weight percent HFO-1234yf, about 7-12 weight percent HFO-1132E, and about 1-4 weight percent cyclopropane.

[0022] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 60-90 weight percent HFO-1234yf, about 3-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propylene.

[0023] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 60-88 weight percent HFO-1234yf, about 4-17 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent propylene.

[0024] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 85 to 90 weight percent HFO-1234yf, about 6 to 12 weight percent HFO-1132E, and about 1 to 4 weight percent propylene.

[0025] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 51-90 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent isobutane.

[0026] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 51-88 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent isobutane.

[0027] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 77-88 weight percent HFO-1234yf, about 11-19 weight percent HFO-1132E, and about 1-4 weight percent isobutane.

[0028] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 56-90 weight percent HFO-1234yf, about 8-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.

[0029] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of about 56-87 weight percent HFO-1234yf, about 8-20 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.

[0030] Also disclosed herein is a composition, according to any of the foregoing embodiments, wherein the refrigerant blend consists essentially of about 82-88 weight percent HFO-1234yf, about 11-14 weight percent HFO-1132E, and about 1-4 weight percent n-butane.

[0031] Also disclosed herein are compositions, according to any of the foregoing embodiments, wherein the refrigerant blend provides an average temperature gradient of from about 0.1 K to less than about 4 K.

[0032] Also disclosed herein are compositions, according to any of the foregoing embodiments, wherein the refrigerant blend provides an average temperature gradient of from about 0.1 K to less than about 3 K.

[0033] Also disclosed herein are compositions, according to any of the foregoing embodiments, wherein the refrigerant blend provides an average temperature gradient of from about 0.1 K to less than about 2.5 K.

[0034] Also disclosed herein are compositions, according to any of the foregoing embodiments, wherein the refrigerant blend provides an average temperature gradient of from about 0.1 K to less than about 2.0 K.

[0035] Also disclosed herein is a composition, according to any of the foregoing embodiments, wherein the refrigerant blend has a GWP of about 35 or less.

[0036] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition consisting essentially of the refrigerant blend having a GWP of less than about 30.

[0037] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition consisting essentially of the refrigerant blend having a GWP of less than about 20.

[0038] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition consisting essentially of the refrigerant blend having a GWP of less than about 10.

[0039] According to any of the above embodiments, the method further comprises at least one additional compound, the additional compound being: a) comprises at least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-245fa, HFC-245eb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropyne, HCC-1140, HFC-1225ye, HFO-1225zc, HFC-134a, HFC-236ea, HFO-1243zf, and HCFO-1131; or b) comprises at least one compound selected from the group consisting of HFC-32, HCFC-31, HFC-143a, HCFC-22, HCC-40, HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, HCC-160, HCFO-1130a, HCFC-141b, HFC-143a, HCFO-1122, and HCFC-142b; or c) HFO-1132Z, HFO-1132a, HCFO-1131a, HCFC-142a, CFO-1122a, HFO-1123, HCFC-132, CFO-1113, d) a combination of a) and b), a) and c), b) and c), or a), b) and c); Also disclosed herein are compositions in which the total amount of additional compounds comprises greater than 0 weight percent and less than 1 weight percent.

[0040] Also disclosed herein, according to any of the preceding embodiments, is a composition 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.

[0041] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend consists essentially of additional compounds including HFC-143a, HCC-40, HFC-161, and HCFC-151a.

[0042] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition wherein the additional compound includes HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a.

[0043] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition wherein the additional compound comprises HFO-1243zf, HCC-40, and HFC-161.

[0044] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend has a burning velocity of 10 cm / s or less as measured according to the ISO 817 vertical tube method.

[0045] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the refrigerant blend is classified as 2L for flammability as defined in ANSI / ASHRAE Standard 34.

[0046] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the refrigerant blend has an LFL of less than 10 volume percent as measured according to ASTM-E681.

[0047] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition further comprising a lubricant.

[0048] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition wherein the lubricant comprises at least one selected from the group consisting of polyalkylene glycols, polyol esters, poly-α-olefins, and polyvinyl ethers.

[0049] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the polyol ester lubricant is obtained by reacting a carboxylic acid with a polyol comprising a neopentyl backbone selected from the group consisting of neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mixtures thereof.

[0050] Also disclosed herein, according to any of the preceding embodiments, is a composition wherein the carboxylic acid has 2-18 carbon atoms.

[0051] According to any of the preceding embodiments, the lubricant has a viscosity of 10 10 Also disclosed herein are compositions having a volume resistivity greater than Ω·m.

[0052] Also disclosed herein is a composition, according to any of the preceding embodiments, wherein the lubricant has a surface tension at 20° C. of about 0.02 N / m to 0.04 N / m.

[0053] Also disclosed herein, according to any of the foregoing embodiments, is a composition wherein the lubricant has a kinematic viscosity at 40° C. of from about 20 cSt to about 500 cSt.

[0054] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the lubricant has a breakdown voltage of at least 25 kV.

[0055] Also disclosed herein, according to any of the preceding embodiments, is a composition wherein the lubricant has a hydroxyl value of up to 0.1 mg KOH / g.

[0056] Also disclosed herein, according to any of the foregoing embodiments, is a composition further comprising 0.1 to 200 ppm by weight of water.

[0057] Also disclosed herein are compositions, according to any of the preceding embodiments, further comprising about 10 ppm by volume to about 0.35 percent by volume of oxygen.

[0058] Also disclosed herein are compositions, according to any of the foregoing embodiments, further comprising about 100 ppm by volume to about 1.5 percent by volume air.

[0059] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition further comprising a stabilizer.

[0060] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

[0061] Also disclosed herein, according to any of the preceding embodiments, is a composition wherein the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

[0062] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the stabilizer is present in an amount of about 0.001 to 1.0 weight percent based on the weight of the refrigerant.

[0063] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition further comprising at least one tracer.

[0064] Also disclosed herein, according to any of the preceding embodiments, is a composition wherein the at least one tracer is present in an amount of about 1.00 ppm to about 1000 ppm by weight.

[0065] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition wherein the at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

[0066] According to any of the foregoing embodiments, the at least one tracer is selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-227ea, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-12 Also disclosed herein are compositions selected from the group consisting of HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-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.

[0067] In another embodiment, disclosed herein is a refrigerant storage vessel containing a composition according to any of the previous embodiments, wherein the refrigerant comprises a gas phase and a liquid phase.

[0068] In another embodiment, also disclosed herein is a system for heating and cooling a passenger compartment of an electric vehicle, the system including an evaporator, a compressor, a condenser, and an expansion device, each operatively connected to perform a vapor-compression cycle, wherein a refrigerant composition of any of the preceding embodiments is circulated through each of the evaporator, the compressor, the condenser, and the expansion device.

[0069] Also disclosed herein are cooling and heating systems, according to any of the preceding embodiments, where the average temperature gradient is less than 4.0K, less than 3.0K, or less than 2.5K.

[0070] Also disclosed herein are cooling and heating systems that do not include a PTC heater, according to any of the aforementioned embodiments.

[0071] According to any of the aforementioned embodiments, cooling and heating systems that are not reversible cooling loops are also disclosed herein.

[0072] Also disclosed herein, in accordance with any of the foregoing embodiments, is a cooling and heating system further comprising a reheater operatively connected between the compressor and the condenser.

[0073] In another embodiment, also disclosed herein is a method for replacing HFO-1234yf in heating and cooling systems contained within an electric vehicle, the method comprising providing to the heating and cooling system any of the aforementioned compositions as a heat transfer fluid.

[0074] Also disclosed herein, according to any of the foregoing embodiments, is a method of replacing HFO-1234yf, where the refrigerant blend produces at least 20% higher volumetric capacity than HFO-1234yf alone when operated under the same set of conditions.

[0075] Also disclosed herein, according to any of the foregoing embodiments, is a method for replacing HFO-1234yf, wherein the refrigerant blend produces a COP that is equal to or greater than the COP of HFO-1234yf alone when operated under the same conditions.

[0076] In another embodiment, also disclosed herein is a method of servicing an electric vehicle heating and cooling system, comprising removing any used refrigerant from the system and charging the system with any of the aforementioned compositions.

[0077] In another embodiment, disclosed herein is the use of any of the preceding compositions as a heat transfer fluid in a system for heating and cooling the passenger compartment of an electric vehicle.

[0078] Various aspects and embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will be apparent from the following more detailed description of preferred embodiments, which illustrate, by way of example, the principles of the invention. [Brief description of the drawings]

[0079] [Figure 1] 1 illustrates a reversible cooling or heating loop system according to an embodiment. [Diagram 2] 1 illustrates a reversible cooling or heating loop system according to an embodiment. [Diagram 3] 1 illustrates a cooling or heating loop system according to an embodiment. [Figure 4] 1 illustrates a cooling or heating loop system according to an embodiment. [Diagram 5] 1 illustrates a cooling or heating loop system according to an embodiment. [Figure 6] 1 illustrates a cooling or heating system according to an embodiment. [Figure 7] 1 illustrates a cooling or heating system according to an embodiment. [Figure 8] 1 illustrates a cooling or heating system according to an embodiment. [Figure 9] 1 illustrates a cooling or heating system according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0080] definition As used herein, the term heat transfer composition or heat transfer fluid means a composition used to transport heat from a heat source to a heat sink.

