[go: up one dir, main page]

WO2024249542A1 - Compositions de hfo-1234ze(e), hfc-32 et hfc-152a et systèmes d'utilisation de ces compositions - Google Patents

Compositions de hfo-1234ze(e), hfc-32 et hfc-152a et systèmes d'utilisation de ces compositions Download PDF

Info

Publication number
WO2024249542A1
WO2024249542A1 PCT/US2024/031534 US2024031534W WO2024249542A1 WO 2024249542 A1 WO2024249542 A1 WO 2024249542A1 US 2024031534 W US2024031534 W US 2024031534W WO 2024249542 A1 WO2024249542 A1 WO 2024249542A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
hfc
hfo
composition
refrigerant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/031534
Other languages
English (en)
Inventor
Jason R. Juhasz
David Matthew Snyder
Luke David SIMONI
Siddarth SITAMRAJU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Priority to CN202480030536.XA priority Critical patent/CN121057799A/zh
Priority to AU2024279576A priority patent/AU2024279576A1/en
Publication of WO2024249542A1 publication Critical patent/WO2024249542A1/fr
Priority to MX2025013747A priority patent/MX2025013747A/es
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds

Definitions

  • the present invention is directed to compositions comprising HFO- 1234zeE, HFC-32, and HFC-152a and uses thereof.
  • the ICE In electrified vehicles, the ICE is typically reduced in size (HEV, PHEV, or MHEV) or eliminated (EV) to reduce vehicle weight thereby increasing the electric drive-cycle. While the ICE’s primary function is to provide vehicle propulsion, it also provides heat to the passenger cabin as a secondary function. Typically, heating is required when ambient conditions are 10°C or lower. In a non-electrified vehicle, there is excess heat from the ICE, which can be scavenged and used to heat the passenger cabin. It should be noted that while the ICE may take some time (several minutes) to heat up and generate heat. Therefore, in electrified vehicles, ICE size reduction or elimination is creating a demand for effective alternative heating of the passenger cabin. In current EVs, with no ICE, positive temperature coefficient (PTC) heaters are currently being used. Use of a heat pump for cooling and heating can replace the PTC heater along with the air conditioning system and allow more efficient cooling and heating.
  • PTC positive temperature coefficient
  • R-134a a hydrofluorocarbon or HFC
  • GWP global warming potential
  • HFO-1234yf a hydrofluoroolefin
  • GWP 4 per Pappadimitriou and GWP ⁇ 1 per AR5
  • Refrigerant blends commonly used in stationary refrigerant applications are another option for automotive heat pumps. Examples of compositions comprising HFO-1234ze are disclosed in WO2007/126414; the disclosure of which is hereby incorporated by reference.
  • the instant invention solves certain problems associated with conventional refrigerants and provides compositions which meet the evolving regulatory landscape.
  • the present invention relates to compositions of environmentally friendly refrigerant blends with low GWP, (GWP less than or equal to 100) 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 low temperature glide for use in a hybrid, mild hybrid, plug-in hybrid, or full electric vehicles for complete vehicle thermal management (transferring heat from one part of the vehicle to another).
  • the thermal management system may operate to provide cooling and/or heating of the power electronics, battery, motor and provide air conditioning (A/C) and/or heating to the passenger cabin.
  • Mass transit mobile applications can also be used for mass transit mobile applications which benefit from a heat pump type system enabling both heating and cooling of batteries, motors and passenger compartment areas.
  • Mass transit mobile applications are not limited to, but can include transport vehicles such as ambulances, buses, shuttles, and trains.
  • compositions include refrigerant blends containing HFO-1234zeE, HFC-32, and HFC-152a.
  • refrigerant blends that provide volumetric capacity at least 10% higher than HFO-1234yf alone, COP equal to or higher than the COP of HFO-1234yf alone, with average temperature glide less than 6 K, are non-toxic and that would be classified as class 2 or 2L flammability by ASHRAE (American Society of Heating, Refrigeration, and Air Conditioning Engineers).
  • compositions useful as refrigerants and heat transfer fluids comprise: E-1,3,3,3- tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC-32), and 1 ,1- difluoroethane (HFC-152a).
  • compositions comprising a refrigerant blend comprising from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent H FC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent H FC-32, and from about 1 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides average temperature glide less than or equal to 6 K.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 10% higher than HFO-1234yf alone.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 15% higher than HFO-1234yf alone.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 20% higher than HFO-1234yf alone.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, provides capacity 10% higher than HFO-1234yf, and displays less than 6 K average temperature glide.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, provides capacity 15% higher than HFO-1234yf, and displays less than 6 K average temperature glide.
  • compositions comprising a refrigerant blend consisting essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a.
  • compositions comprising a refrigerant blend consisting essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, and displays less than 5 K average temperature glide.
  • compositions comprising a refrigerant blend consisting essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, and displays less than 4 K average temperature glide.
  • compositions wherein said refrigerant blend provides average temperature glide of about 0.1 K to less than about 6 K.
  • compositions wherein said refrigerant blend provides average temperature glide of about 0.1 K to less than about 5 K.
  • compositions wherein said refrigerant blend provides average temperature glide of about 0.1 K to less than about 4 K.
  • compositions wherein said refrigerant blend has a GWP of equal to or less than about 150.
  • compositions wherein said refrigerant blend has a GWP of equal to or less than about 120.
  • compositions further comprising at least one additional compound selected from: a) at least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropyne, HCC- 1140, HFC-1234yf, HFO-1234ze(Z), HFO-1225yeE, HFO-1225yeZ, HFO- 1225zc, HFC-134a, HFO-1243zf, and HCFO-1131 ; or b) at least one compound selected from the group consisting of: H FC-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, H
  • compositions wherein the additional compound includes at least one of HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, or HCC-160 or combinations thereof.
  • compositions wherein the additional compounds comprise HFC-143a, HFC-161 and HCFC-151a.
  • compositions wherein the additional compounds comprise HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a.
  • compositions wherein the additional compounds comprise HFO-1243zf, HCC-40, and HFC-161.
  • compositions wherein the refrigerant blend has a burning velocity of 10 cm/s or less, when measured in accordance with ISO 817 vertical tube method.
  • compositions wherein the refrigerant blend is classified as 2L for flammability as defined in ANSI/ASHRAE Standard 34.
  • compositions wherein the refrigerant blend has an LFL of less than 10 volume percent when measured in accordance with ASTM-E681.
  • compositions further comprising a lubricant.
  • compositions wherein said lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether.
  • compositions 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.
  • compositions wherein the carboxylic acid has 2 to 18 carbon atoms.
  • compositions wherein said lubricant has volume resistivity of greater than 10 10 Q-m at 20°C.
  • compositions wherein said lubricant has surface tension of from about 0.02 N/m to 0.04 N/m at 20°C.
  • compositions wherein said lubricant has a kinemetic viscosity of from about 20 cSt to about 500 cSt at 40°C.
  • compositions wherein said lubricant has a breakdown voltage of at least 25 kV.
  • compositions wherein said lubricant has a hydroxy value of at most 0.1 mg KOH/g.
  • compositions further comprising from 0.1 to 200 ppm by weight of water.
  • compositions further comprising from about 10 ppm by volume to about 0.35 volume percent oxygen.
  • compositions further comprising from about 100 ppm by volume to about 1.5 volume percent air.
  • compositions further comprising a stabilizer.
  • compositions 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.
  • compositions wherein the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-terbutyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, d-limonene, a-terpinene, p-terpinene, a-pinene, p- pinene, or butylated hydroxytoluene.
  • the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-terbutyl-4-methylphenol, fluorinated epoxides, n-butyl
  • compositions wherein the stabilizer is present in an amount from about 0.001 to 1.0 weight percent based on the weight of the refrigerant.
  • compositions further comprising at least one tracer.
  • compositions wherein said at least one tracer is present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight.
  • compositions wherein said at least one tracer is selected from the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.
  • compositions wherein said at least one tracer is selected from the group consisting of HFC-23, HCFC-31, HFC-41 , HFC-161, HFC-143a, HFC-134a, HFC-125, HFC- 236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC- 12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO- 1130,
  • compositions wherein the composition is free of or substantially free of Group A Fluorinated Substances.
  • compositions wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.
  • a refrigerant storage container containing the compositions according to any of the foregoing embodiments, wherein the refrigerant comprises gaseous and liquid phases.
  • systems for heating and cooling the passenger compartment of an electric vehicle comprising an evaporator, compressor, condenser and expansion device, each operably connected to perform a vapor compression cycle, the refrigerant composition of any of the foregoing embodiments being circulated through each of the evaporator, compressor, condenser and expansion device.
