[go: up one dir, main page]

WO2025193321A1 - Compositions comprenant du difluoropropène, du tétrafluoropropène et du difluorométhane et leurs utilisations - Google Patents

Compositions comprenant du difluoropropène, du tétrafluoropropène et du difluorométhane et leurs utilisations

Info

Publication number
WO2025193321A1
WO2025193321A1 PCT/US2025/011628 US2025011628W WO2025193321A1 WO 2025193321 A1 WO2025193321 A1 WO 2025193321A1 US 2025011628 W US2025011628 W US 2025011628W WO 2025193321 A1 WO2025193321 A1 WO 2025193321A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfc
hfo
composition
cop
heating
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/US2025/011628
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
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
Publication of WO2025193321A1 publication Critical patent/WO2025193321A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C09K2205/106—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234

Definitions

  • the present disclosure relates to compositions useful as refrigerants, and in particular, for air-conditioning and heat pump systems.
  • the compositions of the present disclosure are useful in methods for producing cooling and heating, and methods for replacing refrigerants in air-conditioning and heat pump 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 present invention solves certain problems associated with conventional refrigerants and provides refrigerant blends containing 1 ,1-difluoropropene, which meet the evolving regulatory landscape.
  • compositions disclosed herein relate to a fluoropropene composition comprising 1,1 -difluoropropene (also called HFO-1252zc, or R-1252zc).
  • HFO-1252zc 1,1 -difluoropropene
  • R-1252zc 1,1 -difluoropropene
  • This compound is shown herein to have advantageous properties for its use in refrigerant applications, such as air-conditioning and heat pumps.
  • compositions comprising HFO-1252zc, HFO- 1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2., including:
  • HFO-1252zc HFO-1234zeE, HFC-32, and CO2;
  • HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a are HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or
  • HFO-1252zc HFO-1234zeE, HFC-32, HFC-134a, and CO2.
  • compositions of the above-described embodiment have a AGW of less than 300 or less than 150 or less than 149.
  • compositions of the above-described embodiment have an average temperature glide of no more than 10.0 K.
  • compositions of the above-described embodiment are classified as class 1 , class 2L, class 2, or class 3, by ASHRAE for flammability.
  • compositions of any of the abovedescribed embodiments further comprise at least one additional compound selected from HCFC-22, HFC-23, HCC-30, HCFC-31 , HCC-40, HFC-41, methane, HFC-125, HFC-134a, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, 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
  • compositions of any of the abovedescribed embodiments further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252ze, HFO- 1252yf, HFO-1252zf, or HFO-1252ye.
  • compositions of any of the abovedescribed embodiments further comprise 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 of any of the abovedescribed embodiments further comprising a stabilizer, preferably one or more from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones, or preferably one or more from the group consisting of 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
  • a stabilizer preferably one
  • compositions of the any of the abovedescribed embodiments further comprises a lubricant, preferably selected from one or more of the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether, or preferably a polyol ester or a polyvinyl ether.
  • a lubricant preferably selected from one or more of the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether, or preferably a polyol ester or a polyvinyl ether.
  • compositions of any of the abovedescribed embodiments includes a lubricant that 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; kinematic 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.
  • a lubricant that 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; kinematic 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 of any of the abovedescribed embodiments comprises at least one tracer, preferably present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight and preferably selected from one or more of the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.
  • tracer preferably present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight and preferably selected from one or more of the group consisting of hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochlorofluorocarbons, hydrochlorofluor
  • any of the compositions of the abovedescribed embodiments further comprise at least one tracer 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 , HC
  • compositions of any of the abovedescribed embodiments 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.
  • methods for cooling comprising evaporating the composition of any of the above-described embodiments in the vicinity of a body to be cooled and thereafter condensing said composition, wherein said cooling is provided by an air-conditioner or heat pump.
  • the systems comprise an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • said air-conditioner or heat pump is a residential, light commercial, or industrial air-conditioner or heat pump.
  • the system may be a secondary system.
  • composition of any of the above-described embodiments in air-conditioning or heat pump systems.