[0081] A heat source is defined as any space, location, thing or object where it is desirable to add, transfer, move or remove heat. An example of a heat source in this embodiment is a vehicle passenger compartment requiring air conditioning.

[0082] A heat sink is defined as any space, place, thing or object that can absorb heat. An example of a heat sink in this embodiment is the passenger compartment of a vehicle that requires heating.

[0083] A heat transfer system is a system (or device) used to produce a heating or cooling effect at a specific location. A heat transfer system in this invention can refer to a heating or cooling system that provides heating or cooling to the passenger compartment of an automobile. This system is sometimes called a heat pump system and can be a reversible heating system or a reversible cooling system, or simply a heating and cooling system.

[0084] The heat transfer system in the present invention may further refer to a stationary heat pump system for a single-family home or large building. Furthermore, the heat transfer system may further refer to a stationary or mobile refrigeration system. The refrigeration system may be a low temperature refrigeration system or a medium temperature refrigeration system. The refrigeration system may further be a domestic refrigerator or freezer, or a commercial, such as a supermarket or convenience store, refrigeration system or freezer system.

[0085] The heat transfer fluid includes at least one refrigerant and at least one component selected from the group consisting of lubricants, stabilizers, tracers, UV dyes, and flame suppressants.

[0086] Volumetric capacity is the amount of heat absorbed or rejected divided by theoretical compressor displacement. The heat removed or absorbed is the enthalpy difference between the heat exchangers multiplied by the refrigerant mass flow rate. Theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., compressor suction density). More simply, volumetric capacity is the suction density multiplied by the heat exchanger enthalpy difference. Higher volumetric capacity allows the use of smaller compressors 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.

[0087] The coefficient of performance (COP) is the amount of heat absorbed or rejected divided by the energy input required for the cycle to operate (approximated by the compressor capacity). The COP is specific to the operating mode of the heat pump, hence the COP for heating or COP for cooling. The COP is directly related to the energy efficiency ratio (EER).

[0088] Subcooling refers to lowering the temperature of a liquid below its saturation point at a given pressure. The liquid saturation point is the temperature at which vapor completely condenses into a liquid. By cooling a liquid below its saturation temperature (or boiling point temperature), the net refrigeration effect can be increased. Subcooling thereby increases the refrigeration capacity and energy efficiency of the system. The amount of subcooling is the amount of cooling below the saturation temperature (in degrees).

[0089] Superheating refers to raising the temperature of a vapor above the saturation point of that vapor at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into a vapor. Superheating continues to heat the vapor to a hotter vapor at a given pressure. By heating the vapor above the saturation temperature (or dew point temperature), the net refrigeration effect can be increased. Superheating thereby increases the refrigeration capacity and energy efficiency of the system when it occurs in the evaporator. Superheating of the suction line does not add net refrigeration effect and can reduce efficiency and capacity. Superheat is the amount of heating above the saturation temperature (in degrees).

[0090] The temperature gradient (sometimes simply referred to as "gradient") is the absolute value of the difference between the start and end temperatures of the phase change process by the refrigerant in the condenser of a refrigerant system, excluding any subcooling or superheating. In the case of an evaporator, the gradient is the temperature difference between the dew point and the evaporator inlet. 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 or heat pump system, it is common to provide the average temperature gradient, which is the average of the temperature gradient in the evaporator and the temperature gradient of the condenser. Gradient is applicable to blended refrigerants, i.e., refrigerants composed of at least two components.

[0091] A small gradient is defined herein as an average gradient under heating and cooling conditions that is less than 4 K over the operating range of interest, more preferably less than 3 K over the operating range of interest, more preferably less than 2.5 K over the operating range of interest, and most preferably less than 2.0 K over the operating range of interest (e.g., a gradient in the range of from greater than 0 to less than about 2.0 K).

[0092] 2,3,3,3-Tetrafluoropropene (HFO-1234yf or R-1234yf) and 1,1-difluoroethane (HFC-152a or R-152a) are commercially available from Chemours™ (Wilmington, Del., USA). E-1,2-difluoroethylene (trans-1,2-difluoroethylene, HFO-1132E, or R-1132E) can be produced by methods known in the art, such as dehydrofluorination of 1,1,2-trifluoroethane, as described in US Patent Publication No. 20210070678(A1). Propane, cyclopropane, propylene, isobutane, and n-butane are commercially available from a number of chemical suppliers.

[0093] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover non-exclusive inclusions. For example, a composition, process, method, article, or device that includes recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or inherent in such composition, process, method, article, device, etc. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0094] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase closes the claim to including materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0095] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, ingredients, or elements have a substantial effect on the basic and novel characteristics of the claimed invention, particularly the manner of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0096] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description (unless otherwise expressly stated) should be interpreted to also include inventions using the terms "consisting essentially of" or "consisting of," including, for example, compositions consisting essentially of or consisting of.

[0097] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0098] Refrigerant Blend Global Warming Potential (GWP) is an index for estimating the relative global warming contribution due to the atmospheric emission of one kilogram of a particular greenhouse gas compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for various time horizons and indicates the impact of a given gas's atmospheric lifetime. The GWP for a 100-year time horizon is the commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. The United Nations Intergovernmental Panel on Climate Change (IPCC) provides vetted values ​​of refrigerant GWP in its official assessment reports (AR). The fourth assessment report is designated as AR4 and the fifth assessment report is designated as AR5. The GWP values ​​reported herein for the refrigerant blends of the present invention refer to the AR5 values ​​of the compounds listed herein.

[0099] Ozone depletion potential (ODP) is a number that refers to the amount of ozone destruction caused by a substance. ODP is the ratio of a chemical's effect 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 causes ozone depletion. Further, CFC-11 is defined as having an ODP of 1.0. Other CFCs and hydrofluorochlorocarbons (HCFCs) have ODPs ranging from 0.01 to 1.0. The hydrofluorocarbons (HFCs) and hydrofluoro-olefins (HFOs) described herein have an ODP of zero because they do not contain chlorine, bromine, or iodine, species known to contribute to ozone decomposition and destruction.

[0100] The composition comprises a refrigerant blend consisting essentially of 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2-difluoroethylene (HFO-1132E), at least one hydrocarbon selected from the group consisting of propane, cyclopropane, propylene, isobutane, and n-butane, and optionally 1,1-difluoroethane (HFC-152a). Suitable amounts of HFO-1234yf in the refrigerant blend include, but are not limited to, amounts of about 51 weight percent to 90 weight percent, or about 56 weight percent to 90 weight percent, or about 58 weight percent to 90 weight percent, or about 60 weight percent to 90 weight percent, or about 61 weight percent to 90 weight percent, or about 77 weight percent to 90 weight percent, or about 84 weight percent to 90 weight percent, or about 85 weight percent to 90 weight percent, or about 77 weight percent to 88 weight percent, or about 82 weight percent to 88 weight percent based on the total refrigerant blend composition. Suitable amounts of HFO-1132E in the refrigerant blend include, but are not limited to, amounts of about 3 weight percent to 25 weight percent, or about 8 weight percent to 25 weight percent, or about 3 weight percent to 20 weight percent, or about 4 weight percent to 18 weight percent, or about 3 weight percent to 18 weight percent, or about 8 weight percent to 20 weight percent, or about 6 weight percent to 19 weight percent, or about 11 weight percent to 19 weight percent, or about 6 weight percent to 12 weight percent, or about 7 weight percent to 12 weight percent, or about 8 weight percent to 13 weight percent, or about 9 weight percent to 13 weight percent, or about 11 weight percent to 14 weight percent based on the total refrigerant blend composition.Suitable amounts of hydrocarbons in the refrigerant blend include, but are not limited to, amounts of about 1 weight percent to 4 weight percent, or about 1 weight percent to 3 weight percent, or about 1 weight percent to 2 weight percent, or about 2 weight percent to 4 weight percent, or about 3 weight percent to 4 weight percent based on the total refrigerant blend composition.Suitable amounts of HFC-152a in the refrigerant blend include, but are not limited to, amounts from about 0 weight percent to about 20 weight percent, or from about 1 weight percent to 20 weight percent, or from about 1 weight percent to 18 weight percent, or from about 3 weight percent to 16 weight percent, or from about 5 weight percent to 14 weight percent, or from about 7 weight percent to 12 weight percent, or from about 10 weight percent to 20 weight percent, or from about 2 weight percent to 10 weight percent, or from about 4 weight percent to 12 weight percent, or from about 6 weight percent to 10 weight percent, or from about 8 weight percent to 14 weight percent based on the total refrigerant blend composition.