  • cooling and heating systems wherein the average temperature glide is less than 6.0 K, less than 5.0 K, or less than 4.0 K.
  • cooling and heating systems wherein the system does not include a PTC heater.
  • cooling and heating systems wherein the system is not a reversible cooling loop.
  • cooling and heating systems wherein the system further comprises a reheater operably connected between the compressor and the condenser.
  • a method for replacing HFO-1234yf in a cooling system contained within an internal combustion engine or hybrid vehicle comprising adding any of the foregoing compositions to said cooling system as a heat transfer fluid.
  • a method for replacing HFO-1234yf wherein the refrigerant blend produces volumetric capacity at least 10% higher than HFO-1234yf alone when operating under the same set of conditions.
  • the refrigerant blend may provide capacity at least 15% higher than HFO-1234yf alone, or the refrigerant blend may provide capacity at least 20% higher than 1234yf alone.
  • the refrigerant blend produces COP equal to or greater than the COP of HFO-1234yf alone when operating under the same conditions.
  • the refrigerant blend may provide COP that is 5% higher, 6% higher, or even 7% higher than 1234yf alone.
  • compositions as a heat transfer fluid in a system for heating and cooling the passenger compartment of an hybrid or electric vehicle.
  • FIG. 1 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 2 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 3 illustrates a cooling or heating loop system, according to an embodiment.
  • FIG. 4 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 5 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 6 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 7 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 8 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 9 illustrates a cooling or heating system, according to an embodiment.
  • a heat source is defined as any space, location, object, or body from which it is desirable to add, transfer, move or remove heat.
  • Example of a heat source in this embodiment is the vehicle passenger compartment requiring air conditioning.
  • a heat sink is defined as any space, location, object, or body capable of absorbing heat.
  • Example of a heat sink in this embodiment is the vehicle passenger compartment requiring heating.
  • a heat transfer system is the system (or apparatus) used to produce a heating or cooling effect in a particular location.
  • a heat transfer system in this invention implies the heating or cooling system which provides heating or cooling of the passenger compartment of an automobile. Sometimes this system is called a heat pump system and may be a reversible heating system or a reversible cooling system, or simply a heating and cooling system.
  • a heat transfer fluid comprises at least one refrigerant and at least one member selected from the group consisting of lubricants, stabilizers, tracers, UV dyes, and flame suppressants.
  • Volumetric capacity is the amount of heat absorbed or rejected divided by the theoretical compressor displacement. Heat removed or absorbed is the enthalpy difference across a heat exchanger multiplied by the refrigerant mass flowrate. Theoretical compressor displacement is the refrigerant mass flowrate 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 a smaller compressor for the same heat load.
  • cooling capacity refers to the volumetric capacity in cooling mode and heating capacity refers to the volumetric capacity in heating mode.
  • Coefficient of performance is the amount of heat absorbed or rejected divided by the required energy input to operate the cycle (approximated by the compressor power).
  • COP is specific to the mode of operation of a heat pump, thus COP for heating or COP for cooling.
  • COP is directly related to the energy efficiency ratio (EER).
  • Superheating refers to the increase of the temperature of a vapor above that vapor’s saturation point for a given pressure.
  • the vapor saturation point is the temperature at which the liquid is completely evaporated to a vapor.
  • Superheating continues to heat the vapor to a higher temperature vapor at the given pressure.
  • the net refrigeration effect can be increased.
  • Superheating thereby improves refrigeration capacity and energy efficiency of a system when it occurs in the evaporator.
  • Suction line superheat does not add to the net refrigeration effect and can reduce efficiency and capacity.
  • the superheat amount is the amount of heating above the saturation temperature (in degrees).
  • Temperature glide (sometimes referred to simply as "glide") is the absolute value of the difference between the starting and ending temperatures of a phasechange process by a refrigerant within a condenser of a refrigerant system, exclusive of any subcooling or superheating.
  • the glide is the difference in temperature between the dew point and the evaporator inlet.
  • Glide may be used to describe condensation or evaporation of a near azeotrope or non-azeotropic composition. When referring to the temperature glide of an air conditioning or heat pump system, it is common to provide the average temperature glide being the average of the temperature glide in the evaporator and the temperature glide in the condenser.
  • Glide is applicable to blend refrigerants, i.e. refrigerants that are composed of at least 2 components.
  • E-1,3,3,3-Tetrafluoropropene (HFO-1234zeE or R-1234zeE) is available commercially from Honeywell (Charlotte, North Carolina, USA). 1,1-difluoroethane (HFC-152a or R-152a) is available commercially from ChemoursTM (Wilmington, DE, USA). Difluoromethane (HFC-32 or R-32) is available commercially from various sources worldwide.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase "consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • the term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of'.
  • Global warming potential is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide.
  • GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas.
  • the GWP for the 100-year time horizon is commonly the value referenced.
  • 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 for refrigerant GWPs in official assessment reports (ARs.)
  • the fourth assessment report is denoted as AR4 and the fifth assessment report is denoted as AR5.
  • the GWP values reported for refrigerant blends of the present invention herein refer to the AR5 values, for those compounds listed therein.
  • ODP Ozone-depletion potential
  • the ODP is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of R-11 or trichlorofluoromethane.
  • R-11 is a type of chlorofluorocarbon (CFC) and as such has chlorine in it which contributes to ozone depletion.
  • CFC-11 is a type of chlorofluorocarbon (CFC) and as such has chlorine in it which contributes to ozone depletion.
  • the ODP of CFC-11 is defined to be 1.0.
  • Other CFCs and hydrofluorochlorocarbons (HCFCs) have ODPs that range from 0.01 to 1.0.
  • Hydrofluorocarbons HFCs
  • HFO hydrofluoro-olefins
  • compositions comprise a refrigerant blend consisting essentially of E- 1 ,3,3,3-tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC-32), and 1 ,1- difluoroethane (HFC-152a).
  • HFO-1234zeE E- 1 ,3,3,3-tetrafluoropropene
  • HFC-32 difluoromethane
  • HFC-152a 1 ,1- difluoroethane
  • Suitable amounts of HFO-1234zeE in the refrigerant blend include, but are not limited to an amount between about 63 weight percent to 93 weight percent or between about 68 weight percent to 93 weight percent or between about 71 weight percent to 93 weight percent or between about 63 weight percent to 86 weight percent or between about 63 weight percent to 84 weight percent, or between about 63 weight percent to 82 weight percent, or between about 63 weight percent to 80 weight percent, or between about 63 weight percent to 76 weight percent, or between about 63 weight percent to 69 weight percent, based on the total refrigerant blend composition.
  • Suitable amounts of HFC-32 in the refrigerant blend include, but are not limited to an amount between about 6 weight percent to 21 weight percent or between about 6 weight percent to 17 weight percent or between about 6 weight percent to 12 weight percent or between about 6 weight percent to 9 weight percent or between about 11 weight percent to 21 weight percent, or between about 11 weight percent to 17 weight percent, or between about 14 weight percent to 17 weight percent, or between about 16 weight percent to 17 weight percent, based on the total refrigerant blend composition.
  • Suitable amounts of H FC- 152a in the refrigerant blend include but are not limited to an amount between 1 weight percent to about 20 weight percent or between about 7 weight percent to 20 weight percent, or between about 10 weight percent to 20 weight percent, or between about or between about 15 weight percent to 20 weight percent on the total refrigerant blend composition.
  • the composition comprises a refrigerant blend comprising from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 86 weight percent HFO- 1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 80 weight percent HFO- 1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • the refrigerant blend consists essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 68 to 93 weight percent HFO- 1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the refrigerant blend consists essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend comprising a refrigerant blend consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASH RAE, and also provides average temperature glide less than or equal to 6 K.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 10% higher than HFO-1234yf alone.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 15% higher than HFO-1234yf alone.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. This range provides GWP ⁇ 150 and would be classified as class 2L, low flammability, by ASHRAE, and also provides capacity 20% higher than HFO-1234yf alone.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, provides capacity 10% higher than HFO-1234yf, and displays less than 6 K average temperature glide.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, provides capacity 15% higher than HFO-1234yf, and displays less than 6 K average temperature glide.
  • the composition comprises a refrigerant blend consisting essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC- 152a.
