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WO2025193322A1 - Compositions à faible gwp comprenant du hfo-1252 zc et leurs utilisations - Google Patents

Compositions à faible gwp comprenant du hfo-1252 zc et leurs utilisations

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Publication number
WO2025193322A1
WO2025193322A1 PCT/US2025/011631 US2025011631W WO2025193322A1 WO 2025193322 A1 WO2025193322 A1 WO 2025193322A1 US 2025011631 W US2025011631 W US 2025011631W WO 2025193322 A1 WO2025193322 A1 WO 2025193322A1
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WO
WIPO (PCT)
Prior art keywords
hfc
hfo
composition
cooling
1234zee
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/US2025/011631
Other languages
English (en)
Inventor
Joshua Hughes
Luke David SIMONI
Mary E. Koban
Konstantinos Kontomaris
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
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Filing date
Publication date
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Publication of WO2025193322A1 publication Critical patent/WO2025193322A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C09K2205/106—Carbon dioxide
    • 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
    • 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
    • C09K2205/40—Replacement mixtures

Definitions

  • the present disclosure relates to compositions useful as refrigerants, and in particular, for refrigeration systems.
  • the compositions of the present disclosure are useful in methods for producing cooling, and methods for replacing refrigerants and refrigeration systems, including low and medium temperature refrigeration and transport refrigeration systems.
  • HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,430 and 3,500 according to the UN's IPCC Fourth Assessment Report (AR4).
  • GWP global warming potentials
  • the instant invention solves certain problems associated with conventional refrigerants and provides refrigerant blends containing 1 ,1-difluoropropene, which meets the evolving regulatory landscape.
  • a fluoropropene composition comprising 1,1- difluoropropene (also called HFO-1252zc, or R-1252zc). This compound is shown herein to have advantageous properties for its use in refrigerant applications.
  • compositions comprising HFO- 1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 .
  • % means weight percent
  • compositions comprising:
  • HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a are HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or
  • compositions comprising, consisting of, or essentially consisting of 1% to 21% HFO- 1252zc, 57% to 80% HFO-1234zeE, 13% to 22% HFC-32, and 1% to 2% weight percent CO 2 .; or 1.0% to 6.0% of CO 2 , 1.0% to 96.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 49.0% of HFC-32; or 1 .0% to 6.0% of CO 2 , 1.0% to 96.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 28.0% of HFC-32; or 1.0% to 6.0% of CO 2 , 16.0% to 85.0% of HFO-1252zc, 1.0% to 61.0% of HFO1234zeE 1234ZEE, and 1.0% to 28.0% of HFC-32; or 1 .0%
  • compositions comprising, consisting of, or essentially consisting of: 1% to 21 % HFO- 1252zc, 57% to 80% HFO-1234zeE, 13% to 22% HFC-32, and 1% to 6% HFC-134; or 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, 1.0% to 43.0% of HFC-32, and 1.0% to 28.0% of HFC-134; or 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, 1.0% to 43.0% of HFC-32, and 1.0% to 28.0% of HFC- 134; or 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, 1.0% to 43.0% of HFC-32, and 1.0% to 28.0% of HFC-134; or 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.
  • compositions comprising, consisting of, or essentially consisting of: 1% to 21 % HFO- 1252zc, 57% to 80% HFO-1234zeE, 17% to 22% HFC-32, and 1% to 3% HFC-134a; or 1.0% to 23.0% of HFC-134a, 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 52.0% of HFC-32; or 1.0% to 23.0% of HFC-134a, 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 52.0% of HFC-32; or 1.0% to 22.0% of HFC-134a, 1.0% to 80.0% of HFO-1252zc, 1.0% to 71.0% of HFO-1234zeE, and 1.0% to 49.0% of HFC-32; or
  • compositions comprising, consisting of, or essentially consisting of: 1% to 21 % HFO- 1252zc, 54% to 80% HFO-1234zeE, 11% to 22% HFC-32, 1% to 6% HFC-134, and 1 % to 3% CO 2 ; or 1.0% to 3.0% of CO 2 , 1 .0% to 6.0% of HFC-134, 1 .0% to 20.0% of HFO-1252zc, 42.0% to 73.0% of HFO-1234zeE, and 11.0% to 38.0% of HFC-32; or 1.0% to 3.0% of CO 2 , 1.0% to 6.0% of HFC-134, 1.0% to 20.0% of HFO-1252zc, 42.0% to 73.0% of HFO-1234zeE, and 11 .0% to 38.0% of HFC-32; or 2.0% to 2.0% of CO 2 , 1.0% to 1.0% of HFC-134, 18.0% to 18.