[0101] In one embodiment, the composition comprises a refrigerant blend including about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane. In another embodiment, the refrigerant blend consists essentially of about 58-90 weight percent HFO-1234yf, about 3-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propane. Alternatively, the refrigerant blend consists essentially of about 58-89 weight percent HFO-1234yf, about 6-18 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent propane. Alternatively, the refrigerant blend consists essentially of about 84-89 weight percent HFO-1234yf, about 8-13 weight percent HFO-1132E, and about 1-4 weight percent propane. In another embodiment, the refrigerant blend consists essentially of about 61-90 weight percent HFO-1234yf, about 4-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane. Alternatively, the refrigerant blend consists essentially of about 61-89 weight percent HFO-1234yf, about 5-15 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane. Alternatively, the refrigerant blend consists essentially of about 84-90 weight percent HFO-1234yf, about 7-12 weight percent HFO-1132E, and about 1-4 weight percent cyclopropane. In another embodiment, the refrigerant blend consists essentially of about 60-90 weight percent HFO-1234yf, about 3-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propylene.Alternatively, the refrigerant blend consists essentially of about 60-88 weight percent HFO-1234yf, about 4-17 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent propylene. Alternatively, the refrigerant blend consists essentially of about 85-90 weight percent HFO-1234yf, about 6-12 weight percent HFO-1132E, and about 1-4 weight percent propylene. In another embodiment, the refrigerant blend consists essentially of about 51-90 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent isobutane. Alternatively, the refrigerant blend consists essentially of about 51-88 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 1-20 weight percent HFC-152a, and about 1-4 weight percent isobutane. Alternatively, the refrigerant blend consists essentially of about 77-88 weight percent HFO-1234yf, about 11-19 weight percent HFO-1132E, and about 1-4 weight percent isobutane. In another embodiment, the refrigerant blend consists essentially of about 56-90 weight percent HFO-1234yf, about 8-20 weight percent HFC-32, about 0-20 weight percent HFC-152a, and about 1-4 weight percent n-butane. Alternatively, the refrigerant blend consists essentially of about 56-87 weight percent HFO-1234yf, about 8-20 weight percent HFC-32, about 1-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.Alternatively, the refrigerant blend consists essentially of about 82-88 weight percent HFO-1234yf, about 11-14 weight percent HFC-32, and about 1-4 weight percent n-butane.

[0102] In some embodiments, the refrigerant blend does not contain HFC-152a. In one embodiment, the refrigerant blend consists essentially of about 77-90 weight percent HFO-1234yf, about 6-19 weight percent HFO-1132E, and about 1-4 weight percent of at least one hydrocarbon selected from the group consisting of propane, cyclopropane, propylene, isobutane, and n-butane. In another embodiment, the refrigerant blend consists essentially of about 84-89 weight percent HFO-1234yf, about 8-13 weight percent HFO-1132E, and about 1-4 weight percent propane. In another embodiment, the refrigerant blend consists essentially of about 84-90 weight percent HFO-1234yf, about 7-12 weight percent HFO-1132E, and about 1-4 weight percent cyclopropane. In another embodiment, the refrigerant blend consists essentially of about 85-90 weight percent HFO-1234yf, about 6-12 weight percent HFO-1132E, and about 1-4 weight percent propylene. In another embodiment, the refrigerant blend consists essentially of about 77-88 weight percent HFO-1234yf, about 11-19 weight percent HFO-1132E, and about 1-4 weight percent isobutane. In another embodiment, the refrigerant blend consists essentially of about 82-88 weight percent HFO-1234yf, about 11-14 weight percent HFO-1132E, and about 1-4 weight percent n-butane.

[0103] The refrigerant blends have zero ODP and low GWP, or GWP≦30, or preferably GWP≦20, or more preferably GWP≦10 (according to AR5 values). Table 1 shown below is a summary table showing refrigerants and GWP according to the Fifth Assessment Report conducted by the Intergovernmental Panel on Climate Change (IPCC) for 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoromethane (HFC-152a). The GWP values ​​for propylene and cyclopropane were taken from Domanski, et al., "Low-GWP Refrigerants for Medium and High-Pressure Applications", Int. J. Refrigeration, 2017, 84, 198-209. The GWP values ​​for HFO-1132E, propane, isobutane, and n-butane are estimates (see Table 1 below).

[0104] For 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., weight %) of each component in the blend. Table 1 provides the GWP values ​​for each component of the refrigerant blends of the present invention, along with two example GWP values ​​for refrigerant blends.

[0105] [Table 1]

[0106] The refrigerant blends described herein operate in heat exchangers, i.e., evaporators and / or condensers, with low temperature gradients, thus limiting compositional fractionation in operation to provide efficient and consistent performance for cooling and heating.

[0107] In some embodiments, the refrigerant blend provides an average temperature gradient of less than 4 K over the operating range of interest, more preferably a small gradient is less than 3 K over the operating range of interest, more preferably less than 2.5 K over the operating range of interest, and most preferably less than 2.0 K over the operating range of interest (e.g., a gradient in the range from greater than 0 to less than about 2.0 K). This effect is observed when any of the aforementioned refrigerant blends are used in a heat pump.

[0108] Refrigerant Additives The compositions of the present invention containing the refrigerant blends may further contain a lubricant and may be used as heat transfer fluids. The compositions of the present invention containing the refrigerant blends and lubricants of the present invention may contain additives such as stabilizers, leak detection materials (e.g., UV dyes), tracers, and other beneficial additives.

[0109] The lubricant selected for this composition preferably has sufficient solubility in the refrigerant blend to ensure that the lubricant can be 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 the 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.

[0110] Lubricants of the present invention can include polyalkylene glycol lubricants (PAGs), polyol ester lubricants (POEs), polyvinyl ether lubricants (PVEs), as well as poly-α-olefins (PAOs), alkylbenzenes, mineral oils, fluorinated polyethers, and even silicone lubricants.

[0111] Preferred lubricants may be one or more polyalkylene glycol type lubricants (PAG), one or more polyol ester type lubricants (POE), one or more poly-alpha-olefins (PAO), or one or more polyvinyl ether lubricants. In addition, the lubricant for combination with the refrigerant blend of the present invention may be any mixture of PAG, POE, and / or PVE lubricants.

[0112] Polyalkylene glycol (PAG) oil may be a homopolymer or copolymer of two or more oxypropylene groups. PAG oil may be uncapped, capped at one end, or capped at both ends. Examples of commercially available PAG oils include, but are not limited to, ND-8, Castorl PAG 46, Castrol PAG 100, Castrol PAG 150, Daphne Hermetic PAG PL, and Daphne Hermetic PAG PR.

[0113] The PAG lubricant properties using them in this invention are 10 10 These include a volume resistivity of greater than Ω-m, a surface tension of about 0.02 N / m to about 0.04 N / m at 20° C., a kinematic viscosity of about 20 cSt to about 500 cSt at 40° C., a dielectric breakdown voltage of at least 25 kV, and a hydroxyl number of up to 0.1 mg KOH / g.

[0114] In one embodiment, the lubricant comprises a PAG and is stable when exposed to the composition of the invention where the refrigerant blend composition has a Total Acid Number (TAN), mg KOH / g, 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 about 0.4. In an aspect of this embodiment, the lubricant comprises a PAG and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane. In another embodiment, the lubricant includes a PAG and the refrigerant consists essentially of about 58-90 weight percent HFO-1234yf, about 3-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propane. In another embodiment, the lubricant includes a PAG and the refrigerant consists essentially of about 61-90 weight percent HFO-1234yf, about 4-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane. In another embodiment, the lubricant includes a PAG and the refrigerant consists essentially of about 60-90 weight percent HFO-1234yf, about 3-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propylene. In another embodiment, the lubricant includes a PAG and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent isobutane.In another embodiment, the lubricant includes a PAG and the refrigerant consists essentially of about 56-90 weight percent HFO-1234yf, about 8-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.And in additional embodiments, the lubricant comprises a PAG and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 2-4 weight percent. And in additional embodiments, the lubricant comprises a PAG and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 3-4 weight percent. And in additional embodiments, the lubricant comprises a PAG and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 1-3 weight percent. And in further aspects, the refrigerant composition further comprises greater than 0 weight percent to less than 1 weight percent of an additional compound.

[0115] Preferred lubricants may be one or more polyol ester type lubricants (POE) or one or more polyvinyl ether lubricants. POE lubricants are typically formed by the chemical reaction (esterification) of a carboxylic acid or mixture of carboxylic acids with an alcohol or mixture of alcohols.

[0116] In one embodiment, polyol esters, as used herein, include esters of diols or polyols having from about 3 to 20 hydroxyl groups and carboxylic acids (or fatty acids) having from about 1 to 24 carbon atoms, preferably used as polyols. Esters that can be used as base oils are described in European Patent Application No. 2 727 980(A1), published pursuant to Article 153(4), which is incorporated herein by reference. Examples of the diol 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.

[0117] Examples of the polyols include polyhydric alcohols such as trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerin, polyglycerin (glycerin dimer to decamer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol-glycerin condensates, adonitol, arabitol, xylitol, mannitol, and the like; polysaccharides such as, in particular, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, melezitose; partial etherification products thereof, and methyl glucoside, and the like. 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.

[0118] The number of carbon atoms of the 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 the refrigerant, fatty acids having 18 or less carbon atoms are preferred, fatty acids having 12 or less carbon atoms are more preferred, and fatty acids having 9 or less carbon atoms are even more preferred. In one embodiment, the carboxylic acid has 2 to 18 carbon atoms.

[0119] In addition, the fatty acid may be either a straight-chain fatty acid or a branched-chain fatty acid, and from the viewpoint of lubrication properties, the straight-chain fatty acid is preferred, while from the viewpoint of hydrolysis stability, the 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 fatty acid 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, icosanoic acid, oleic acid, and the like; and the so-called neo acid, in which a carboxylic acid group is bonded to a quaternary carbon atom. More specifically, preferred examples thereof 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, 3,5,5-trimethylhexanoic acid, etc. Incidentally, the polyol ester may be a partial ester in which the hydroxyl groups of the polyol remain not completely esterified; a complete ester in which all the hydroxyl groups are esterified; or a mixture of a partial ester and a complete ester, and a complete ester may be preferred in some cases.