  • the composition comprises a refrigerant blend consisting essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, and displays less than 5 K average temperature glide.
  • the composition comprises a refrigerant blend consisting essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. This range provides GWP ⁇ 150, would be classified as class 2L, low flammability, by ASHRAE, and displays less than 4 K average temperature glide.
  • the refrigerant blends have zero ODP and low GWP, or GWP ⁇ 150, or preferably GWP ⁇ 120, or more preferably GWP ⁇ 100, (by AR5 values).
  • Table 1 shown below, is a summary table showing refrigerant and GWP per the 5 th assessment report conducted by the Intergovernmental Panel on Climate Change (IPCC).
  • GWP may be calculated as a weighted average of the individual GWP values for the components in the blend, taking into account the mass (e.g., weight %) of each ingredient in the blend.
  • Table 1 provides the GWP values for each of the components of the refrigerant blends of the present invention along with a couple of examples of refrigerant blend GWP values.
  • the refrigerant blends as described herein operate in heat exchangers, i.e., evaporators and/or condensers with low temperature glide. Thus, there is limited fractionation of the composition in operation providing efficient and consistent performance for cooling and heating.
  • the refrigerant blends provide average temperature glides less than 6K over operating range of interest, more preferably low glide is less than 5K over operating range of interest, with most preferable being less than 4.0 K over operating range of interest, (e.g., a glide ranging from great than 0 to less than about 4. OK). This effect is observed, when any of the foregoing refrigerant blends are used in a heat pump.
  • compositions comprising, consisting essentially of, or consisting of HFO-1234ze(E), HFC-152a, and HFC-32 according to the present invention and the degradation products thereof are preferably free of or substantially free of Group A Fluorinated Substances.
  • Group A Fluorinated Substances includes any substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H/CI/Br/l attached to it); and (ii) meets the criterion for persistence in soil/sediment and water established in Annex XIII (Section 1.1.1) of the European Union’s REACH Regulation (https://reachonline.eu/reach/en/annex-xiii-1-1.1-1.1.1.html as accessed on May 2, 2023) and referenced in the Annex XV Restriction Report dated March 22, 2023, the disclosure of which is hereby incorporated by reference (https://echa.europa.eu/documents/10162/f605d4b5-7c17-7414-8823-b49b9fd43aea as accessed on May 2, 2023).
  • Group A Fluorinated Substances include
  • Group A Fluorinated Substances includes any substance that has a Henry’s Law constant ⁇ 250 Pa*m 3 /mol and contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H/CI/Br/l attached to it).
  • Group A Fluorinated Substances include, but are not limited to, TFA.
  • compositions of the present invention comprise HFO-1234ze(E), HFC-152a, and HFC-32, and are free of or substantially free of Group A Fluorinated Substances, such as TFA.
  • the phrase "free of" as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas sample or liquid sample, and/or ion chromatography by analysis of a water sample after bubbling the thermal fluid through water.
  • the phrase "substantially free of” as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is> 0 wt.% and ⁇ _15 or wt.%, > 0 wt.% and ⁇ _10 wt.%, or > 0 wt.% and ⁇ _5 wt.%, or > 0 wt.% and ⁇ 4 wt.%, or > 0 wt.% and ⁇ 3 wt.%, or > 0 wt.% and ⁇ 2 wt.%, or > 0 wt.% and ⁇ 1 wt.%, and all values and ranges therebetween, when measured by gas chromatographic (GO) techniques, for example gas chromatography (GO) with a flame ionization or electron-capture detector, or GO coupled with a mass detector (gas chromatography
  • GO gas chromatographic
  • TFA analytical standard may be used in either gas chromatography or ion chromatography and is available from, for example, Sigma Aldrich.
  • degradation products of such compositions of the present invention which comprise HFO-1234ze(E), HFC-152a, and HFC-32, are free of or substantially free of Group A Fluorinated Substances, such as TFA.
  • the phrase "free of" as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil/sediment and water produced during tropospheric degradation of the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by GO techniques, for example GO with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • the phrase "substantially free of” as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil/sediment and water produced during tropospheric degradation of the compositions is > 0% and ⁇ 5%, or > 0% and ⁇ 4%, or > 0% and ⁇ 3%, or > 0% and ⁇ 2%, or > 0% and ⁇ 1%, and all values and ranges therebetween, when measured by GO techniques, for example GO with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • GO techniques for example GO with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • compositions of the present invention comprising a refrigerant blend may further comprise a lubricant and be used as a heat transfer fluid.
  • the composition of the present invention containing the refrigerant blend of the present invention and the lubricant may contain additives such as a stabilizer, a leakage detection material (e.g., UV dye), a tracer, and other beneficial additives.
  • the lubricant chosen for this composition preferably has sufficient solubility in the refrigerant blend to ensure that the lubricant can return to the compressor from the evaporator. Furthermore, the miscibility must not be so great as to reduce the effective viscosity of the lubricant for lubricating the compressor.
  • the lubricant and refrigerant blend are miscible over a broad range of temperatures. For use in mobile air-conditioning and heating, miscibility over a temperature range from about -40°C to about +40°C is desirable.
  • Lubricants of the invention may include polyalkylene glycol lubricants (PAG), polyol ester lubricants (POE), polyvinyl ether lubricants (PVE), and even poly-a-olefins (PAO), alkylbenzenes, mineral oils, fluorinated polyethers, and even silicon lubricants.
  • PAG polyalkylene glycol lubricants
  • POE polyol ester lubricants
  • PVE polyvinyl ether lubricants
  • PAO poly-a-olefins
  • Preferred lubricants may be one or more polyalkylene glycol type lubricants (PAG), one or more polyol ester type lubricants (POE), one or more poly-a-olefins (PAO), or one or more polyvinyl ether lubricants. Additionally, lubricants for combination with the refrigerant blends of the present invention may be mixtures of any of PAG, POE, and/or PVE lubricants.
  • PAG polyalkylene glycol type lubricants
  • POE polyol ester type lubricants
  • PAO poly-a-olefins
  • lubricants for combination with the refrigerant blends of the present invention may be mixtures of any of PAG, POE, and/or PVE lubricants.
  • Polyalkylene glycol (PAG) oils may be homopolymers or copolymers consisting of two or more oxypropylene groups. PAG oils can be un-capped, singleend capped, or double-end capped. Examples of commercial 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.
  • PAG lubricant properties that make them of use in the present invention include volume resistivity of greater than 10 10 Q-m at 20°C, surface tension of from about 0.02 N/m to 0.04 N/m at 20°C, kinemetic viscosity of from about 20 cSt to about 500 cSt at 40°C, breakdown voltage of at least 25 kV, and hydroxy value of at most 0.1 mg KOH/g.
  • the lubricant comprises PAG is stable when exposed to the inventive composition wherein the refrigerant blend composition has a Total Acid Number (TAN), mg KOH/g number of less than about 1 , greater than 0 and less than 1, greater than 0 and less than about 0.75 and, in some cases, greater than 0 and less than about 0.4.
  • TAN Total Acid Number
  • the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 93 weight percent HFO- 1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. In another embodiment, the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PAG and the refrigerant consists essentially of about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PAG and the refrigerant consists essentially of about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PAG and the refrigerant consists essentially of about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the refrigerant composition further comprises greater than about 0 and less than 1 wt.% of additional compounds.
  • 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 a chemical reaction (esterification) of a carboxylic acid, or a mixture of carboxylic acids, with an alcohol, or mixture of alcohols.
  • the polyol esters as used herein include esters of a diol or a polyol having from about 3 to 20 hydroxyl groups and a carboxylic acid (or fatty acid) having from about 1 to 24 carbon atoms is preferably used as the polyol.
  • An ester which can be used as the base oil is described in EUROPEAN Patent Application published in accordance with Art. 153(4) EP 2 727 980 A1 , which is hereby incorporated 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,
  • polyol examples include a polyhydric alcohol such as trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerin, polyglycerin (dimer to eicosamer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, a sorbitol-glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc.; a saccharide such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose,
  • a polyhydric alcohol such
  • a hindered alcohol such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri (pentaerythritol), etc. is preferable as the polyol
  • the fatty acid is not particularly limited on its carbon number, in general, a fatty acid having from 1 to 24 carbon atoms is used. In the fatty acid having from 1 to 24 carbon atoms, a fatty acid having 3 or more carbon atoms is preferable, a fatty acid having 4 or more carbon atoms is more preferable, a fatty acid having 5 or more carbon atoms is still more preferable, and a fatty acid having 10 or more carbon atoms is the most preferable from the standpoint of lubricating properties.
  • a fatty acid having not more than 18 carbon atoms is preferable, a fatty acid having not more than 12 carbon atoms is more preferable, and a fatty acid having not more than 9 carbon atoms is still more preferable from the standpoint of compatibility with the refrigerant.
  • the carboxylic acid has 2 to 18 carbon atoms.