  • compositions comprising, consisting of, or essentially consisting of: 1.0% to 96.0% of HFO-1252zc, 1.0% to 96.0% of HFO-1234ze(E), 1.0% to 25.0% of HFC-134, 1.0% to 21.0% of HFC-134a, and 1.0% to 40.0% of HFC-32; or 1.0% to 96.0% of HFO- 1252zc, 1.0% to 96.0% of HFO-1234ze(E), 1.0% to 11.0% of HFC-134, 1.0% to 10.0% of HFC-134a, and 1.0% to 18.0% of HFC-32; or 41.0% to 82.0% of HFO- 1252zc, 1.0% to 39.0% of HFO-1234ze(E), 1.0% to 3.0% of HFC-134, 1.0% to 2.0% of HFC-134a, and 15.0% to 18.0% of HFC-32; or 41.0% to 63.0% of HFO-1252
  • compositions comprising, consisting of, or essentially consisting of: 0.2% to 89.1 % of CO2, 0.2% to 97.5% of HFO-1252zc, 0.2% to 97.5% of HFO-1234ze(E), 0.2% to 22.0% of HFC-134a, and 0.2% to 43.8% of HFC-32; or 0.2% to 89.1% of CO 2 , 0.2% to 97.5% of HFO-1252zc, 0.2% to 97.5% of HFO-1234ze(E), 0.2% to 10.0% of HFC- 134a, and 0.2% to 19.9% of HFC-32; or 0.2% to 4.0% of CO2, 25.7% to 85.6% of HFO-1252zc, 0.2% to 53.5% of HFO-1234ze(E), 0.2% to 8.0% of HFC-134a, and 5.9% to 19.9% of HFC-32; or .2% to 4.0% of CO2, 25.7% to 63.7%
  • compositions further comprising at least one additional compound selected from HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC- 143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-374, n-butane, allene, 2-butene, cyclobutene, 2-methyl propene, HCFO-1122, HFO-1132, HFO- 1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO- 1243zf, HCFO-1251, HCO-1260zf, HFO-12
  • compositions further comprising at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO- 1252yf, HFO-1252zf, and HFO-1252ye.
  • compositions wherein said composition further comprises from 0.1 to 200 ppm by weight of water; from about 10 ppm by volume to about 0.35 volume percent oxygen; and/or from about 100 ppm by volume to about 1.5 volume percent air or NAG.
  • compositions wherein said composition comprises 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, - 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 g
  • 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 wherein the composition further comprises a lubricant are also disclosed herein.
  • 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 said lubricant has at least one property selected from the group consisting of 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; a breakdown voltage of at least 25 kV; and a hydroxy value of at most 0.1 mg KOH/g.
  • compositions wherein the composition comprises at least one tracer.
  • compositions wherein said 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-141 b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141 ,
  • compositions wherein the composition is free of or substantially free of Group A Fluorinated Substances, and wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.
  • compositions wherein the composition is classified as class 2 or 2L for flammability.
  • refrigeration systems comprising a composition of any of the foregoing embodiments.
  • refrigeration systems comprising a composition of any of the foregoing embodiments, for use in high ambient applications, wherein outdoor temperatures are above about 35°C.
  • refrigeration systems comprising an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • refrigeration systems comprising an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • refrigeration systems wherein said refrigeration system is for residential, light commercial, or industrial refrigeration.
  • refrigeration systems containing any of the compositions of the foregoing embodiments, wherein said system is for medium temperature refrigeration, low temperature refrigeration, or transport refrigeration.
  • compositions of any of the foregoing embodiments as refrigerant in low temperature refrigeration systems, medium temperature refrigeration systems, and/or transport refrigeration systems.
  • This invention relates to compositions containing 1 ,1 -difluoropropene (HFO-1252zc), E-1 ,3,3,3-tetrafluoropropene (HFO-1234zeE), difluoromethane (HFC- 32), and at least one of 1 ,1 ,2,2-tetrafluoroethane (HFC-134) or carbon dioxide (CO2).
  • the compositions may potentially be candidates to replace refrigerants such as R- 454C, R-410A, or propane with low Global Warming Potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).
  • compositions comprise HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2. These blends provide refrigerant blends with low global warming potential, improved glide as compared to other suggested refrigerant blends, and improved coefficient of performance as compared to existing refrigerants and other proposed replacements.
  • a refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during a cycle used to transfer of heat.
  • a heat transfer system is the system (or apparatus) used to produce a heating or cooling effect in a particular space.
  • a heat transfer system may be a mobile system or a stationary system.
  • Examples of heat transfer systems are any type of refrigeration systems and air conditioning systems including, but are not limited to, stationary heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, flooded evaporator heat pumps, direct expansion chillers heat pumps, chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile heat transfer systems, mobile heat pumps (including heat pumps for cabin comfort cooling and heating in automobiles), mobile air conditioning units (for cooling of passenger compartments in automobiles), dehumidifiers, and combinations thereof.
  • the focus of the present application is refrigeration systems, including low temperature refrigeration systems and medium temperature refrigeration systems.
  • 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).
  • Subcooling refers to the reduction of the temperature of a liquid below that liquid’s saturation point for a given pressure.
  • the liquid saturation point is the temperature at which the vapor is completely condensed to a liquid.
  • the subcool amount is the amount of cooling below the saturation temperature (in degrees).
  • 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.
  • the net refrigeration effect is the quantity of heat that each kilogram of refrigerant absorbs in the evaporator to produce useful cooling.
  • the mass flow rate is the quantity of refrigerant in kilograms circulating through the refrigeration, heat pump or air conditioning system over a given period of time.
  • lubricant means any material added to a composition or a compressor (and in contact with any heat transfer composition in use within any heat transfer system) that provides hydrodynamic lubrication to the compressor to aid in preventing parts from seizing.
  • 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 GWP values are those reported in the United Nations Intergovernmental Panel on climate Change (IPCC) Fourth Assessment Report (AR4).
  • IPCC Intergovernmental Panel on climate Change
  • AR4 Fourth Assessment Report
  • ODP Ozone depletion potential
  • HFCs Hydrofluorocarbons
  • HFO hydrofluoro-olefins
  • 1,1 -Difluoropropene (HFO-1252zc or R-1252zc) may be prepared by hydrogenation of 3,3,3-trifluoropropene (HFO-1243zf) over palladium on carbon catalyst to form 1,1,1 -trifluoropropane (HFC-263fb), followed by dehydrofluorination of the HFC-263fb over chrome catalyst or by pyrolysis at high temperatures (see attorney docket number FL2084, filed herewith, and herein incorporated by reference).