[0120] In the polyol ester, from the viewpoint of better hydrolytic stability, esters of hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol) and the like are more preferred, and esters of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, or pentaerythritol are even more preferred; from the viewpoint of particularly good compatibility with refrigerants and hydrolytic stability, esters of pentaerythritol are most preferred.

[0121] Specific preferred examples of polyol esters include diesters of neopentyl glycol and 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 and 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 trimethylolpropane and 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 one or more fatty acids selected from methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; triesters of trimethylolbutane and 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 and 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, the ester of two or more fatty acids may be a mixture of two or more esters of one fatty acid and a polyol, and an ester of two or more mixed fatty acids and a polyol. In particular, the ester of a mixed fatty acid and a polyol is excellent in low-temperature properties and compatibility with refrigerants.

[0122] POE lubricants used for electric vehicle air conditioning applications may have a kinematic viscosity (measured at 40°C according to ASTM D445) of 20-500 cSt or 75-110 cSt, ideally about 80 cSt-100 cSt, most specifically 85 cSt-95 cSt. However, without wishing to limit the invention, it should be noted that other lubricant viscosities may be included depending on the needs of the electric vehicle heat pump compressor. Suitable characteristics of automotive POE type lubricants for use with the compositions of the present invention are listed below.

[0123] [Table 2]

[0124] In one embodiment, the lubricant comprises POE, the POE being stable upon exposure to the composition of the present invention, and the refrigerant composition has an F-ion amount of less than about 500 ppm, in some cases greater than 0 ppm to less than 500 ppm, greater than 0 ppm to less than 100 ppm, and in some cases greater than 0 ppm to less than 50 ppm. In one aspect of this embodiment, the refrigerant is selected from about 51-90 weight percent, or about 56-90 weight percent, or about 58-90 weight percent, or about 60-90 weight percent, or about 61-90 weight percent, or about 77-90 weight percent, or about 84-90 weight percent, or about 85-90 weight percent, or about 77-88 weight percent, or about 82-88 weight percent HFO-1234yf and about 3-25 weight percent, or about 3-20 weight percent, or about 4-18 weight percent, or about 3-18 weight percent, or about 8-25 weight percent, or about 11-19 weight percent, or about 8-13 weight percent, or about 7-12 weight percent, or about 6-18 weight percent, or about 11-14 weight percent HFO-1234yf. 100% HFO-1132E, about 1-4 weight percent, or about 1-3 weight percent, or about 1-2 weight percent, or about 2-4 weight percent, or about 2-3 weight percent, or about 3-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and about 0-20 weight percent, or about 1-20 weight percent, or about 1-18 weight percent, or about 3-16 weight percent, or about 5-14 weight percent, or about 7-12 weight percent, or about 10-20 weight percent, or about 2-10 weight percent, or about 4-12 weight percent, or about 6-10 weight percent, or about 8-14 weight percent of HFC-152a. And in a further embodiment, the refrigerant composition further comprises greater than 0 and less than 1 weight percent of an additional compound.

[0125] In one embodiment, the lubricant comprises POE and is stable when exposed to the composition of the present invention, where the refrigerant blend composition has a Total Acid Number (TAN), mg KOH / g, 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 about 0.4. In an aspect of this embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane. In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 58-90 weight percent HFO-1234yf, about 3-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propane. In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 61-90 weight percent HFO-1234yf, about 4-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane. In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 60-90 weight percent HFO-1234yf, about 3-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propylene. In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent isobutane.In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 56-90 weight percent HFO-1234yf, about 8-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.And in additional embodiments, the lubricant comprises POE and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 2-4 weight percent. And in additional embodiments, the lubricant comprises POE and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 3-4 weight percent. And in additional embodiments, the lubricant comprises POE and the refrigerant consists essentially of any of the aforementioned compositions, wherein the hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane is present at about 1-3 weight percent. And in a further aspect, the refrigerant composition further comprises from greater than about 0 weight percent to less than about 1 weight percent of an additional compound.

[0126] In another embodiment, PVE lubricants may be included as lubricants in the compositions of the present invention. Without intending to limit the scope of the present invention in any way, in an embodiment of the present invention, the polyvinyl ether oil includes those taught in the literature, such as those described in U.S. Patents 5,399,631 and 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: -[C(R1,R2)-C(R3,-R4)]- Equation 1 wherein R1, R2, R3, and R4 are independently selected from hydrogen and a hydrocarbon, which 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. -[CH2-CH(-O-R4)]- Formula 2

[0127] In another embodiment of the present invention, the polyvinyl ether oil is composed of structural units of the type shown by formula 3: -[CH2-CH(-O-R5)] m -[CH2-CH(-O-R6)] n formula 3 wherein R5 and R6 are independently selected from hydrogen and a hydrocarbon, and m and n are integers.

[0128] In one embodiment, the polyvinyl ether oil comprises a copolymer of the following two units:

[0129] [ka]

[0130] The lubricant properties (viscosity, refrigerant solubility, and miscibility with the refrigerant) can be adjusted by varying the m / n ratio and the sum of m+n. In another embodiment, the PVE lubricant is one that is 50 to 95 weight percent unit 1.

[0131] In one embodiment, the lubricant comprises a PVE and is stable when exposed to a composition of the invention where the refrigerant blend composition has a Total Acid Number (TAN), mg KOH / g, 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 about 0.4. In an aspect of this embodiment, the lubricant comprises a PVE and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane. In another embodiment, the lubricant includes a PVE and the refrigerant consists essentially of about 58-90 weight percent HFO-1234yf, about 3-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propane. In another embodiment, the lubricant includes a PVE and the refrigerant consists essentially of about 61-90 weight percent HFO-1234yf, about 4-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent cyclopropane. In another embodiment, the lubricant includes a PVE and the refrigerant consists essentially of about 60-90 weight percent HFO-1234yf, about 3-18 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent propylene. In another embodiment, the lubricant comprises a PVE and the refrigerant consists essentially of about 51-90 weight percent HFO-1234yf, about 8-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent isobutane.In another embodiment, the lubricant comprises a PVE and the refrigerant consists essentially of about 56-90 weight percent HFO-1234yf, about 8-20 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent n-butane.And in additional embodiments, the lubricant comprises a PVE and the refrigerant consists essentially of any of the aforementioned compositions, with a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane present at about 2-4 weight percent. And in additional embodiments, the lubricant comprises a PVE and the refrigerant consists essentially of any of the aforementioned compositions, with a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane present at about 3-4 weight percent. In additional embodiments, the lubricant comprises a PVE and the refrigerant consists essentially of any of the aforementioned compositions, with a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane present at about 1-2 weight percent. And in further aspects, the refrigerant composition further comprises greater than 0 weight percent and less than 1 weight percent of an additional compound.

[0132] As with POE lubricants, similar properties and characteristics may be required for the use of PVE lubricants in the compositions described herein, particularly for use in automotive cooling and heating systems.

[0133] In a preferred embodiment, the lubricant is soluble in the refrigerant at temperatures within the range of about −40° C. to about 80° C., more preferably about −30° C. to about 40° C., and even more specifically −25° C. to 40° C. In another embodiment, high temperature insolubility is not preferred, since attempting to maintain the lubricant within the compressor is not a priority.

[0134] The amount of lubricant can range from about 1 to about 20 weight percent, from about 1 to about 7 weight percent, and in some cases from about 1 to about 3 weight percent.

[0135] To limit hydrolysis of the lubricating oil, the water concentration in the heating / cooling systems of electric type vehicles must be controlled, and therefore the lubricant in this embodiment must have a low water content, typically less than 100 ppm water by weight.

[0136] 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 within the range of about -35°C to about 100°C, more preferably about -35°C to about 50°C, and even more specifically, at temperatures between -30°C and 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.

[0137] Of particular note is the 10 10 PAG, POE, PAO, and PVE lubricants having a volume resistivity of greater than Ω-m; a surface tension of about 0.02 N / m to about 0.04 N / m at 20° C.; a kinematic viscosity of about 20 cSt to about 500 cSt, or about 50 cSt to about 200 cSt, or about 75 cSt to about 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.

[0138] Due to the presence of double bonds, HFO type refrigerants can be thermally unstable and decompose under extreme use, handling or storage conditions. It may therefore be advantageous to add stabilizers to HFO type refrigerants. In particular, stabilizers may include nitromethane, ascorbic acid, terephthalic acid; azoles such as tolutriazole or benzotriazole; phenolic compounds such as tocopherol; hydroquinone, t-butylhydroquinone, 2,6-di-tertbutyl-4-methylphenol; epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether; cyclic monoterpenes; terpenes such as d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene or β-pinene; phosphites, phosphates, phosphonates, thiols and lactones. Examples of suitable stabilizers are disclosed in WO 2019213004, WO 2020222864, and WO 2020222865, the disclosures of which are incorporated herein by reference.