  • the fatty acid may be either of a linear fatty acid and a branched fatty acid, and the fatty acid is preferably a linear fatty acid from the standpoint of lubricating properties, whereas it is preferably a branched fatty acid from the standpoint of hydrolysis stability. Furthermore, the fatty acid may be either of a saturated fatty acid and an unsaturated fatty acid.
  • examples of the above-described fatty acid include a linear or branched fatty acid 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, etc.; a so-called neo acid in which a carboxylic group is attached to a quaternary carbon atom; and the like.
  • a linear or branched fatty acid such as pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,
  • 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-octadecenoic acid
  • isopentanoic acid (3-methylbutanoic acid), 2- methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5- trimethylhexanoic acid, and the like.
  • the polyol ester maybe a partial ester in which the hydroxyl groups of the polyol remain without being fully esterified; a complete ester in which all of the hydroxyl groups are esterified; or a mixture of a partial ester and a complete ester, with a complete ester being preferable.
  • an ester of a hindered alcohol such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), tri(pentaerythritol), etc.
  • an ester of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, or pentaerythritol being still more preferable, from the standpoint of more excellent hydrolysis stability; and an ester of pentaerythritol is the most preferable from the standpoint of especially excellent compatibility with the refrigerant and hydrolysis stability.
  • Preferred specific examples of the polyol ester include a diester of neopentyl glycol with one kind or two or more kinds of 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; a triester of trimethylolethane with one kind or two or more kinds of 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;
  • the ester with two or more kinds of fatty acids may be a mixture of two or more kinds of esters of one kind of a fatty acid and a polyol, and an ester of a mixed fatty acid of two or more kinds thereof and a polyol, particularly an ester of a mixed fatty acid and a polyol is excellent in low-temperature properties and compatibility with the refrigerant.
  • the POE lubricant used for electrified automotive air-conditioning application may have a kinematic viscosity (measured at 40°C, according to ASTM D445) between 20-500 cSt, or 75-110 cSt, and ideally about 80 cSt-100 cSt and most specifically, between 85 cSt-95 cSt.
  • a kinematic viscosity measured at 40°C, according to ASTM D445
  • other lubricant viscosities may be included depending on the needs of the electrified vehicle heat pump compressor. Suitable characteristics of an automotive POE type lubricant for use with the inventive composition are listed below.
  • the lubricant comprises POE and the POE is stable when exposed to the inventive compositions wherein the refrigeration composition has an F-ion of less than about 500 ppm and in some cases an F-ion amount of greater than 0 and less than 500 ppm, greater than 0 and less than 100 ppm and, in some cases, greater than 0 and less than 50 ppm.
  • the refrigerant consists essentially of about 63 to 93 weight percent or between about 68 to 93 weight percent or between about 71 to 93 weight percent or between about 63 to 86 weight percent or between about 63 to 84 weight percent, or between about 63 to 82 weight percent, or between about 63 to 80 weight percent, or between about 63 to 76 weight percent, or between about 63 to 69 weight percent HFO-1234zeE; between about 6 to 21 weight percent or between about 6 to 17 weight percent or between about 6 to 12 weight percent or between about 6 to 9 weight percent or between about 11 to 21 weight percent, or between about 11 to 17 weight percent, or between about 14 to 17 weight percent, or between about 16 to 17 weight percent H FC-32; and about between 1 weight percent to about 20 weight percent or between about 7 weight percent to 20 weight percent, or between about 10 weight percent to 20 weight percent, or between about or between about 15 weight percent to 20 weight percent HFC-152a.
  • the refrigerant composition further comprises greater
  • the lubricant comprises POE is stable when exposed to the inventive composition wherein the refrigerant blend composition has a Total Acid Number (TAN), mg KOH/g number of less than about 1, greater than 0 and less than 1, greater than 0 and less than about 0.75 and, in some cases, greater than 0 and less than about 0.4.
  • TAN Total Acid Number
  • the lubricant comprises POE and the refrigerant consists essentially of about 63 to 93 weight percent HFO- 1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. In another embodiment, the lubricant comprises POE and the refrigerant consists essentially of about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises POE and the refrigerant consists essentially of about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises POE and the refrigerant consists essentially of about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises POE and the refrigerant consists essentially of about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. And, in a further aspect, the refrigerant composition further comprises greater than about zero and less than 1 wt.% of additional compounds.
  • PVE lubricants can be included as lubricant in the compositions of the present invention.
  • the polyvinyl ether oil includes those taught in the literature such as described in U.S. Pat. Nos. 5,399,631 and 6,454,960.
  • the polyvinyl ether oil is composed of structural units of the type shown by Formula 1 :
  • R1, R2, and R3 are each hydrogen, as shown in Formula 2:
  • polyvinyl ether oil is composed of structural units of the type shown by Formula 3:
  • R5 and R6 are independently selected from hydrogen and hydrocarbons and where m and n are integers.
  • the properties of the lubricant may be adjusted by varying the m/n ratio and the sum of m+n.
  • the PVE lubricants are those that are 50-95 weight percent of unit 1.
  • the lubricant comprises PVE is stable when exposed to the inventive composition wherein the refrigerant blend composition has a Total Acid Number (TAN), mg KOH/g number of less than about 1 , greater than 0 and less than 1 , greater than 0 and less than about 0.75 and, in some cases, greater than 0 and less than about 0.4.
  • the lubricant comprises PVE and the refrigerant consists essentially of about 63 to 93 weight percent HFO- 1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PVE and the refrigerant consists essentially of about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. In another embodiment, the lubricant comprises PVE and the refrigerant consists essentially of about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PVE and the refrigerant consists essentially of about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PVE and the refrigerant consists essentially of about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment the lubricant comprises PVE and the refrigerant consists essentially of about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the lubricant comprises PVE and the refrigerant consists essentially of about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. And, in a further aspect, the refrigerant composition further comprises greater than about zero and less than 1 wt.% of additional compounds.
  • the lubricant is soluble in the refrigerant at temperatures between about -40°C and about 80°C, and more preferably in the range of about -30°C and about 40°C, and even more specifically between -25°C and 40°C.
  • attempting to maintain the lubricant in the compressor is not a priority and thus high temperature insolubility is not preferred.
  • the amount of lubricant can range from about 1 wt% to about 20 wt%, about 1 wt% to about 7 wt%, and, in some cases, about 1 wt% to about 3 wt%.
  • the lubricant in this embodiment needs to have low moisture, typically less than 100 ppm by weight of water.
  • the lubricant comprises a POE lubricant that is soluble in the vehicle heat pump system refrigerant blend at temperatures between about -35°C and about 100°C, and more preferably in the range of about -35°C and about 50°C, and even more specifically between -30°C and 40°C.
  • the POE lubricant is soluble at temperatures above about 70°C, more preferably at temperatures above about 80°C, and most preferably at temperatures between 90 -95°C.
  • PAG, POE, PAO, and PVE lubricants having: volume resistivity of greater than 10 10 Q-m at 20°C; surface tension of from about 0.02 N/m to 0.04 N/m at 20°C; a kinematic viscosity of from 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 breakdown voltage of at least 25 kV; and a hydroxy value of at most 0.1 mg KOH/g.
  • HFO type refrigerants due to the presence of a double bond, may be subject to thermal instability and decompose under extreme use, handling or storage situations. Therefore, there may be advantages to adding stabilizers to HFO type refrigerants.
  • Stabilizers may notably include nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 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, butylphenylglycidyl ether, cyclic
  • Blends may or may not include stabilizers depending on the requirements of the system being used. If the refrigerant blend does include a stabilizer, it may include any amount from 0.001 wt% up to 1 wt%, preferably from about 0.01 to about 0.5 weight percent, more preferably, from about 0.01 to about 0.3 weight percent of any of the stabilizers listed above, and, in most case, preferably d-limonene.
  • the compositions as disclosed herein may contain a tracer compound or tracers.
  • the tracer may comprise two or more tracer compounds.
  • the tracer is present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm, based on the weight of the total composition.
  • the tracer is present at a total concentration of about 50 ppm to about 500 ppm.
  • the tracer is present at a total concentration of about 100 ppm to about 300 ppm.
  • the tracer may be present in the compositions of the present invention in predetermined quantities to allow detection of any dilution, contamination or other alteration of the composition.
  • the presence of certain compounds in the composition may indicate by what method or process one of the components has been produced.
  • the tracer may also be added to the composition in a specified amount in order to identify the source of the composition. In this manner, detection of infringement on patent rights may be accomplished.