  • E-1,3,3,3-Tetrafluoropropene (HFO-1234zeE or R-1234zeE) is available commercially from Honeywell (Charlotte, North Carolina, USA). And difluoromethane (HFC-32 or R-32), 1,1,2,2-tetrafluoroethane, (HFC-134 or R-134), 1 ,1 ,1,2-tetrafluoroethane (HFC-134a or R-134a) and carbon dioxide (CO2) are available commercially from various sources worldwide.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof are intended to cover a non-exclusive inclusion. For example, 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.
  • transitional phrase "consisting essentially of” is used to define a composition, method or apparatus 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 not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of'.
  • components of the refrigerant mixtures and the refrigerant mixtures themselves can contain minor amounts (e.g., less than about 0.5 weight percent total) of impurities and/or byproducts (e.g., from the manufacture of the refrigerant components or reclamation of the refrigerant components from other systems) which do not materially affect the novel and basic characteristics of the refrigerant mixture.
  • minor amounts e.g., less than about 0.5 weight percent total
  • impurities and/or byproducts e.g., from the manufacture of the refrigerant components or reclamation of the refrigerant components from other systems
  • compositions comprise, consist of, or consist essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2.
  • GWP Global Warming Potential
  • COP energy efficiency
  • compositions comprise, consist of, or consist essentially of: 1% to 21% HFO-1252zc, 57% to 80% HFO-1234zeE, 13% to 22% HFC-32, and 1 % to 2% CO 2 ; or 1 .0% to 6.0% of CO 2 , 1 .0% to 96.0% of HFO- 1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 49.0% of HFC-32; or 1.0% to 6.0% of CO2, 1.0% to 96.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 28.0% of HFC-32; or 1.0% to 6.0% of CO 2 , 16.0% to 85.0% of HFO-1252zc, 1.0% to 61.0% of HFO1234zeE 1234ZEE, and 1.0% to 28.0% of HFC-32; or 1.0% to 2.0% of CO 2 , 16.0% to 19.0% of HFO-12
  • compositions comprise, consist of, or consist essentially of: 1% to 21% HFO-1252zc, 57% to 80% HFO-1234zeE, 13% to 22% HFC-32, and 1 % to 6% HFC-134; or 1.0% to 97.0% of HFO-1234zeE, 1.0% to 43.0% of HFC-32, and 1.0% to 28.0% of HFC-134; or 1.0% to 97.0% of HFO- 1252zc, 1.0% to 97.0% of HFO-1234zeE, 1.0% to 43.0% of HFC-32, and 1 .0% to 28.0% of HFC-134; or 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO- 1234zeE, 1.0% to 43.0% of HFC-32, and 1.0% to 28.0% of HFC-134; or 1.0% to 27.0% of HFO-1252zc, 30.0% to 97.0% of HFO-1234zeE
  • compositions comprise, consist of, or consist essentially of: 1% to 21% HFO-1252zc, 57% to 80% HFO-1234zeE, 17% to 22% HFC-32, and 1 % to 3% HFC-134a; or 1.0% to 23.0% of HFC-134a, 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO-1234zeE, and 1.0% to 52.0% of HFC-32; or 1.0% to 23.0% of HFC-134a, 1.0% to 97.0% of HFO-1252zc, 1.0% to 97.0% of HFO- 1234zeE, and 1.0% to 52.0% of HFC-32; or 1.0% to 22.0% of HFC-134a, 1.0% to 80.0% of HFO-1252zc, 1.0% to 71.0% of HFO-1234zeE, and 1.0% to 49.0% of HFC- 32; or 1.0% to 15.0% of HFC-134a, 1.0%
  • compositions comprise, consist of, or consist essentially of: 1% to 21% HFO-1252zc, 54% to 80% HFO-1234zeE, 11% to 22% HFC-32, 1% to 6% HFC-134, and 1 % to 3% CO 2 ; or 1.0% to 3.0% of CO 2 , 1.0% to 6.0% of HFC-134, 1.0% to 20.0% of HFO-1252zc, 42.0% to 73.0% of HFO-1234zeE, and 11 .0% to 38.0% of HFC-32; or 1 .0% to 3.0% of CO 2 , 1.0% to 6.0% of HFC-134, 1.0% to 20.0% of HFO-1252zc, 42.0% to 73.0% of HFO-1234zeE, and 11.0% to 38.0% of HFC-32; or 2.0% to 2.0% of CO 2 , 1 .0% to 1 .0% of HFC-134, 18.0% to 18.0% of HFO-1252zc, 57.0% to
  • compositions comprise, consist of, or consist essentially of: 1.0% to 96.0% of HFO-1252zc, 1.0% to 96.0% of HFO-1234ze(E), 1 .0% to 25.0% of HFC-134, 1 .0% to 21 .0% of HFC-134a, and 1 .0% to 40.0% of HFC-32; or 1.0% to 96.0% of HFO-1252zc, 1.0% to 96.0% of HFO-1234ze(E), 1.0% to 11.0% of HFC-134, 1.0% to 10.0% of HFC-134a, and 1.0% to 18.0% of HFC-32; or 41.0% to 82.0% of HFO-1252zc, 1.0% to 39.0% of HFO-1234ze(E), 1.0% to 3.0% of HFC-134, 1.0% to 2.0% of HFC-134a, and 15.0% to 18.0% of HFC-32; or 41.0% to 63.0% of HFO-1252zc, 17.0% to 39.0%
  • compositions comprise, consist of, or consist essentially of: 0.2% to 89.1 % of CO 2 , 0.2% to 97.5% of HFO-1252zc, 0.2% to 97.5% of HFO-1234ze(E), 0.2% to 22.0% of HFC-134a, and 0.2% to 43.8% of HFC-32; or 0.2% to 89.1 % of CO 2 , 0.2% to 97.5% of HFO-1252zc, 0.2% to 97.5% of HFO- 1234ze(E), 0.2% to 10.0% of HFC-134a, and 0.2% to 19.9% of HFC-32; or 0.2% to 4.0% of CO2, 25.7% to 85.6% of HFO-1252zc, 0.2% to 53.5% of HFO-1234ze(E), 0.2% to 8.0% of HFC-134a, and 5.9% to 19.9% of HFC-32; or .2% to 4.0% of CO2, 25.7% to 63.7% of HFO-1252zc, 15.8%
  • compositions disclosed herein provide GWP less than or equal to 150, COP improved over R-454C, and cooling capacity within 20% of that for R-454C. Additionally, the compositions provide acceptable average temperature glide, preferably less than 10 K, and reasonable compressor discharge temperatures. Further, the compositions as defined above are estimated to be classified as class 2 or 2L for flammability by ASHRAE.