[0139] The blend may or may not contain a stabilizer, depending on the requirements of the system it is being used in. If the refrigerant blend contains a stabilizer, it may contain any amount of from 0.001% to 1% by weight or less, preferably from about 0.01 to about 0.5 weight percent, and more preferably from about 0.01 to about 0.3 weight percent of any of the stabilizers listed above, in most cases preferably d-limonene.

[0140] In some embodiments, the compositions disclosed herein may contain a tracer compound or tracer. The tracer may include two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million (ppm) to about 1000 ppm by weight 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.

[0141] A tracer may be present in the composition of the present invention in a predetermined amount to allow detection of any dilution, contamination, or other change of the composition. The presence of a particular compound in the composition may indicate by which method or process one of the components was produced. A specified amount of a 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 is present in the composition at a level that is unlikely to affect the performance of the refrigerant component of the composition.

[0142] The tracer compound may be a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, and combinations thereof. Examples of tracer compounds include HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-250 (pentafluoroethane), HFC-260 (pentafluoroethane), HFC-270 (pentafluoroethane), HFC-272 (pentafluoroethane), HFC-274 (pentafluoroethane), HFC-276 (pentafluoroethane), HFC-278 (pentafluoroethane), HFC-279 (pentafluoroethane), HFC-280 (pentafluoroethane), HFC-281 (pentafluoroethane), HFC-282 (pentafluoroethane), HFC-283 (pentafluoroethane), HFC-284 (pentafluoroethane), HFC-285 (pentafluoroethane), HFC-286 (pentafluoroethane), HFC-287 (pentafluoroethane), HFC-288 (pentafluoroethane), HFC-289 (pentafluoroethane), HFC-300 (pentafluoroethane), HFC-301 (pentafluoroethane), HFC-302 (pentafluoroethane), HFC-303 (pentafluoroethane), HFC-304 (pentafluoroethane), HFC-305 (pentafluoroethane), HFC-306 (pentafluoroethane), HFC-307 (pentafluoroethane), HFC 36ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1-trifluoro-2-methylpropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane), CFC-12 (dichlorodifluoromethane), CFC-11 (trifluorobutane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (1,1-dichloro-1,2,2,2-tetrafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1-difluoroethane), HCFC-151a (1-chloro-1-fluoroethane), HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (fluoroethene), HCFO-1130 (1,2-dichloroethene), HCFO-1130a (1,1-dichloroethene), HCFO-1131 (1-chloro-2-fluoroethene), HCFO-1122 (2-chloro-1,1-difluoroethene), HFO-1123 (1,1,2-trifluoroethene), HFO-1234ye (1,2,3,3-tetrafluoropropene) , 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.

[0143] Flammability of refrigerant blends Flammability is a term used to mean 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 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.

[0144] To be classified as non-flammable (Class 1, no flame spread) per ANSI / ASHRAE Standard 34 or ISO 817 ISO 817:2014(en) Refrigerants-Designation and Safety Classification, a refrigerant must meet the conditions 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 during a leak scenario as defined by ANSI / ASHRAE Standard 34:2019 or ISO 817:2014(en) Refrigerants-Designation and Safety Classification.

[0145] For a refrigerant blend to be classified as low flammable (Class 2L) by ANSI / ASHRAE (American Society of Heating, Refrigeration and Air-Conditioning Engineers), the worst case of formulation (WCF) and worst case of fractionation for flammability (WCFF) must be determined based on manufacturing tolerances and vapor breakthrough behavior. To be classified as 2L, mildly flammable, the WCF and WCFF must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa) and have an LFL > 0.0062 lb / ft 3 (0.10kg / m 3 ) and 2) have a maximum burning velocity of ≦3.9 in. / s (10 cm / s) 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).

[0146] ASHRAE Standard 34 provides a methodology for calculating the heat of combustion of refrigerant blends using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with sufficient oxygen for the stoichiometric reaction.

[0147] When the HFO-1234yf, HFO-1132E, hydrocarbon, and optionally HFC-152a components are blended in certain ratios, the resulting blend may have Class 2 or Class 2L flammability as defined by ANSI / ASHRAE Standard 34 and ISO 817. Class 2 and Class 2L flammability may be managed in automotive heating / cooling systems.

[0148] In embodiments, the refrigerant blend comprises 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2-difluoroethylene (HFO-1132E), at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and optionally 1,1-difluoroethane (HFC-152a). In some embodiments, the refrigerant blend may comprise, consist essentially of, or consist of 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2-difluoroethylene (HFO-1132E), at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and optionally 1,1-difluoroethane (HFC-152a).In some embodiments, the refrigerant blend is about 51 weight percent to 90 weight percent, or about 56 weight percent to 90 weight percent, or about 58 weight percent to 90 weight percent, or about 60 weight percent to 90 weight percent, or about 61 weight percent to 90 weight percent, or about 77 weight percent to 90 weight percent, or about 84 weight percent to 90 weight percent, or about 85 weight percent to 90 weight percent, or about 77 weight percent to 88 weight percent, or about 82 weight percent or about 88 weight percent HFO-1234yf and about 3 weight percent to about 25 weight percent, or about 3 weight percent to about 20 weight percent, or about 8 weight percent to about 25 weight percent, or about 8 weight percent to about 20 weight percent, or about 4 weight percent to about 19 weight percent, or about 6 weight percent to about 19 weight percent, or about 11 weight percent to about 19 weight percent, or about 4 weight percent to about 19 weight percent, or about 3 weight percent to about 18 weight percent, or about 4 weight percent from about 1 weight percent to about 17 weight percent, or from about 6 weight percent to about 12 weight percent, or from about 11 weight percent to about 14 weight percent HFO-1132E, from about 1 weight percent to about 4 weight percent, or from about 1 weight percent to about 3 weight percent, or from about 1 weight percent to about 2 weight percent, or from about 2 weight percent to about 4 weight percent, or from about 2 weight percent to about 3 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and from about 0 weight percent to about 20 weight percent of a cyclopropane-based hydrocarbon. or about 1 weight percent to 18 weight percent, or about 3 weight percent to 16 weight percent, or about 5 weight percent to 14 weight percent, or about 7 weight percent to 12 weight percent, or about 10 weight percent to 20 weight percent, or about 2 weight percent to 10 weight percent, or about 4 weight percent to 12 weight percent, or about 6 weight percent to 10 weight percent, or about 8 weight percent to 14 weight percent HFC-152a.

[0149] In an embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, HFO-1234ze, CFC-12, HCFC-124, 3,3,3-trifluoropropyne, HCC-1140, HFC-1225ye, HFO-1225zc, HFC-134a, HFO-1243zf, and HCFO-1131.

[0150] In one embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional 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.

[0151] In an embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional compound selected from the group consisting of HFO-1132Z, HFO-1132a, HCFO-1131a, HCFC-142a, CFO-1122a, HFO-1123, HCFC-132, CFO-1113, and ethane.

[0152] In one embodiment, any of the foregoing refrigerant compositions can further comprise any combination of compounds from these lists, with the total amount of additional compounds comprising greater than 0 weight percent and less than 1 weight percent.

[0153] In one embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional compound selected from the group consisting of HFC-143a, HCC-40, HFC-161, and HCFC-151a. Alternatively, the composition may further comprise HFC-143a, HCC-40, HFC-161, and HCFC-151a.

[0154] In one embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional compound selected from the group consisting of HFO-1243zf, HCFC-151a, HFO-1132Z, and HFC-254eb. Alternatively, the composition may comprise HFO-1243zf, HCFC-151a, HFO-1132Z, and HFC-254eb.

[0155] In one embodiment, any of the foregoing refrigerant compositions may further comprise at least one additional compound selected from the group consisting of HFO-1243zf, 3,3,3-trifluoropropyne, HFC-143a, HCC-40, HFO-1132Z, and HCFC-151a. Alternatively, the composition may further comprise HFO-1243zf, HFC-143a, HCC-40, HFO-1132a, and HCFC-151a.

[0156] The amount of additional compounds present in any of the foregoing refrigerant compositions may be greater than 0 ppm and less than 5,000 ppm, particularly in the range of from about 5 to about 1,000 ppm, from about 5 to about 500 ppm, and from about 1 to about 100 ppm.

[0157] In one embodiment, the amount of additional compounds present in any of the foregoing refrigerant compositions may be greater than 0 to less than 1 weight percent, preferably less than 0.5 weight percent, or more preferably less than 0.1 weight percent of the refrigerant composition.

[0158] In an embodiment, any of the aforementioned refrigerant compositions may further comprise additional compounds including at least one of oligomers and / or homopolymers of HFO-1234yf. The amount may range from greater than 0 ppm to about 100 ppm, and in some cases from about 2 ppm to about 100 ppm. In aspects of this embodiment, the refrigerant comprises about 67-91 weight percent HFO-1234yf, about 1-9 weight percent or about 2-7 weight percent or 4-8 weight percent or 5-9 weight percent HFC-32, about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and about 0-20 weight percent HFC-152a, and in further aspects, the refrigerant composition further comprises, in addition to the oligomers and homopolymers, greater than about 0 weight percent and less than 1 weight percent, preferably less than 0.5 weight percent, and even more preferably less than 0.1 weight percent of additional compounds.