  • the tracers may be refrigerant compounds but are present in the composition at levels that are unlikely to impact performance of the refrigerant component of the composition.
  • Tracer compounds may be hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.
  • tracer compounds include, but are not limited to HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1 ,1 ,1 -trifluoroethane), HFC-134a (1,1,1 ,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1 ,1 ,1,3,3, 3-hexafluoropropane), HFC-236ea (1,1,1 ,2,3,3-hexafluoropropane), HFC 245cb (1,1 ,1,2,2-pentafluoropropane), HFC-245fa (1, 1,1, 3,3- pentafluoropropane) , HFC-254eb (1 ,1,1, 2-tetrafluoropropane), HFC-263fb (1 ,1 ,
  • any of the ranges for the presently disclosed compositions may further comprise additional compounds.
  • the refrigerant blends may comprise, consist essentially of, or consist of HFO-1234zeE, HFC-32, and HFC-152a plus optional additional compounds.
  • the composition comprises a refrigerant blend and additional compounds, wherein the refrigerant blend consists essentially of about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 93 weight percent HFO- 1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 84 weight percent HFO- 1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 80 weight percent HFO- 1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent H FC- 152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the composition comprises a refrigerant blend and additional compounds and the refrigerant blend consists essentially of about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the additional compounds are present in an amount of greater than about 0 and less than 1 wt.%.
  • the present compositions further comprise at leat one additional compounds selected from: a) at least one compound selected from the group consisting of HCFC-244bb, HFC-245cb, HFC-254eb, CFC-12, HCFC-124, 3,3,3-trifluoropropyne, HCC- 1140, HFC-1234yf, HFO-1234ze(Z), HFO-1225yeE, HFO-1225yeZ, HFO- 1225zc, HFC-134a, HFO-1243zf, and HCFO-1131 ; or b) at least one compound selected from the group consisting of: H FC-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-143
  • the composition comprises the refrigerant blend in any of the above ranges of components and further contains the additional compounds including at least one of HFC-161, HFO-1141, HCO-1140, HCFC-151a, HCC-150a, or HCC-160 or combinations thereof.
  • the composition comprises the refrigerant blend in any of the above ranges of components and further contains the additional compounds including at least one of HFC-143a, HFC-161 and HCFC-151a or combinations thereof.
  • the composition comprises the refrigerant blend in any of the above ranges of components and further contains the additional compounds including at least one of HFO-1243zf, HFC-143a, HCC-40, HFC-161, and HCFC-151a or combinations thereof.
  • the composition comprises the refrigerant blend in any of the above ranges of components and further contains the additional compounds including at least one of HFO-1243zf, HCC-40, and HFC-161 or combinations thereof.
  • Flammability is a term used to mean the ability of a composition to ignite and/or propagate a flame.
  • the lower flammability limit (“LFL”) is the minimum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under test conditions specified in ASTM (American Society of Testing and Materials) E681.
  • the upper flammability limit (“UFL”) is the maximum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under the same test conditions.
  • the WCF and WCFF In order to be classified as 2L, low flammability, 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 (0.10 kg/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). Additionally, the nominal refrigerant blend must have a heat of combustion ⁇ 8169 Btu/lb (19,000 kJ/kg).
  • ASHRAE Standard 34 provides a methodology to calculate the heat of combustion for refrigerant blends using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with enough oxygen for a stoichiometric reaction.
  • the amount of additional compounds present in any of the foregoing refrigerant compositions can be greater than 0 ppm and less than 5,000 ppm and, in particular, can range from about 5 to about 1,000 ppm, about 5 to about 500 ppm and about 1 to about 100 ppm.
  • the amount of additional compounds present in any of the foregoing refrigerant compositions can be greater than 0 and less than 1 wt% of the refrigerant composition, preferably less than 0.5 weight percent, or more preferably less than 0.1 weight percent.
  • Another embodiment of the invention relates to storing any of the foregoing compositions in gaseous and/or liquid phases within a sealed container.
  • the water concentration within the gas and/or liquid phase in the sealed container ranges from about 0.1 to 200 ppm by weight.
  • the oxygen concentration within the gas and/or liquid phase in the sealed container ranges from about 10 ppm by volume to about 0.35 volume percent at about 25 C.
  • the air concentration within the gas and/or liquid phase in the sealed container ranges from about 100 ppm by volume to about 1.5 volume percent.
  • the container for storing the foregoing compositions can be constructed of any suitable material and design that is capable of sealing the compositions therein while maintaining gaseous and liquids phases.
  • suitable containers comprise pressure resistant containers such as a tank, a filling cylinder, and a secondary filling cylinder.
  • the container can be constructed from any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, among other low-alloy steels, stainless steel and in some case an aluminum alloy.
  • the compositions of the present invention may be prepared by any convenient method to combine the desired amount of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • any of the foregoing refrigerant compositions can be prepared by blending HFO-1234zeE, HFC-32, and HFC-152a, and, in some cases, at least one of the additional compounds.
  • the compositions may be prepared from recycled or reclaimed refrigerant.
  • One or more of the components may be recycled or reclaimed by means of removing contaminants, such as air, water, or residue, which may include lubricant or particulate residue from system components.
  • the means of removing the contaminants may vary widely, but can include distillation, decantation, filtration, and/or drying by use of molecular sieves or other absorbents.
  • the recycled or reclaimed component(s) may be combined with the other component(s) as describe above.
  • a system for heating and cooling the passenger compartment of an electric vehicle comprises an evaporator, compressor, condenser and expansion device, each operably connected to perform a vapor compression cycle, wherein the system contains any of the foregoing compositions comprising a refrigerant blend consisting essentially of HFO-1234zeE, HFC-32, and HFC-152a.
  • the average temperature glide in the inventive system is less than or equal to 6.0 K, preferably less than or equal to 5.0 K, or more preferably less than or equal to 4.0 K.
  • the system is preferably a heat pump. Due to the excellent performance of the heat pump system in both cooling and heating of the passenger compartment of an electric vehicle, the system may no longer require a positive temperature coefficient (PTC) heater.
  • PTC positive temperature coefficient
  • the refrigerant blends may be used in a variety of heating and cooling systems.
  • a reversing valve is used and the same loop is used for cooling and heating.
  • air side bypass or refrigerant valving/system design changes can accomplish the same effect as a reversible cycle, without a reversing valve.
  • 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 first heat exchanger 120 has passing through it the refrigerant of the loop 110 and the stream of air created by a fan.
  • the refrigerant set-in motion by the compressor 150 passes, via the valve 160, through the heat exchanger 120 which acts as a condenser, that is to say gives up heat energy to the outside, then through the pressure regulator 130 then through the heat exchanger 140 that is acting as an evaporator thus cooling the stream of air intended to be blown into the motor vehicle cabin interior.
  • the direction of flow of the refrigerant is reversed using the valve 160.
  • the heat exchanger 140 acts as a condenser while the heat exchanger 120 acts as an evaporator.
  • the heat exchanger 140 can then be used to heat up the stream of air intended for the motor vehicle cabin.
  • Additional heat transfer loops may be connected to the heat pump system and absorb or reject heat at the heat exchangers 120 and/or 140 to allow transfer of heat away from the motor or battery, and therefore serve to provide thermal management of those components of the vehicle as well as cooling and heating for the passenger cabin.
  • a refrigeration system 300 having a refrigeration loop 310 comprises a first heat exchanger 320, a pressure regulator 330, a second heat exchanger 340, a compressor 350 and a four-way valve 360.
  • the first and second heat exchangers 320 and 340 are of the air/refrigerant type.
  • the way in which the heat exchangers 320 and 340 operate is the same as in the first embodiment depicted in FIG. 1.
  • Two fluid/liquid heat exchangers 370 and 380 are installed both on the refrigeration loop circuit 310 and on the engine cooling circuit or on a secondary glycol-water circuit. Installing fluid/liquid heat exchangers without going through an intermediate gaseous fluid (e.g.
  • the system for heating and cooling the passenger compartment of an electric vehicle further comprises a reheater operably connected between the compressor and the condenser for reduction of humidity in the passenger compartment during cooling mode.
  • a refrigeration system 400 having a refrigeration loop 410 comprises a first heat exchanger (condenser) 420, a pressure regulator 430, a second heat exchanger (evaporator) 440, a compressor 450, a three-way valve 460, and a third heat exchanger (for reheat) 470.
  • a first heat exchanger condenser
  • a pressure regulator 430 a second heat exchanger
  • a compressor 450 for reheat
  • three-way valve 460 for reheat
  • a third heat exchanger (for reheat) 470 In cooling mode, at least a portion of the discharge flow exiting the compressor 450 is directed through the three-way valve 460 and into the third heat exchanger 470.