  • 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.
  • refrigerant 1 exhibits flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa), 2) has an LFL ⁇ 0.0062 lb/ft 3 (0.10 kg/m 3 ) or 3) has 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 compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 may further comprise at least one additional compound from the list in Table A.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 may further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO- 1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 may further comprise at least one additional compound comprising HFO-1234yf.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 may further comprise at least one additional compound comprising HFO-1243zf.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, H FC- 134a, or CO2 may further comprise at least one additional compound comprising HFO-263fb.
  • compositions of the present invention identified in Table 1 may exist as different configurational isomers or stereoisomers.
  • the present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof.
  • 1 ,2-difluoroethene HFO-1132 is meant to represent the cis-isomer (Z), trans-isomer (E), or any combination or mixture of both isomers in any ratio.
  • Single isomers or multiple isomers of the same compound may be used in any proportion.
  • 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 greater than zero 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.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 will perform more consistently and be more stable with only minor amounts of water present.
  • the compositions may further comprise less than 100 ppm (by weight) water, preferably less than 20 ppm (by weight) water, and even more preferably less than 10 ppm (by weight) water.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, H FC- 134a, or CO2 will perform more consistently and be more stable with only minor amounts of oxygen or air present. Therefore, the presently claimed compositions may further comprise less than about 5 volume percent non-adsorbable gases (NAG), preferably less than 3 volume percent NAG, and more preferably less than 1 .5 volume percent NAG. Further, the presently claimed compositions, due to the presence of air or NAG, will contain less than 1 volume percent oxygen, preferably less than 0.5 volume percent oxygen, and more preferably less than 0.3 volume percent oxygen.
  • NAG non-adsorbable gases
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 may contain a stabilizer.
  • stabilizer compounds are intended to be present in a small amount and prevent decomposition due to the presence of water, air, NAG, or oxygen in a system while in use or while the composition is stored.
  • 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 also. 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-d i-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 monoterpenes, terpenes, such as d-limonene, a-terpinene, p-terpinene, y-terpinene, a-pinene, or p-
  • composition may include any amount from 0.001 wt% up to 1 wt%, preferably from about 0.001 to about 0.5 weight percent, more preferably, from about 0.001 to about 0.3 weight percent of any of the stabilizers listed above.
  • the compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 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 compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 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-tetrafluor
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 further comprise at least one lubricant.
  • Lubricants may be selected from polyol ester, polyvinyl ether, and polyalkylene glycol. Lubricants may also comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e.
  • Lubricants of the present invention further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and polyalphaolefins.
  • Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), napthenic mineral oil commercially available under the trademark from Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil commercially available from Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 and branched alkylbenzene, sold by Nippon Oil as HAB 22.
  • BVM 100 N paraffinic mineral oil sold by BVA Oils
  • napthenic mineral oil commercially available under the trademark from Suniso® 3GS and Suniso® 5GS by Crompton Co.
  • naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT
  • naphthenic mineral oil commercially
  • Lubricants of the present invention further comprise those which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air- conditioning apparatus' operating conditions
  • lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs) such as PVE-FVC68D.
  • POEs polyol esters
  • PAGs polyalkylene glycols
  • PVEs polyvinyl ethers
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 are combined with a PAG lubricant or a PVE lubricant or a POE lubricant for usage in a low or medium temperature refrigeration system.
  • the lubricant may be present in an amount of less than 80 weight percent of the total composition.
  • the lubricant may further be present in an amount of less than 60 weight percent of the total composition.
  • the amount of lubricant may be between about 0.1 and 50 weight percent of the total composition.
  • the lubricant may also be between about 0.1 and 20 weight percent of the total composition The lubricant may also be between about 0.1 and 5 weight percent of the total composition.
  • a system may include an oil separator in order to function more reliably.
  • the inventive composition comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 is used to introduce lubricant into the air- conditioning or heat pump system as well as or alternatively other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants.
  • the present compositions comprise an acid scavenger.
  • Examples of the acid scavengers that may be included in the present compositions include, but are not limited, the stabilizers and/or the epoxide component of the stabilizers disclosed in U.S. Patent No. 8,535,555 and the acid scavengers disclosed in International Application Publication No. WO 2020/222864, the disclosure of each of which is incorporated herein by reference in its entirety.
  • an acid scavenger may comprise one or more epoxides, one or more amines and/or one or more hindered amines, such as, for example but not limited to, epoxybutane.
  • the acid scavenger e.g., the activated aromatic compound, the siloxane, or both
  • the acid scavenger may be present in any concentration that results in a relatively low total acid number, a relatively low total halides concentration, a relatively low total organic acid concentration, or any combination thereof.