[0159] Another embodiment of the invention relates to storing any of the aforementioned compositions in a gas and / or liquid phase in a sealed container. The water concentration in the gas and / or liquid phase in the sealed container ranges from about 0.1 to 200 ppm by weight. The oxygen concentration in the gas and / or liquid phase in the sealed container ranges from about 10 ppm by volume to about 0.35 percent by volume at about 25° C. The air concentration in the gas and / or liquid phase in the sealed container ranges from about 100 ppm by volume to about 1.5 percent by volume.

[0160] The container for storing the aforementioned composition can be constructed of any suitable material and design that can seal the composition while maintaining the gas and liquid phases. Examples of suitable containers include pressure vessels such as tanks, filled cylinders, and secondary filled cylinders. The container can be constructed from any suitable material, such as carbon steel, manganese steel, chromium-molybdenum steel, especially low alloy steel, stainless steel, and in some cases aluminum alloy.

[0161] The compositions of the present invention can be prepared by any convenient method for combining the desired amounts of individual components. A preferred method is to weigh the desired amounts of components and then combine the components in a suitable vessel. Agitation may be used if desired. In another embodiment, any of the aforementioned refrigerant compositions can be prepared by blending at least one of HFO-1234yf, HFO-1132E, a hydrocarbon, optionally HFC-152a, and optionally additional compounds.

[0162] In further embodiments, compositions may be prepared from recycled or regenerated refrigerants. One or more of the components may be recycled or regenerated by removing contaminants such as air, water, or residues that may include lubricants or particulate residues from the system components. Means for removing contaminants may vary widely, but may include distillation, decantation, filtration, and / or drying with the use of molecular sieves or other absorbents. The recycled or regenerated components may then be combined with other components as described above.

[0163] In an embodiment of the present invention, a system for heating and cooling the passenger compartment of an electric vehicle is provided. The system includes an evaporator, a compressor, a condenser, and an expansion device, each operatively connected to perform a vapor compression cycle, and the system contains any of the aforementioned compositions including a refrigerant blend consisting essentially of HFC-1234yf, HFO-1132E, at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane, and optionally HFC-152a. The average temperature gradient in the system of the present invention is less than 4.0K, preferably less than 3.0K, or more preferably less than 2.5K. The system is preferably a heat pump. Due to the excellent performance of the heat pump system in both cooling and heating the passenger compartment of an electric vehicle, the system may no longer require a positive temperature coefficient (PTC) heater.

[0164] The refrigerant blends can be used in a variety of heating and cooling systems. In some embodiments, a reversing valve is used and the same loop is used for cooling and heating. In other embodiments, an air-side bypass or refrigerant valve / system design modification can achieve the same effect as a reversible cycle without a reversing valve.

[0165] 1, a 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 of the loop 110 and the air flow generated by the fan pass through the first heat exchanger 120.

[0166] In cooling mode, the refrigerant started by the compressor 150 passes through the valve 160, through the heat exchanger 120 which acts as a condenser, i.e. it gives up its thermal energy to the outside, then through the pressure regulator 130 and then through the heat exchanger 140 which acts as an evaporator, thereby cooling the air flow intended to be blown into the passenger compartment of the vehicle.

[0167] In heat pump mode, the direction of 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 a flow of air that is directed into the passenger compartment of the vehicle.

[0168] Additional heat transfer loops may be connected to the heat pump system and allow for the transfer of heat away from the motor or battery by absorbing or rejecting heat in heat exchangers 120 and / or 140, thus providing thermal management of those sections of the vehicle as well as cooling and heating for the passenger compartment.

[0169] In the embodiment of Fig. 2, a refrigeration system 300 with 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 manner in which the heat exchangers 320 and 340 work is the same as in the first embodiment shown in Fig. 1. Two fluid / liquid heat exchangers 370 and 380 are installed both in the refrigeration loop circuit 310 and in the engine cooling circuit or the secondary glycol-water circuit. The installation of the fluid / liquid heat exchangers without passing an intermediate gaseous fluid (e.g. air) contributes to an improved heat exchange compared to an air / fluid heat exchanger.

[0170] In one embodiment, in a system for heating and cooling a passenger compartment of an electric vehicle, the system further comprises a reheater operably connected between the compressor and the condenser to reduce humidity within the passenger compartment during a cooling mode.

[0171] In the embodiment of FIG. 3, a refrigeration system 400 having a refrigeration loop 410 includes 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 reheat) 470. In a 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 to 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 subcooled 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. The refrigerant is evaporated in the second heat exchanger 440 by the use of a second fan 490, which is external to the cooling loop. The air passing through the second heat exchanger 440 is cooled below the air dew point temperature. This causes the moisture in the air to partially condense, thereby reducing the absolute humidity of the air. The air then passes through the third heat exchanger 470, which transfers heat to the air, raising the air temperature above the dew point and reducing the relative humidity of the air, which is then supplied to the passenger compartment. This process of cooling below the dew point temperature to remove moisture, and then reheating above the dew point temperature allows for cooling and relative humidity control of the vehicle cabin. In the heating mode, the three-way valve 460 is adjusted to prevent the flow of refrigerant to the first heat exchanger 420, and all vehicle cabin heating is achieved using the third heat exchanger 470 in the heat pump configuration described in FIG. 1.

[0172] In the embodiment of FIG. 4, an air conditioning (AC) and heat pump (HP) system 500 can achieve 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 an air conditioning only mode, an HP control valve 530 upstream of the heat pump condenser 540 is closed and refrigerant flows from the compressor 550 to the air-cooled AC condenser 560, through an AC expansion valve 570, and into the AC evaporator 580 to provide cooling to the passenger compartment. From the AC evaporator 580, the refrigerant will return to the compressor 550. In a heat pump only mode, an AC control valve 535 upstream of the AC condenser 560 is closed and refrigerant flows from the compressor 550 to the HP condenser 540 to provide heating to the passenger compartment. From the HP condenser 540, the refrigerant will flow through an HP expansion valve 575 to the HP evaporator 585. The separate humidity control modes can be achieved by directing a portion of the compressor discharge gas to the AC circuit 510 and a remaining portion to the HP circuit 520.

[0173] In the embodiment of FIG. 5, a system 600 for heating, cooling, or both for a vehicle passenger compartment or other vehicle load can be realized. The system 600 includes an AC circuit 610 and a water-cooled / HP circuit 620. In an AC-only mode, a water loop control valve 630 upstream of the water-cooled condenser 640 is closed, and refrigerant flows from the compressor 650 to the AC condenser 660, through the AC expansion valve 670, and into the AC evaporator 680 to provide cooling to the passenger compartment. In an HP-only mode, an AC control valve 635 upstream of the AC condenser 660 is closed, and refrigerant flows from the compressor 650 to the water-cooled condenser 640. A heat transfer fluid (e.g., water or other heat transfer fluid) receives heat generated in the water-cooled condenser 640 and transfers it to the passenger compartment heater core 690 to provide heat to the passenger compartment. The heat transfer fluid can return from the passenger compartment heater core 690 to the water-cooled condenser 640. From the water-cooled condenser 640, the refrigerant flows through an HP expansion valve 675 to an HP evaporator 685 which cools a heat transfer fluid that may 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 may be used to heat and / or cool various other components of the vehicle. Separate humidity control modes can be achieved by sending a portion of the compressor discharge gas to the AC circuit 610 and the remaining portion to the water-cooled / HP circuit 620.

[0174] In the embodiment of Figures 6-9, the same components are present in the system, however, depending on the mode of operation, only some of the components are utilized.

[0175] In one embodiment, in a heating mode where certain conditions exist where both the vehicle cabin and other vehicle components require heat, the refrigerant circuit 700 operates as shown in FIG. 6. Starting from the compressor 750, the discharge refrigerant vapor will take two paths. One path is through the cabin condenser 740. The cabin condenser 740 is typically a fin-tube or microchannel type refrigerant-to-air heat exchanger and may be single-pass or multi-pass. A first fan 745 in the vehicle ventilation duct will direct a flow of either 100% outside air or a mixture of outside air and return air from the vehicle cabin across this cabin condenser 740, where the refrigerant will heat the air as it condenses. In this mode, a physical bypass 735 in the vehicle ventilation duct will prevent any air from flowing past the cabin evaporator 730. The second path of the refrigerant leaving the compressor is through a valve 770 and into the 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). This vehicle heat transfer loop can then 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. The condensed refrigerant leaving the exchanger 720 then merges with the liquid refrigerant outlet of the condenser 740 and the combined flow flows through an expansion device 775, which reduces the pressure of the liquid refrigerant and creates a liquid-vapor mixture. This liquid-vapor mixture then flows through an exterior heat exchanger 780 (i.e., an evaporator in this configuration). The exterior heat exchanger 780 is typically a fin-tube or microchannel type refrigerant-to-air heat exchanger and may be single-pass or multi-pass. A second fan 785 will induce airflow across the exterior heat exchanger 780, allowing the liquid-vapor refrigerant mixture to pick up heat from the ambient air and completely evaporate before returning to the compressor 750.