  • the exit stream from the third heat exchanger 470 discharges into the inlet of the first heat exchanger 420.
  • the refrigerant is condensed by the first heat exchanger 420 using an external fan 480 and ambient air as the heat sink.
  • the existing saturated or subcooled liquid is expanded in the pressure regulator 430 and the resulting lower pressure saturated mixture of refrigerant liquid and vapor enters the second heat exchanger 440.
  • the refrigerant evaporates in the second heat exchanger 440 through the use of a second fan 490 that is external to the refrigeration loop.
  • the air passing across the second heat exchanger 440 is cooled to below the air dew point temperature. This causes the moisture in the air to partially condense, thereby lowering the absolute humidity of the air.
  • the air then passes over the third heat exchanger 470, which transfers heat into the air, increasing the air temperature to above the dew point and lowering the relative humidity of the air, which is then supplied to the passenger compartment.
  • the three-way valve 460 is modulated to prohibit the flow of refrigerant to the first heat exchanger 420 and all vehicle cabin heating is accomplished using the third heat exchanger 470 in the heat pump configuration described in FIG. 1.
  • an air-conditioning (AC) and heat pump (HP) system 500 heating, cooling, or both can be accomplished in a vehicle cabin or for other vehicle loads.
  • the system 500 includes an AC circuit 510 and a HP circuit 520.
  • the HP control valve 530 upstream of the heat pump condenser 540 will be closed and the refrigerant will flow from the compressor 550 into the air-cooled AC condenser 560, through an AC expansion valve 570, and into the AC evaporator 580; providing cooling to the cabin. From the AC evaporator 580, the refrigerant will flow back to the compressor 550.
  • the AC control valve 535 upstream of the AC condenser 560 will be closed and the refrigerant will flow from the compressor 550 into the HP condenser 540 to provide heating to the cabin. From the HP condenser 540 the refrigerant will flow through the HP expansion valve 575 to the HP evaporator 585.
  • a separate humidity control mode could be accomplished by sending a portion of the compressor discharge gas into the AC circuit 510 and the remaining portion into the HP circuit 520.
  • a system 600 for heating, cooling, or both can be accomplished for a vehicle cabin or for other vehicle loads.
  • the system 600 includes an AC circuit 610 and a water-cooled/HP circuit 620.
  • the water loop control valve 630 upstream of the water-cooled condenser 640 will be closed and the refrigerant will flow from the compressor 650 into the AC condenser 660, through an AC expansion valve 670, and into the AC evaporator 680; providing cooling to the cabin.
  • the AC control valve 635 upstream of the AC condenser 660 will be closed and the refrigerant will flow from the compressor 650 into the water-cooled condenser 640.
  • a heat transfer fluid (e.g., water or other heat transfer fluid) will take the heat generated in the water-cooled condenser 640 and transfer it to the cabin heater core 690; providing heat to the cabin.
  • the heat transfer fluid may return from the cabin heater core 690 to the water-cooled condenser 640.
  • the refrigerant will flow from the water-cooled condenser 640 through an HP expansion valve 675 into the HP evaporator 685 that cools a heat transfer fluid, which may be used to cool other components of the automobile and then back to the compressor 650.
  • there is one or more water/heat transfer fluid loop that may be used to heat and/or cool various other components of the vehicle.
  • a separate humidity control mode could be accomplished by sending a portion of the compressor discharge gas into the AC circuit 610 and the remaining portion into the water cooled/HP circuit 620.
  • the refrigerant circuit 700 in heating mode wherein specific conditions exist where both the vehicle cabin and other vehicle components require heat, the refrigerant circuit 700 operates as shown in FIG. 6. Starting at the compressor 750, discharge refrigerant vapor will take two paths. One path is through the cabin condenser 740.
  • the cabin condenser 740 is a refrigerant-to-air heat exchanger typically of the fin-tube or microchannel type and can be single or multiple pass.
  • a first fan 745 in the vehicle ventilation ductwork will induce 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 and the refrigerant as it condenses will heat the air.
  • a physical bypass 735 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin evaporator 730.
  • the second path of refrigerant out of the compressor is through valve 770 and into a liquid/heat transfer fluid heat exchanger 720, which allows heat to be transferred from the warm refrigerant to the vehicle’s heat transfer fluid loop (not shown).
  • This vehicle heat transfer loop can then be used to manage other vehicle heat loads.
  • the heat transfer fluid of the heat transfer fluid loop may be water or a water/glycol solution.
  • the condensed refrigerant out of exchanger 720 then combines with the condenser 740 liquid refrigerant outlet and the combined stream flows through an expansion device 775, which will drop the pressure of the liquid refrigerant and generate a liquid-vapor mixture.
  • This liquid-vapor mixture then flows through the outdoor heat exchanger 780 (i.e. , evaporator in this setup).
  • the outdoor heat exchanger 780 will be a refrigerant-to-air heat exchanger typically of the fin-tube or microchannel type and can be single or multiple pass.
  • a second fan 785 will induce airflow across the outdoor heat exchanger 780 and allow the liquid-vapor refrigerant mixture to pick up heat from the ambient air and vaporize completely before it flows back to the compressor 750.
  • the refrigerant circuit 800 in heating mode when specific conditions exist where only cabin heating is required, operates as shown in FIG. 7. Starting at the compressor 850, discharge vapor will first flow through the cabin condenser 840. A first fan 845 in the vehicle ventilation ductwork will induce a flow of either 100% outside air or a mixture of outside air and return air from the vehicle cabin across this cabin condenser 840 and the refrigerant will exchange heat between the condenser 840 and the air. In this mode, a physical bypass 835 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin evaporator 830.
  • the refrigerant will condense in the cabin condenser 840 and flow to an expansion device 875 which will drop the pressure of the liquid refrigerant and generate a liquid-vapor mixture.
  • This liquid-vapor mixture flows through the outdoor heat exchanger 880 (i.e. , evaporator in this setup).
  • a second fan 885 will induce airflow across the outdoor heat exchanger 880 and allow the liquid-vapor refrigerant mixture to pick up heat from the ambient air and vaporize completely before it travels back to the compressor 850.
  • the refrigerant circuit 900 in cooling mode when specific conditions exist where both the vehicle cabin and the vehicle components require cooling, operates as shown in FIG. 8. Starting at the compressor 950, discharge refrigerant vapor will first flow through the cabin condenser 940, wherein there will be no heat transfer as in this mode, a physical bypass 945 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin condenser 940. Vapor refrigerant will pass through the cabin condenser 940 and flow through valve 975 and into the outdoor heat exchanger 980.
  • the outdoor 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 to a liquid. A portion of this liquid refrigerant will leave the outdoor heat exchanger 980 and enter the internal heat exchanger 990. Liquid refrigerant will be subcooled in the internal heat exchanger 990 and then flow to an expansion device 910 and into the cabin evaporator 930. This air-to-refrigerant cabin evaporator 930 will be of the fin-tube or microchannel type of heat exchanger and can be single or multiple pass.
  • a second fan (or cabin blower fan) 935 will induce a flow of either 100% outside air or a mixture of outside air and return air from the cabin across the coil of the cabin evaporator 930 where heat will be exchanged between the air and refrigerant.
  • the refrigerant will vaporize and travel back to the internal heat exchanger 990 where it will be further superheated until it finally re-enters the compressor 950.
  • the remaining portion of refrigerant exiting the condenser 980 will flow through expansion valve 915 and into the liquid/heat transfer fluid heat exchanger 920 wherein vehicle component heat is transferred via a heat transfer fluid loop (not shown) into the refrigerant. This vehicle heat transfer loop can then be used to manage other vehicle heat loads.
  • the refrigerant vaporizes in heat exchanger 920 and joins the refrigerant exiting internal heat exchanger 990 at the suction of the compressor 950.
  • the refrigerant circuit 1000 in cooling mode when specific conditions exist where only vehicle cabin cooling is required, operates as shown in FIG. 9. Starting at the compressor 1050, discharge refrigerant vapor will first flow through the cabin condenser 1040, wherein there will be no heat transfer, as in this mode, a physical bypass 1045 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin condenser 1040. Vapor refrigerant will pass through the cabin condenser 1040 and flow through a valve 1075 to the outdoor heat exchanger 1080.
  • the outdoor heat exchanger 1080 acts as a condenser as a first fan 1085 induces flow across the heat exchanger 1080 and the hot refrigerant vapor exchanges heat and condenses to a liquid.
  • This liquid refrigerant will leave the outdoor heat exchanger 1080 and enter the internal heat exchanger 1090.
  • Liquid refrigerant will be subcooled in the internal heat exchanger 1090 and then flow to an expansion device 1010 and into the cabin evaporator 1030.
  • a second fan (or cabin blower fan) 1035 will induce 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 refrigerant.
  • the refrigerant will vaporize and flow back to the internal heat exchanger 1090 where it will be further superheated until it finally returns to the compressor 1050.