  • the acid scavenger is present at a concentration greater than about 0.0050 wt%, more preferably greater than about 0.05 wt% and even more preferably greater than about 0.1 wt% (e.g., greater than about 0.5 wt%) based on the total weight of the refrigerant composition.
  • the acid scavenger preferably is present in a concentration less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, more preferably less than about 2.5 wt% and most preferably greater than about 2 wt% (e. g. less than about 1.8 wt%) based on the total weight of the refrigerant composition.
  • Preferred additives include those described in U.S. Pat. Nos. 5,152,926; 4,755,316, which are hereby incorporated by reference.
  • the preferred extreme pressure additives include mixtures of (A) tolyltriazole or substituted derivatives thereof, (B) an amine (e.g. Jeffamine M-600) and (C) a third component which is (i) an ethoxylated phosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol (e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g.
  • Lubrizol 5139, 5604, 5178, or 5186 type or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.
  • a mercaptobenzothiazole or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.
  • Additional examples of additives which may be used are given in U.S. Pat. No.
  • Acid number is measured according to ASTM D664-01 in units of mg KOH/g.
  • the total halides concentration, the fluorine ion concentration, and the total organic acid concentration is measured by ion chromatography.
  • Chemical stability of the refrigerant system is measured according to ASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”.
  • the viscosity of the lubricant is tested at 40°C according to ASTM D-7042.
  • Phosphates, phosphites, epoxides, and phenolic additives also have been employed in certain refrigerant compositions. These are described for example by Kaneko (U.S. patent application Ser. No. 11/575,256, published as U.S. Publication 2007/0290164) and Singh et al. (U.S. patent application Ser. No. 11/250,219, published as U.S. Publication 2006/0116310). All of these aforementioned applications are expressly incorporated herein by reference.
  • Preferred flame suppressants include the flame retardants described in patent application “Refrigerant compositions containing fluorine substituted olefins CA 2557873 A1” and incorporated by reference, as well as fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and/or Krytox® lubricants, also incorporated by reference and described in patent application “Refrigerant compositions comprising fluoroolefins and uses thereof W02009018117A1.”
  • 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 which comprise, consist of, or consist essentially of HFO-1252zc, HFO- 1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 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.
  • gas chromatography with a flame ionization detector gas chromatography with a mass detector by analysis of a gas sample or liquid sample
  • 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 ⁇ _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 (GC) techniques, for example gas chromatography (GC) with a flame ionization or electron-capture detector, or GC coupled with a mass detector (gas chromatography/mass spectral (GC/MS) method), by ion chromatograph(IC) or ion chromatography mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (GC) techniques
  • degradation products of such compositions of the present invention which comprise, consist of, or consist essentially of HFO- 1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 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 GC techniques, for example GC 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 GC techniques, for example GC 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 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-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2, 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.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 are useful in numerous methods and systems that provide refrigeration and freezing.
  • a method of cooling comprising evaporating a composition comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 in the vicinity of a body to be cooled and thereafter condensing said composition.
  • the cooling is provided by a refrigeration system.
  • the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods.
  • Low and medium temperature refrigeration systems include supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.
  • a refrigeration system comprising a composition comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 .
  • the composition comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, H FC- 134a, or CO 2 comprised within the refrigeration system further includes a lubricant.
  • the refrigeration system comprises an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods.
  • the refrigeration system may be for providing low temperature refrigeration, medium temperature refrigeration, and/or transport refrigeration.
  • Low and medium temperature refrigeration systems include supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.
  • the refrigeration system is a secondary loop system.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 will have some temperature glide in the heat exchangers.
  • the systems will operate more efficiently if the heat exchangers are operated in counter-current mode or cross-current mode with counter-current tendency.
  • Counter-current tendency means that the closer the heat exchanger can get to counter-current mode the more efficient the heat transfer.
  • refrigeration heat exchangers in particular, evaporators, are designed to provide some aspect of counter-current tendency.
  • an refrigeration system wherein said system includes one or more heat exchangers (either evaporators, condensers, or both) that operate in counter-current mode or cross-current mode with counter-current tendency.
  • the system may be a medium temperature system, a low temperature system or a transport refrigeration system.
  • compositions of the present invention can be used in systems with heat exchangers operating in cross-current mode.
  • a refrigeration system containing compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2, wherein said system includes one or more heat exchangers (either evaporators, condensers, or both) that operate in counter-current mode, cross-current mode, or cross-current mode with counter-current tendency.
  • heat exchangers either evaporators, condensers, or both
  • a method for replacing R-454C, R-513A, R- 448A, R-449a, R-452A, R-404A, or R-410A in refrigeration systems HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 to the system in place of R-454C, R-513A, R-448A, R-449a, R-452A, R-404A, or R-410A.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 are useful as refrigerant in low temperature refrigeration systems, medium temperature refrigeration systems, and/or transport refrigeration systems.
  • compositions comprising, consisting of, or consisting essentially of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CC>2 are useful as refrigerant in any of the refrigeration systems described herein above.
  • compositions containing HFO-1252zc, HFO-1234zeE, HFC-32, and CO2 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21 .5 wt% HFC-32) and R- 404A (ASHRAE designation for a refrigerant containing 44 wt% H FC- 125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 1 provides the calculated results.
  • compositions provide GWP less than 150, Capacity within 20% or 15%, or even 10% of that for R-454C, and COP that is at least 2% higher, or even 3% higher than that for R-454C. Additionally, the compositions provide average temperature glide less than 10 K and reasonable compressor discharge temperatures.