[0176] In another embodiment, in a heating mode when certain conditions exist that require only passenger compartment heating, the refrigerant circuit 800 operates as shown in FIG. 7. Starting from the compressor 850, the discharge vapor will first flow through the passenger compartment condenser 840. A first fan 845 in the vehicle ventilation duct will induce a flow of either 100% outside air or a mixture of outside air and return air from the vehicle passenger compartment across this passenger compartment condenser 840, and the refrigerant will exchange heat between the condenser 840 and the air. In this mode, a physical bypass 835 in the vehicle ventilation duct will prevent any air from flowing past the passenger compartment evaporator 830. The refrigerant will condense in the passenger compartment condenser 840 and flow to the expansion device 875, which will reduce the pressure of the liquid refrigerant and create a liquid-vapor mixture. This liquid-vapor mixture will flow through the exterior heat exchanger 880 (i.e., the evaporator in this configuration). The second fan 885 will induce airflow across the outdoor heat exchanger 880, allowing the liquid-vapor refrigerant mixture to pick up heat from the ambient air and completely evaporate before returning to the compressor 850.

[0177] In another embodiment, in a cooling mode when certain conditions exist that require cooling for both the vehicle cabin and vehicle components, the refrigerant circuit 900 operates as shown in FIG. 8. Starting from the compressor 950, the discharge refrigerant vapor first flows through the cabin condenser 940, but in this mode there is no heat transfer because a physical bypass 945 in the vehicle ventilation duct prevents any air from flowing past the cabin condenser 940. The vapor refrigerant will pass through the cabin condenser 940 and flow through a valve 975 into the exterior heat exchanger 980. In this mode, the exterior heat exchanger 980 acts as a condenser as a first fan 985 induces flow across the heat exchanger and the hot refrigerant vapor exchanges heat and condenses into a liquid. A portion of this liquid refrigerant will leave the exterior heat exchanger 980 and enter the interior heat exchanger 990. The liquid refrigerant will be subcooled in the interior heat exchanger 990 and then flow into the expansion device 910 and into the cabin evaporator 930. This air-refrigerant cabin evaporator 930 is a fin-tube or microchannel type heat exchanger and may be single-pass or multi-pass. A second fan (or cabin blower fan) 935 directs 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 interior heat exchanger 990 where it is further superheated before finally re-entering the compressor 950. The remaining portion of the refrigerant leaving the condenser 980 flows through the expansion valve 915 into the liquid / heat transfer fluid heat exchanger 920 where the heat of the 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 in the heat exchanger 920 and meets with the refrigerant leaving the interior heat exchanger 990 at the intake of the compressor 950.

[0178] In another embodiment, in cooling mode when certain conditions exist that require only vehicle cabin cooling, the refrigerant circuit 1000 operates as shown in FIG. 9. Starting from the compressor 1050, the discharge refrigerant vapor first flows through the cabin condenser 1040, and in this mode there is no heat transfer since a physical bypass 1045 in the vehicle ventilation duct prevents any air from flowing past the cabin condenser 1040. The vapor refrigerant will pass through the cabin condenser 1040 and flow through the valve 1075 into the exterior heat exchanger 1080. In this mode, the exterior heat exchanger 1080 functions as a condenser as the first fan 1085 induces flow across the heat exchanger 1080 and the hot refrigerant vapor exchanges heat and condenses into a liquid. This liquid refrigerant will leave the exterior heat exchanger 1080 and enter the interior heat exchanger 1090. The liquid refrigerant will be subcooled in the internal heat exchanger 1090 and then flow to the expansion device 1010 and then to the cabin evaporator 1030. A second fan (or cabin blower 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 will be exchanged between the air and the refrigerant. The refrigerant will evaporate and return to the internal heat exchanger 1090 where it will be further superheated before finally returning to the compressor 1050.

[0179] The refrigerant blend for use in a hybrid, mild hybrid, plug-in hybrid, or all-electric vehicle for passenger compartment thermal management (heat transfer from one part of the vehicle to another) to provide air conditioning (A / C) or heating to the passenger compartment has low GWP, low toxicity, and low flammability along with small temperature gradients. In addition, the refrigerant blend provides improved performance under the same conditions compared to HFO-1234yf, in particular providing a capacity higher than HFO-1234yf alone, even 20% or more higher than HFO-1234yf alone, and a COP equal to or higher than HFO-1234yf alone when operated under the same conditions. The COP is preferably at least 1% higher than HFO-1234yf alone, or more preferably at least 2% higher than HFO-1234yf alone, or most preferably at least 3% higher than HFO-1234yf alone when operated under the same conditions.

[0180] In another embodiment, also disclosed herein is a method for replacing HFO-1234yf in heating and cooling systems contained within electric vehicles, comprising providing any of the aforementioned compositions to the heating and cooling systems as a heat transfer fluid. According to any of the aforementioned embodiments, the refrigerant blend produces at least 20% higher, or 23% higher, or 25% higher volumetric heating capacity than HFO-1234yf alone when operated under the same conditions. In the method of replacing HFO-1234yf, the average temperature gradient with the replacement composition is less than 4.0 K, preferably less than 3.0 K, or more preferably less than 2.5 K, or more preferably less than 2.0 K.

[0181] In one embodiment, a method of servicing an electric vehicle heating and cooling system is provided. The method includes removing all of the used refrigerant from the system and charging the system with a composition comprising a refrigerant blend consisting essentially of HFO-1234yf, HFO-1132E, at least one hydrocarbon selected from the group consisting of propane, cyclopropane, propylene, isobutane, and n-butane, and optionally HFC-152a. The used refrigerant may be any of the aforementioned compositions, or the used refrigerant may be a composition that has changed from any of the aforementioned compositions due to some fractionation and preferential leakage of the low boiling components of the refrigerant blend. Due to fractionation that may occur during operation of the refrigerant with a temperature gradient, leakage of the 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, when the system is underperforming, it becomes necessary to remove all of the refrigerant present in the cooling and heating system and recharge the system with a fresh refrigerant blend having an optimized refrigerant blend composition.

[0182] In one embodiment there is provided the use of any of the aforementioned compositions comprising a refrigerant blend consisting essentially of HFO-1234yf, HFO-1132E, at least one hydrocarbon selected from the group consisting of propane, cyclopropane, propylene, isobutane, and n-butane, and optionally HFC-152a, as a heat transfer fluid in a system for heating and cooling the passenger compartment of an electric vehicle. This use of the compositions of the invention is described in detail in the preceding description and will be demonstrated in the examples below.

[0183] In other embodiments, including compositions intended to replace traditional high GWP refrigerants in refrigeration, air conditioning, and heat pump applications, it is desirable for the refrigerant compositions to exhibit a low GWP and similar or improved refrigerant properties compared to traditional refrigerants.

[0184] 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 may serve as replacements for traditional refrigerants with much higher GWP, particularly R-404A, R-410A, R-407A, R-407C, or R-407F. Stationary systems may include supermarket refrigerated cases, supermarket freezer cases, chillers that provide air conditioning for large buildings such as apartments, office buildings, hospitals, and / or school buildings, residential air conditioners, residential heat pumps for heating or cooling air or for heating water or other heat transfer fluids, or residential refrigerators or freezers.

[0185] In one embodiment, disclosed herein is a stationary refrigeration, air conditioning, or heat pump system containing a refrigerant consisting essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane.

[0186] In another embodiment, disclosed herein is a method of replacing a first refrigerant selected from R-22, R-404A, R-507A, R-507B, R-410A, R-407A, R-407C, or R-407F comprising removing at least a portion of the first refrigerant and charging with a second refrigerant consisting essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane.

[0187] In another embodiment, disclosed herein is a method of 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 comprising removing at least a portion of the first refrigerant and charging with a second refrigerant consisting essentially of about 51-90 weight percent HFO-1234yf, about 3-25 weight percent HFO-1132E, about 0-20 weight percent HFC-152a, and about 1-4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane.

[0188] The following examples are provided to illustrate certain aspects of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0189] A thermodynamic modeling program was used to model the predicted performance of blends containing HFO-1234yf, HFO-1132E, at least one hydrocarbon, and optionally HFC-152a compared to HFO-1234yf alone. Fourteen different sets of conditions were modeled as specified by the Society of Automotive Engineers (SAE) for characterization of refrigerant performance in automotive heat pump systems. Component properties were taken from NIST REFPROP version 10.

[0190] The conditions used were as described herein and in Table 2 below. Evaporator superheat = 10K Suction line overheat = 0K Supercooling=5K Compressor isentropic efficiency = 70% Compressor volumetric efficiency = 95%

[0191] [Table 3] * PTC = Positive coefficient heater

[0192] Example 1 Thermodynamic Modeling Comparison for Heat Pump Systems: HFO-1234yf / HFO-1132E / Propane vs. HFO-1234yf. Results shown in Table 3 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends versus HFO-1234yf alone.

[0193] [Table 4]

[0194] The above data demonstrates that refrigerant blends containing HFO-1234yf, HFO-1132E, and propane provide performance with significantly higher volumetric capacity (at least 20% higher) than HFO-1234yf, low average temperature gradients of less than 3K, and COPs comparable (within <1%) to that of HFO-1234yf alone. In addition, the refrigerant blends have normal boiling points below -30°C, allowing operation at temperatures below -30°C without subatmospheric pressures in the system. The improved performance of the blends of the present invention indicates that the new fluids can be readily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0195] Example 2 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFO-1132E / cyclopropane. The results shown in Table 4 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0196] [Table 5]

[0197] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, and cyclopropane provides performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradients of less than 3K, and a COP similar to or higher than that of HFO-1234yf alone. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be readily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0198] Example 3 Comparison of Thermodynamic Modeling of Heat Pump Systems: HFO-1234yf / HFO-1132E / Propylene. Results shown in Table 5 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends versus HFO-1234yf alone.