  • the refrigerant blends of the present disclosure containing HFO-1234zeE, HFC-32, and HFC-152a have low GWP, low toxicity, and low flammability with low temperature glide for use in a hybrid, mild hybrid, plug-in hybrid, or full electric vehicles for thermal management (transferring heat from one part of the vehicle to the other) of the passenger compartment providing air conditioning (A/C) or heating to the passenger cabin. Additionally, the refrigerant blends provide improved performance under the same conditions as compared to HFO-1234yf in particular capacity higher than HFO-1234yf alone, even 20% higher or more than HFO-1234yf alone when operating under the same conditions, and COP higher than HFO-1234yf alone.
  • the COP is preferably at least 5% higher than HFO-1234yf alone, or more preferably at least 6% higher than HFO-1234yf alone, or most preferably at least 7% higher than HFO-1234yf alone when operating under the same conditions.
  • a method for replacing HFO-1234yf in a heating and cooling system contained within an electric vehicle comprising providing any of the foregoing compositions to said heating and cooling system as a heat transfer fluid.
  • the composition for replacing HFO-1234yf comprises a refrigerant blend consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC- 152a. In another embodiment, said refrigerant blend consisting essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consisting essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consisting essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consisting essentially of from about 63 to 69 weight percent HFO- 1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consisting essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. According to any of the foregoing embodiments, the refrigerant blend produces volumetric heating capacity at least 10% higher, or 15% higher, or 20% higher than HFO-1234yf alone when operating under the same conditions.
  • the average temperature glide with the replacing composition is less than 6.0 K, preferably less than 5.0 K, or more preferably less than 4.0 K.
  • a method for replacing HFO-1234yf in a cooling system contained within an internal combustion engine or hybrid vehicle comprising adding any of the foregoing compositions to said cooling system as a heat transfer fluid.
  • the replacement may be made at the time of servicing the vehicle due to leakage or loss of refrigerant performance or at the initial charging of the system that was designed for using HFO-1234yf.
  • the composition for replacing HFO-1234yf comprises a refrigerant blend consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consisting essentially of from about 63 to 80 weight percent HFO- 1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consisting essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • said refrigerant blend consisting essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consisting essentially of from about 68 to 93 weight percent HFO- 1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consisting essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • the refrigerant blend produces volumetric heating capacity at least 10% higher, or 15% higher, or 20% higher than HFO-1234yf alone when operating under the same conditions.
  • the average temperature glide with the replacing composition is less than 6.0 K, preferably less than 5.0 K, or more preferably less than 4.0 K.
  • a method of servicing the heating and cooling system of an electric vehicle comprising removing all of a used refrigerant from the system and charging the system with the compositions comprising a refrigerant blend consisting essentially of HFO-1234zeE, HFC-32, and H FC- 152a.
  • the used refrigerant may be any of the foregoing compositions, or the used refrigerant may be a composition that is altered from any of the foregoing compositions due to some degree of fractionation and preferential leakage of the lower boiling components of the refrigerant blend.
  • compositions comprising a refrigerant blend consisting essentially of HFO-1234zeE, HFC-32, and H FC- 152a as a heat transfer fluid in a system for heating and cooling the passenger compartment of an electric vehicle.
  • the refrigerant composition exhibit a low GWP as well as similar or improved refrigerant properties compared to conventional refrigerants.
  • the compositions as disclosed herein may be used in stationary systems, such as refrigeration, air conditioning and heat pump systems.
  • the present inventive compositions may serve as replacements for conventional refrigerants with much higher GWP, in particular, such as R-404A, R-410A, R-407A, R-407C, or R-407F.
  • the stationary systems may include supermarket refrigerated cases, supermarket freezer cases, chillers that provide air conditioning to large buildings, such as apartment buildings, 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.
  • the chiller systems mentioned may be centrifugal, screw, or scroll systems as defined by the compressor being used. Additionally, the chiller may operate with direct expansion heat exchangers or with flooded evaporator heat exchangers.
  • a stationary refrigeration, air conditioning or heat pump apparatus containing a refrigerant consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 82 weight percent HFO- 1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a.
  • the refrigerant blend consists essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC- 152a. In another embodiment, said refrigerant blend consists essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consists essentially of from about 71 to 93 weight percent HFO- 1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • a method for replacing a first refrigerant selected from R-22, R-404A, R-507A, R-507B, R-410A, R-407A, R-407C, or R-407F comprising removing at least a portion of said first refrigerant and charging a second refrigerant consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 86 weight percent HFO-1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 84 weight percent HFO- 1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 80 weight percent HFO-1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consists essentially of from about 63 to 76 weight percent HFO- 1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 68 to 93 weight percent HFO-1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consists essentially of from about 71 to 93 weight percent HFO- 1234zeE, from about 6 to 9 weight percent H FC-32, and from about 1 to 20 weight percent HFC-152a.
  • a method for replacing a first refrigerant selected from R-513A, R-448A, R-448B, R-449A, R-452A, R-454A, R- 454B, R-454C, R-466A, R-1234yf, or R-1234ze comprising removing at least a portion of said first refrigerant and charging a second refrigerant consisting essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 93 weight percent HFO-1234zeE, from about 6 to 17 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 86 weight percent HFO- 1234zeE, from about 11 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 84 weight percent HFO-1234zeE, from about 14 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 82 weight percent HFO-1234zeE, from about 16 to 21 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 63 to 80 weight percent HFO- 1234zeE, from about 11 to 17 weight percent HFC-32, and from about 7 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consists essentially of from about 63 to 76 weight percent HFO-1234zeE, from about 14 to 17 weight percent HFC-32, and from about 10 to 20 weight percent HFC-152a.
  • said refrigerant blend consists essentially of from about 63 to 69 weight percent HFO-1234zeE, from about 16 to 17 weight percent HFC-32, and from about 15 to 20 weight percent HFC-152a. In another embodiment, said refrigerant blend consists essentially of from about 68 to 93 weight percent HFO- 1234zeE, from about 6 to 12 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. In another embodiment, the refrigerant blend consists essentially of from about 71 to 93 weight percent HFO-1234zeE, from about 6 to 9 weight percent HFC-32, and from about 1 to 20 weight percent HFC-152a. [0195] This use of the present inventive compositions has been described in detail in the foregoing description and will be demonstrated in the forthcoming examples. The following Examples are provided to illustrate certain aspects of the invention and shall not limit the scope of the appended claims.
  • thermodynamic modeling program was used to model the expected performance of the blends containing HFO-1234zeE, HFC-152a, and HFC-32, as compared to HFO-1234yf alone. Fourteen different sets of conditions were modeled, the conditions being specified by the Society of Automotive Engineers (SAE) for characterization of refrigerant performance in an automobile heat pump system. Physical properties for the components were taken from NIST REFPROP Version 10.
  • Compressor isentropic efficiency 70%
  • Compressor volumetric efficiency 95 %
  • compositions as listed in Table 3 have performance similar enough to neat HFO-1234yf that those compositions containing HFO-1234zeE, HFC-32, and HFC-152a might be used to top off the heat transfer fluid in an existing automobile in need of additional refrigerant. Or the compositions may be useful when a new full charge of refrigerant is needed as well to replace the HFO-1234yf entirely at time of service.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des mélanges réfrigérants respectueux de l'environnement utilisant des réfrigérants comprenant du E-1,3,3,3-tétrafluoropropène (HFO-1234zeE), du difluorométhane (HFC-32) et du 1,1-difluoroéthane (HFC-152a). Les mélanges ont un faible GWP, une faible toxicité et une faible inflammabilité avec un rendement amélioré pour une utilisation dans des véhicules hybride, semi-hybride, hybride rechargeable ou tout électrique pour la gestion thermique (transfert de chaleur d'une partie du véhicule à l'autre) de l'habitacle fournissant une climatisation (A/C) ou un chauffage de la cabine passagers.
PCT/US2024/031534 2023-05-31 2024-05-30 Compositions de hfo-1234ze(e), hfc-32 et hfc-152a et systèmes d'utilisation de ces compositions Pending WO2024249542A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202480030536.XA CN121057799A (zh) 2023-05-31 2024-05-30 HFO-1234ze(E)、HFC-32和HFC-152a的组合物以及使用该组合物的系统
AU2024279576A AU2024279576A1 (en) 2023-05-31 2024-05-30 Compositions of hfo-1234ze(e), hfc-32, and hfc-152a and systems for using the compositions
MX2025013747A MX2025013747A (es) 2023-05-31 2025-11-18 Composiciones de e-1,3,3,3-tetrafluoropropeno (hfo-1234ze(e)), difluorometano (hfc-32) y 1,1-difluoroetano (hfc-152a) y sistemas para usar las composiciones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363469887P 2023-05-31 2023-05-31
US63/469,887 2023-05-31