  • a composition range of 1.0% to 6.0% of CO2, 1.0% to 96.0% of R-1252ZC, 1.0% to 97.0% of R1234ZEE, and 1.0% to 49.0% of R32 will have a GWP less than 298, a maximum average glide of about 10.0 K, a cooling capacity range that has a deviation range of -45.8% to 37.1% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -1.1% to 6.5% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 1 lists example compositions within the GWP ⁇ 298 range that have ASHRAE flammability classifications of 2L, 2 and 3.
  • a composition range of 1 .0% to 6.0% of CO2, 1.0% to 96.0% of R-1252ZC, 1 .0% to 97.0% of R1234ZEE, and 1.0% to 28.0% of R32 will have a GWP less than 150, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 2L, 2 and 3, a cooling capacity range has a deviation of -45.8% to 8.1% from the cooling capacity of R- 454C evaluated with the same conditions set, and the cooling COP range has a deviation of -0.5% to 6.5% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 1.0% to 6.0% of CO2, 16.0% to 85.0% of R-1252ZC, 1.0% to 61.0% of R1234ZEE, and 1.0% to 28.0% of R32 will have a GWP ⁇ 150, a maximum average heat exchanger glide of 10.0 K, an ASHRAE flammability classification of 2L, 2 and 3, the minimum and maximum cooling capacities are -10.0% and 8.1% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are -0.4% and 6.1 % than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is -4.8% than that of R-454C, is 2.0 wt-% CO2, 17.0 wt-% R-1252ZC, 59.0 wt- % R1234ZEE and 22.0 wt-% R32, where the COP for cooling is 4.7% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.9 K and its ASHRAE flammability classification is 2L.
  • composition for the even more preferred maximum cooling COP efficiency which is 4.7% than that of R-454C, is 2.0 wt-% CO2, 17.0 wt-% R- 1252ZC, 59.0 wt-% R1234ZEE, and 22.0 wt-% R32, where the CAP for cooling is - 4.8% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.9 K and its ASHRAE flammability classification is 2L.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-32, and HFC-134 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% H FC- 125, 4 wt% H FC- 1343 and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 2 provides the calculated results.
  • compositions provide GWP less than 150, Capacity within 20% or 15% of that for R-454C, and COP that is at least 3% higher, or even 4% higher than that for R-454C. Additionally, the compositions provide average temperature glide less than 10 K and reasonable compressor discharge temperatures.
  • a composition range of 1.0% to 97.0% of R- 1252ZC, 1.0% to 97.0% of R1234ZEE, 1.0% to 43.0% of R32, and 1.0% to 28.0% of R134 will have a GWP less than 300, a maximum average glide of about 9.6 K, a cooling capacity range that has a deviation range of -47.7% to 16.3% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from 1.6% to 57.0% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 2 lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2, 2L, 3 and 1.
  • a composition range of 1.0% to 97.0% of R-1252ZC, 1.0% to 97.0% of R1234ZEE, 1.0% to 43.0% of R32, and 1.0% to 28.0% of R134 will have a GWP less than 300, a maximum average glide of about 9.6 K, an ASHRAE flammability classification of 2, 2L, 3 and 1 , a cooling capacity range has a deviation of -47.7% to 16.3% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of 1 .6% to 57.0% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 1.0% to 97.0% of R-1252ZC, 1.0% to 97.0% of R1234ZEE, 1.0% to 43.0% of R32, and 1 .0% to 28.0% of R134 will have a GWP ⁇ 300, a maximum average heat exchanger glide of 9.6 K, an ASHRAE flammability classification of 2, 2L, 3 and 1 , the minimum and maximum cooling capacities are -47.7% and 16.3% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 1 .6% and 57.0% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is 14.4% than that of R-454C, is 15.0 wt-% R-1252ZC, 41.0 wt-% R1234ZEE, 42.0 wt-% R32 and 2.0 wt-% R134, where the COP for cooling is 1 .6% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 6.8 K and its ASHRAE flammability classification is 2L.
  • composition for the even more preferred maximum cooling COP efficiency which is 56.4% than that of R-454C, is 10.0 wt-% R-1252ZC, 68.0 wt-% R1234ZEE, 1.0 wt-% R32, and 21.0 wt-% R134, where the CAP for cooling is - 16.2% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 1.4 K and its ASHRAE flammability classification is 2L TABLE 2
  • compositions containing HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC- 32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% HFC-125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 3 provides the calculated results.
  • compositions provide average temperature glide less than 10 K and reasonable compressor discharge temperatures.
  • a composition range of 1.0% to 23.0% of R134A, 1.0% to 97.0% of R-1252ZC, 1.0% to 97.0% of R1234ZEE, and 1.0% to 52.0% of R32 will have a GWP less than 300, a maximum average glide of about 9.5 K, a cooling capacity range that has a deviation range of -48.9% to 14.8% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from 1 .7% to 55.3% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 3 lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2L, 2, 3 and 1.
  • a composition range of 1 .0% to 23.0% of R134A, 1 .0% to 97.0% of R-1252ZC, 1.0% to 97.0% of R1234ZEE, and 1.0% to 52.0% of R32 will have a GWP less than 300, a maximum average glide of about 9.5 K, an ASHRAE flammability classification of 2L, 2, 3 and 1 , a cooling capacity range has a deviation of -48.9% to 14.8% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of 1 .7% to 55.3% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 1.0% to 22.0% of R134A, 1.0% to 80.0% of R-1252ZC, 1.0% to 71.0% of R1234ZEE, and 1.0% to 49.0% of R32 will have a GWP ⁇ 300, a maximum average heat exchanger glide of 9.5 K, an ASHRAE flammability classification of 2L, 2 and 3, the minimum and maximum cooling capacities are -10.0% and 10.0% than that of R- 454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 1 .9% and 55.3% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is 10.0% than that of R-454C, is 1.0 wt-% R134A, 25.0 wt-% R-1252ZC, 35.0 wt-% R1234ZEE and 39.0 wt-% R32, where the COP for cooling is 2.0% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 6.7 K and its ASHRAE flammability classification is 2L.