[0199] [Table 6]

[0200] The above data demonstrates that refrigerant blends containing HFO-1234yf, HFO-1132E, and propylene provide performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradients of less than 3K, and COPs comparable (within <1%) to that of HFO-1234yf alone. In addition, the refrigerant blends have normal boiling points below -30°C, allowing operation at temperatures below -30°C without subatmospheric pressures in the system. The improved performance of the blends of the present invention indicates that the new fluids can be readily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0201] Example 4 Comparison of Thermodynamic Modeling of Heat Pump Systems: HFO-1234yf / HFO-1132E / Isobutane. Results shown in Table 6 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0202] [Table 7]

[0203] The above data demonstrates that refrigerant blends containing HFO-1234yf, HFO-1132E, and isobutane provide performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradients of less than 3K, and COPs that are comparable or higher than that of HFO-1234yf alone. In addition, the refrigerant blends have normal boiling points below -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be readily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0204] Example 5 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFO-1132E / n-butane. Results shown in Table 7 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0205] [Table 8]

[0206] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, and n-butane provides performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradients of less than 3K, and a COP similar to or higher than that of HFO-1234yf alone. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be readily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0207] Example 6 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFC-152a / HFO-1132E / propane. The results shown in Table 8 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0208] [Table 9-1]

[0209] [Table 9-2]

[0210] [Table 9-3]

[0211] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, HFC-152a, and propane provides performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradient of less than 3K, and a COP equal to or higher than that of HFO-1234yf alone. The addition of HFC-152a further increases the COP over that of HFO-1234yf alone. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be easily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0212] Example 7 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFC-152a / HFO-1132E / cyclopropane. The results shown in Table 9 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0213] [Table 10-1]

[0214] [Table 10-2]

[0215] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, HFC-152a, and cyclopropane provides performance with significantly higher volumetric capacity (at least 20% higher) than HFO-1234yf, low average temperature gradient of less than 3K, and a COP equal to or higher than that of HFO-1234yf alone. The addition of HFC-152a further increases the COP. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be easily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0216] Example 8 Comparison of Thermodynamic Modeling of Heat Pump Systems: HFO-1234yf / HFC-152a / HFO-1132E / Propylene. The results shown in Table 10 are the averages of the temperature gradient, volumetric capacity, and COP for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blend for HFO-1234yf alone.

[0217] [Table 11-1]

[0218] [Table 11-2]

[0219] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, HFC-152a, and propane provides performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradient of less than 3K, and a COP equal to or higher than that of HFO-1234yf alone. The addition of HFC-152a further increases the COP compared to HFO-1234yf alone. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be easily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0220] Example 9 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFC-152a / HFO-1132E / isobutane. Results shown in Table 11 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent over the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0221] [Table 12-1]

[0222] [Table 12-2]

[0223] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, HFC-152a, and isobutane provides performance with significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, low average temperature gradient of less than 3K, and a COP equal to or higher than that of HFO-1234yf alone. The addition of HFC-152a increases the COP even further. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be easily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0224] Example 10 Comparison of thermodynamic modeling of heat pump systems: HFO-1234yf / HFC-152a / HFO-1132E / n-butane. Results shown in Table 12 are averages of temperature gradients, volumetric capacities, and COPs for SAE points 1-13 in Table 2. Capacity and COP are percent above the corresponding values ​​for the refrigerant blends relative to HFO-1234yf alone.

[0225] [Table 13-1]

[0226] [Table 13-2]

[0227] The above data demonstrates that the refrigerant blend containing HFO-1234yf, HFO-1132E, HFC-152a, and n-butane provides performance with a significantly higher (at least 20% higher) volumetric capacity than HFO-1234yf, a low average temperature gradient of less than 3K, and a COP equal to or higher than that of HFO-1234yf alone. The addition of HFC-152a increases the COP even further. In addition, the refrigerant blend has a normal boiling point of less than -30°C, allowing operation at temperatures below -30°C without subatmospheric pressure in the system. The improved performance of the blends of the present invention indicates that the new fluids can be easily used to provide adequate cooling and heat to the passenger compartment of electric or hybrid vehicles.

[0228] Although the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize that various changes can be made without departing from the scope of the invention and equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A composition comprising a refrigerant blend comprising HFO-1234yf, HFO-1132E, and at least one hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane.

2. The composition of claim 1 further comprising HFC-152a.

3. the refrigerant blend consists essentially of about 51 to 90 weight percent HFO-1234yf, about 1 to 25 weight percent HFO-1132E, about 0 to 20 weight percent HFC-152a, and about 1 to 4 weight percent of a hydrocarbon selected from the group consisting of propane, propylene, cyclopropane, n-butane, and isobutane; or the refrigerant blend consists essentially of about 58 to 90 weight percent HFO-1234yf, about 3 to 20 weight percent HFO-1132E, about 0 to 20 weight percent HFC-152a, and about 1 to 4 weight percent propane; or the refrigerant consists essentially of about 61 to 90 weight percent HFO-1234yf, about 4 to 18 weight percent HFO-1132E, about 0 to 20 weight percent HFC-152a, and about 1 to 4 weight percent cyclopropane; or the refrigerant consists essentially of about 60 to 90 weight percent HFO-1234yf, about 4 to 18 weight percent HFO-1132E, about 0 to 20 weight percent HFC-152a, and about 1 to 4 weight percent propylene; or the refrigerant consists essentially of about 51 to 90 weight percent HFO-1234yf, about 5 to 25 weight percent HFO-1132E, about 5 to 20 weight percent HFC-152a, and about 1 to 4 weight percent isobutane; or the refrigerant consists essentially of about 56 to 90 weight percent HFO-1234yf, about 8 to 20 weight percent HFO-1132E, about 0 to 20 weight percent HFC-152a, and about 1 to 4 weight percent n-butane; The composition according to claim 1 or 2.

4. 3. The composition of claim 1, wherein the refrigerant provides an average temperature gradient of from about 0.1 K to less than about 4 K.

5. 3. The composition of claim 1 or 2, wherein the refrigerant has a GWP of about 35 or less.

6. and further comprising at least one additional compound, said additional compound being: a) comprises 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-1225ye, HFO-1225zc, HFC-134a, HFO-1243zf, and HCFO-1131; or b) comprising 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, HFC-143a, HCFO-1122, and HCFC-142b; or c) comprises at least one compound selected from the group consisting of HFO-1132Z, HFO-1132a, HCFO-1131a, HCFC-142a, CFO-1122a, HFO-1123, HCFC-132, CFO-1113, and ethane; or d) a combination of a) and b), a) and c), b) and c), or a), b) and c); 3. The composition of claim 1 or 2, wherein the total amount of additional compounds comprises greater than 0 weight percent and less than 1 weight percent.

7. 7. The composition of claim 6, 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.

8. the additional compounds include HFC-143a, HFO-1132Z, HFC-161, and HCFC-151a; or the additional compounds include HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a; or the additional compounds include HFO-1243zf, HCC-40, and HFC-161; The composition of claim 6.

9. 3. The composition of claim 1 or 2, wherein the refrigerant has a burning velocity of 10 cm / s or less as measured according to the ISO 817 vertical tube method.

10. 3. The composition of claim 1 or 2, wherein the refrigerant is classified as 2L for flammability as defined in ANSI / ASHRAE Standard 34.

11. The composition of claim 1 or 2, further comprising a lubricant.

12. The composition of claim 11, wherein the lubricant is at least one selected from the group consisting of polyalkylene glycols, polyol esters, poly-α-olefins, and polyvinyl ethers.

13. 13. The composition of claim 12, wherein the polyol ester lubricant is obtained by reacting a carboxylic acid with a polyol containing a neopentyl backbone selected from the group consisting of neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mixtures thereof.

14. The composition of claim 1 or 2, further comprising a stabilizer.

15. 15. The composition of claim 14, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

16. 3. The composition of claim 1 or 2, further comprising at least one tracer.

17. 17. The composition of claim 16, wherein the at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

18. 10. A system for heating and cooling a 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, the system comprising the composition of claim 1 or 2.

19. 20. The system of claim 18, wherein the average temperature gradient is less than 4.0K, preferably less than 3.0K, more preferably less than 2.5K, or most preferably less than 2.0K.

20. 20. The system of claim 18, wherein the system does not include a PTC heater.

21. The system of claim 18 , wherein the system further comprises a reheater operably connected between the compressor and the condenser.

22. 10. A method for replacing HFO-1234yf in heating and cooling systems provided in electric vehicles, comprising providing the composition of claim 1 or 2 as a heat transfer fluid.

23. 23. The method of claim 22, wherein the refrigerant produces at least 20% more volumetric heating capacity than HFO-1234yf alone when operated under the same conditions.

24. 23. The method of claim 22, wherein said refrigerant produces a COP that is equal to or greater than the COP of HFO-1234yf alone when operated under said same conditions.

25. 10. A method of servicing an electric vehicle heating and cooling system, comprising the steps of removing all spent refrigerant from said system and charging said system with the composition of claim 1 or 2.

26. 3. Use of a composition according to claim 1 or 2 as a heat transfer fluid in a system for heating and cooling the passenger compartment of an electric vehicle.

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