Publications (1)

Publication Number Publication Date
WO2024249542A1 true WO2024249542A1 (fr) 2024-12-05

Family

ID=91664780

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/031534 Pending WO2024249542A1 (fr) 2023-05-31 2024-05-30 Compositions de hfo-1234ze(e), hfc-32 et hfc-152a et systèmes d'utilisation de ces compositions

Country Status (4)

Country Link
CN (1) CN121057799A (fr)
AU (1) AU2024279576A1 (fr)
MX (1) MX2025013747A (fr)
WO (1) WO2024249542A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120795874A (zh) * 2025-09-16 2025-10-17 浙江巨化新材料研究院有限公司 传热组合物及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5399631A (en) 1992-06-04 1995-03-21 Idemitsu Kosan Co., Ltd. Polyvinyl ether compound
US6454960B1 (en) 1996-11-28 2002-09-24 Sanyo Electric Co., Ltd. Refrigerator using a polyvinyl ether refrigerator oil
WO2007126414A2 (fr) 2006-03-30 2007-11-08 E. I. Du Pont De Nemours And Company Préparations comprenant une fluoroléfine
EP2727980A1 (fr) 2011-07-01 2014-05-07 Idemitsu Kosan Co., Ltd Composition d'huile lubrifiante pour réfrigérateur à compression
US8926856B2 (en) * 2010-02-16 2015-01-06 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US9169427B2 (en) * 2011-07-13 2015-10-27 Honeywell International Inc. Low GWP heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
WO2019213004A1 (fr) 2018-04-30 2019-11-07 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5399631A (en) 1992-06-04 1995-03-21 Idemitsu Kosan Co., Ltd. Polyvinyl ether compound
US6454960B1 (en) 1996-11-28 2002-09-24 Sanyo Electric Co., Ltd. Refrigerator using a polyvinyl ether refrigerator oil
WO2007126414A2 (fr) 2006-03-30 2007-11-08 E. I. Du Pont De Nemours And Company Préparations comprenant une fluoroléfine
US8926856B2 (en) * 2010-02-16 2015-01-06 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
EP2727980A1 (fr) 2011-07-01 2014-05-07 Idemitsu Kosan Co., Ltd Composition d'huile lubrifiante pour réfrigérateur à compression
US9169427B2 (en) * 2011-07-13 2015-10-27 Honeywell International Inc. Low GWP heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
WO2019213004A1 (fr) 2018-04-30 2019-11-07 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation
WO2020222865A1 (fr) 2018-04-30 2020-11-05 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation
WO2020222864A1 (fr) 2018-04-30 2020-11-05 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120795874A (zh) * 2025-09-16 2025-10-17 浙江巨化新材料研究院有限公司 传热组合物及其制备方法和应用

Also Published As

Publication number Publication date
MX2025013747A (es) 2025-12-01
CN121057799A (zh) 2025-12-02
AU2024279576A1 (en) 2025-10-23

Similar Documents

Publication Publication Date Title
JP7654730B2 (ja) Ｈｆｏ－１２３４ｙｆ及び炭化水素の共沸組成物
AU2024279576A1 (en) Compositions of hfo-1234ze(e), hfc-32, and hfc-152a and systems for using the compositions
US20250145876A1 (en) Compositions of hfo-1234yf, hfo-1132e, and hfc-152a and systems for using the compositions
US20250145875A1 (en) Compositions of hfo-1234yf, hfo-1132e, and hydrocarbons and systems for using the compositions
US20240409797A1 (en) Compositions of hfo-1234yf, hfc-32, hfc-152a, and hydrocarbons and systems for using the compositions
US20240279521A1 (en) Compositions of hfo-1234yf, hfc-32, and hfc-152a and systems for using the compositions
US20240209249A1 (en) Compositions of hfo-1234yf and hfc-152a and systems for using the compositions
US20240287367A1 (en) Compositions of hfo-1234yf, hfc-152a, and hfc-32, and systems for using the compositions
WO2025019198A1 (fr) Procédés et systèmes utilisant du 1,1-difluoropropène
WO2025072113A1 (fr) Appareil et procédés d'utilisation de z-1,2-difluoroéthylène
KR20210070329A (ko) Hfo-1234yf 및 프로필렌의 공비 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24736176

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: AU2024279576

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2024279576

Country of ref document: AU

Date of ref document: 20240530

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2501007667

Country of ref document: TH

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112025025967

Country of ref document: BR