  • composition for the even more preferred maximum cooling COP efficiency which is 54.6% than that of R-454C, is 14.0 wt-% R134A, 15.0 wt-% R- 1252ZC, 66.0 wt-% R1234ZEE, and 5.0 wt-% R32, where the CAP for cooling is - 3.8% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 4.1 K and its ASHRAE flammability classification is 2L.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-32, HFC-134, and CO 2 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC- 32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% HFC-125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 4 provides the calculated results.
  • a composition range of 1.0% to 3.0% of CO2, 1.0% to 6.0% of R134, 1.0% to 20.0% of R-1252ZC, 42.0% to 73.0% of R1234ZEE, and 11.0% to 38.0% of R32 will have a GWP less than 149, a maximum average glide of about 10.0 K, a cooling capacity range that has a deviation range of -20.0% to -9.8% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from 2.8% to 3.9% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 4 lists example compositions within the GWP ⁇ 149 range that have ASHRAE flammability classifications of 2L.
  • a composition range of 1.0% to 3.0% of CO2, 1.0% to 6.0% of R134, 1.0% to 20.0% of R-1252ZC, 42.0% to 73.0% of R1234ZEE, and 11.0% to 38.0% of R32 will have a GWP less than 149, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 2L, a cooling capacity range has a deviation of -20.0% to -9.8% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of 2.8% to 3.9% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 2.0% to 2.0% of CO2, 1.0% to 1.0% of R134, 18.0% to 18.0% of R-1252ZC, 57.0% to 57.0% of R1234ZEE, and 22.0% to 22.0% of R32 will have a GWP ⁇ 149, a maximum average heat exchanger glide of 9.7 K, an ASHRAE flammability classification of 2L, the minimum and maximum cooling capacities are -9.8% and - 9.8% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 3.0% and 3.0% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is -9.8% than that of R-454C, is 2.0 wt-% CO2, 1.0 wt-% R134, 18.0 wt-% R- 1252ZC, 57.0 wt-% R1234ZEE, and 22.0 wt-% R32, where the COP for cooling is 3.0% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.7 K and its ASHRAE flammability classification is 2L.
  • composition for the even more preferred maximum cooling COP efficiency which is 3.0% than that of R-454C, is 2.0 wt-% CO2, 1.0 wt-% R134, 18.0 wt-% R-1252ZC, 57.0 wt-% R1234ZEE, and 22.0 wt-% R32, where the CAP for cooling is -9.8% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.7 K and its ASHRAE flammability classification is 2L
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134, HFC-134a and HFC-32 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC- 32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% HFC-125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 5 provides the calculated results.
  • a composition range of 1.0% to 96.0% of R- 1252ZC, 1.0% to 96.0% of R1234ZE(E), 1.0% to 25.0% of R134, 1.0% to 21.0% of R134A, and 1.0% to 40.0% of R32 will have a GWP less than 300, a maximum average glide of about 9.8 K, a cooling capacity range that has a deviation range of - 48.6% to 21.3% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -0.7% to 6.3% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 5 lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2L, 3, 2 and 1.
  • a composition range of 1 .0% to 96.0% of R-1252ZC, 1 .0% to 96.0% of R1234ZE(E), 1 .0% to 11.0% of R134, 1.0% to 10.0% of R134A, and 1.0% to 18.0% of R32 will have a GWP less than 150, a maximum average glide of about 9.1 K, an ASHRAE flammability classification of 2, 3 and 2L, a cooling capacity range has a deviation of -48.6% to - 5.5% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of 2.3% to 5.9% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 41.0% to 82.0% of R-1252ZC, 1.0% to 39.0% of R1234ZE(E), 1.0% to 3.0% of R134, 1.0% to 2.0% of R134A, and 15.0% to 18.0% of R32 will have a GWP ⁇ 150, a maximum average heat exchanger glide of 7.6 K, an ASHRAE flammability classification of 3 and 2, the minimum and maximum cooling capacities are -10.0% and -5.5% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 2.3% and 2.8% than that of R- 454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is -6.3% than that of R-454C, is 63.0 wt-% R-1252ZC, 17.0 wt-% R1234ZE(E), 1 .0 wt-% R134, 1 .0 wt-% R134A, and 18.0 wt-% R32, where the COP for cooling is 2.3% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 7.0 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.6% than that of R-454C, is 62.0 wt-% R-1252ZC, 19.0 wt-% R1234ZE(E), 2.0 wt-% R134, 1.0 wt-% R134A, and 16.0 wt-% R32, where the CAP for cooling is -9.4% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 6.7 K and its ASHRAE flammability classification is 2.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134, HFC-32, and CO 2 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC- 32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% HFC-125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 6 provides the calculated results.
  • a composition range of 0.2% to 89.5% of CARBON DIOXIDE, 0.2% to 97.5% of R-1252ZC, 0.2% to 97.5% of R1234ZE(E), 0.2% to 25.9% of R134, and 0.2% to 43.8% of R32 will have a GWP less than 300, a maximum average glide of about 10.0 K, a cooling capacity range that has a deviation range of -49.8% to 227.6% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -56.1% to 6.2% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 6 lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2L, 1, 3 and 2.
  • a composition range of 0.2% to 89.5% of CARBON DIOXIDE, 0.2% to 97.5% of R-1252ZC, 0.2% to 97.5% of R1234ZE(E), 0.2% to 12.0% of R134, and 0.2% to 19.9% of R32 will have a GWP less than 149, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 1, 3, 2L and 2, a cooling capacity range has a deviation of -49.8% to 224.5% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of -56.1% to 6.0% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 0.2% to 4.0% of CARBON DIOXIDE, 25.7% to 85.6% of R-1252ZC, 0.2% to 53.5% of R1234ZE(E), 0.2% to 8.0% of R134, and 7.9% to 19.9% of R32 will have a GWP ⁇ 149, a maximum average heat exchanger glide of 10.0 K, an ASHRAE flammability classification of 2 and 3, the minimum and maximum cooling capacities are -10.0% and 2.7% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 0.8% and 2.6% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is 1.9% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 61.7 wt-% R- 1252ZC, 15.9 wt-% R1234ZE(E), 0.5 wt-% R134, and 19.9 wt-% R32, where the COP for cooling is 1.0% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.2 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.4% than that of R-454C, is 0.2 wt-% CARBON DIOXIDE, 55.7 wt-% R-1252ZC, 27.9 wt-% R1234ZE(E), 0.2 wt-% R134, and 15.9 wt-% R32, where the CAP for cooling is -9.8% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 7.2 K and its ASHRAE flammability classification is 2.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134a, HFC-32, and CO 2 are compared to R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC- 32) and R-404A (ASHRAE designation for a refrigerant containing 44 wt% HFC-125, 4 wt% HFC-134a and 52 wt% HFC-143a) under the conditions for refrigeration shown below.
  • Table 7 provides the calculated results.
  • a composition range of 0.2% to 89.1% of CARBON DIOXIDE, 0.2% to 97.5% of R-1252ZC, 0.2% to 97.5% of R1234ZE(E), 0.2% to 22.0% of R134A, and 0.2% to 43.8% of R32 will have a GWP less than 300, a maximum average glide of about 10.0 K, a cooling capacity range that has a deviation range of -49.6% to 227.6% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -54.1% to 7.5% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 7 lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2, 1 , 3 and 2L.
  • a composition range of 0.2% to 89.1% of CARBON DIOXIDE, 0.2% to 97.5% of R-1252ZC, 0.2% to 97.5% of R1234ZE(E), 0.2% to 10.0% of R134A, and 0.2% to 19.9% of R32 will have a GWP less than 149, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 1 , 2, 3 and 2L, a cooling capacity range has a deviation of -49.6% to 224.5% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of -54.1% to 7.5% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for cooling mode within a composition range of 0.2% to 4.0% of CARBON DIOXIDE, 25.7% to 85.6% of R-1252ZC, 0.2% to 53.5% of R1234ZE(E), 0.2% to 8.0% of R134A, and 5.9% to 19.9% of R32 will have a GWP ⁇ 149, a maximum average heat exchanger glide of 10.0 K, an ASHRAE flammability classification of 2 and 3, the minimum and maximum cooling capacities are -10.0% and 2.8% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 0.5% and 2.6% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is 2.1% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 61.7 wt-% R- 1252ZC, 15.9 wt-% R1234ZE(E), 0.5 wt-% R134A, and 19.9 wt-% R32, where the COP for cooling is 1.0% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.1 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.4% than that of R-454C, is 0.2 wt-% CARBON DIOXIDE, 55.7 wt-% R-1252ZC, 27.9 wt-% R1234ZE(E), 0.2 wt-% R134A, and 15.9 wt-% R32, where the CAP for cooling is -9.7% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 7.2 K and its ASHRAE flammability classification is 2. TABLE 7
  • a composition range of 1.0-21.0% of HFO- 1252zc, 49.0-94.0% of HFO-1234ze(E), 1.0-30.0% of HFC-134, and of 1.0-8.0% of HFC-32 will have a GWP less than 150, a maximum average glide of 6.0 K, an ASHRAE flammability rating of 2L, a cooling capacity in a range of 50.0-61.3% of the cooling capacity of R-404A evaluated with the same conditions set, and a cooling COP range in a range of 106.6-108.7% of the cooling COP of R-404A evaluated with the same conditions set.
  • a composition range of 14.0-21.0% of HFO-1252zc, 64.0-73.0% of HFO-1234ze(E), 3.0-8.0% of HFC-134, and of 7.0-8.0% of HFC-32 will have a GWP less than 148, a maximum average glide of 6. OK, an ASHRAE flammability rating of 2L, a cooling capacity in a range of 60.0-62.0% of the cooling capacity of R-404A evaluated with the same conditions set, and a cooling COP range in a range of 106.5-106.8% of the cooling COP of R- 404A evaluated with the same conditions set.
  • compositions of 15.0-19.0% of HFO-1252zc, 68.0- 72.0% of HFO-1234ze(E), 3.0-7.0% of HFC-134, and of 6.0-10.0% of HFC-32 will have a GWP of less than 137, a maximum average glide of 5.9 K, an ASHRAE flammability rating of 2L, a cooling capacity in a range of 58.1-61.3% of the cooling capacity of R-404A evaluated with the same conditions set, and a cooling COP range in a range of 106.6-106.9 % of the cooling COP of R-404A evaluated with the same conditions set.

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Abstract

La présente invention concerne des compositions comprenant du HFO-1252 zc, du HFO-1234 zeE, du HFC-32, et au moins l'un parmi HFC-134, HFC-134 a ou CO2. Les compositions sont utiles dans des procédés de refroidissement, des systèmes de réfrigération, notamment basse température, moyenne température et de réfrigération de transport, et des procédés de remplacement de fluides frigorigènes existants.
PCT/US2025/011631 2024-03-14 2025-01-15 Compositions à faible gwp comprenant du hfo-1252 zc et leurs utilisations Pending WO2025193322A1 (fr)

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