  • This invention relates to compositions containing 1 ,1 -difluoropropene (HFO-1252zc), difluoromethane (HFC-32), E-1,3,3,3-tetrafluoropropene (HFO- 1234zeE), and at least one of 1,1,2,2-tetrafluoroethane (HFC-134), 1 ,1,1 ,2- tetrafluoroethane (HFC-134a), 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, consist of, or consist essentially of HFO- 1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 . They provide refrigerant blends with low global warming potential 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 air-conditioning and heat pump 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.
  • GWP Global warming potential
  • 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, R-134a), and carbon dioxide (CO2) are available commercially from various sources worldwide.
  • HFC-32 or R-32 difluoromethane
  • 1,1,2,2-tetrafluoroethane HFC-134 or R-134
  • 1 ,1 ,1 ,2-tetrafluoroethane HFC-134a, R-134a
  • CO2 carbon dioxide
  • 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.
  • 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 improved energy efficiency
  • many of the presently disclosed compositions provide capacity within 20% of that for R-454C.
  • HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a are HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a; or
  • HFO-1252zc HFO-1234zeE, HFC-32, HFC-134, and HFC-134a; or HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134a, and CO 2 .
  • the compositions comprise, consist of, or consist essentially of: about 1-30% HFO-1252zc, about 48-82% HFO-1234zeE, about 15- 22% HFC-32, and about 1-4% HFC-134; or about 0.2-98.5% HFO-1252zc, about 0.2-98.5% of HFO-1234zeE, about 0.2-26.0% HFC-134, and about 0.2-43.8% HFC- 32; or about 0.2-98.5% of HFO-1252zc, about 0.2%-98.5% of HFO-1234ze(E), about 0.2-12.9% of HFC-134, and about 0.2%-20.9% of HFC-32; or about 19.9-84.6% of HFO-1252zc, about 0.2-58.7% of HFO-1234ze(E), about 0.2-3.0% of HFC-134, and about 14.9%-20.9% of HFC-32; or about 19.9-22.9% of HFO-1252zc, about 55.7- 58.7%
  • compositions comprise, consist of, or consist essentially of: about 13 to 30% HFO-1252zc, about 54 to 72% HFO-1234zeE, about 8 to 14% HFC-32, and about 1 to 4% CO2; or about 13 to about 30% HFO-1252zc, about 54 to about 72% HFO-1234zeE, about 8 to about 14% HFC-32, and about 1 to about 4% CO2; or about 0.2-98.5% of HFO-1252zc, about 0.2-98.5% of HFO- 1234ze(E), about 0.2-44.0% of HFC-32, and about 0.2%-8.0% of CO2 ; or about 0.2- 98.5% of HFO-1252zc, about 0.2-98.5% of HFO-1234ze(E), about 0.2-22.0% of HFC-32, and about 0.2-3.0% of CO2; or about 27.9-84.6% of HFO-1252zc, about 0.2-51.7% of HFO-1234ze
  • compositions comprise, consist of, or consist essentially of: about 5 to 30% HFO-1252zc, about 46 to 77% HFO-1234zeE, about 5 to 22% HFC-32, about 1 to 10% HFC-134, and about 1 to 4% CO2; or about 1 to 21 % HFO-1252zc, about 42 to 82% HFO-1234zeE, about 11 to 22% HFC-32, about 1 to 6% HFC-134, and about 1 to 3% CO 2 ; or about 0.2-98.5% of HFO-1252zc, about 0.2-98.5% of HFO-1234ze(E), about 0.2-26.0% of HFC-134, about 0.2-43.8% of HFC-32, and about 0.2-3.0% of CO2; or about 0.2-98.5% of HFO-1252zc, about 0.2-98.5% of HFO-1234ze(E), about 0.2-12.9% of HFC-134, about 0.2-20.9% of HFC-32, and
  • compositions comprise, consist of, or consist essentially of: about 1 to 21% HFO-1252zc, about 57 to 82% HFO-1234zeE, about 16 to 22% HFC-32, and about 1 to 3% HFC-134a; or about 0.1-21.0% HFO-1252zc, about 58.0-80.0% HFO-1234zeE, about 16.0-20.0% HFC-32, and about 1.0-3.0% H FC- 134a.
  • compositions comprise, consist of, or essentially consist of: about 1.0-96.0% of HFO-1252zc, about 1.0-96.0% of HFO- 1234ze(E), about 1.0-40.0% of HFC-32, about 1.0-24.0% of HFC-134, and about 1.0-21.0% of HFC-134a; or about 1.0-96.0% of HFO-1252zc, about 1.0-96.0% of HFO-1234ze(E), about 1.0-18.0% of HFC-32, about 1.0-11.0% of HFC-134, and about 1.0-10.0% of HFC-134a; or about 36.0-82.0% of HFO-1252zc, about 1.0- 44.0% of HFO-1234ze(E), about 15.0-18.0% of HFC-32, about 1.0-3.0% of HFC- 134, about 1.0-2.0% of HFC-134a; or about 36.0-63.0% of HFO-1252zc, about 17.0- 44.0% of
  • compositions comprise, consist of, or essentially consist of: about 2.0% to 92.0% of HFO-1252zc, 2.0% to 92.0% of HFO- 1234ze(E), 2.0% to 40.0% of HFC-32.
  • HFC-134a 2.0% to 22.0% of HFC-134a, and 2.0% to 78.0% of CO2; or about 2.0% to 92.0% of HFO-1252zc, 2.0% to 92.0% of HFO- 1234ze(E), 2.0% to 18.0% of HFC-32, 2.0% to 10.0% of HFC-134a, and 2.0% to 78.0% of CO2; or about 34.0% to 84.0% of HFO-1252zc, 2.0% to 46.0% of HFO- 1234ze(E), 10.0% to 18.0% of HFC-32, 2.0% to 6.0% of HFC-134a, and 2.0% to 2.0% of CO2; or about 34.0% to 62.0% of HFO-1252zc, 16.0% to 46.0% of HFO- 1234ze(E), 12.0% to 18.0% of HFC-32, 2.0% to 4.0% of HFC-134a, and 2.0% to 2.0% of CO2; or about 62.0% HFO-1252zc, 16.0% HFO-1234ze(
  • compositions disclosed herein provide GWP less than or equal to 300 or less than equal to 150 or less than or equal to 149, a COP comparable to or improved over R-454C, and cooling capacity comparable to or within 20% of that for R-454C. Additionally, the compositions provide acceptable average temperature glide and reasonable compressor discharge temperatures. Further, the compositions as defined above are estimated to be classified as class 1 or 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.
  • 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.
  • HFO-1252zc can be combined with HFC-32 and HFO-1234zeE and at least one of HFC-134, HFC-134a, and/or CO2 and provide estimated class 1 or class 2 or class 2L flammability as defined by ANSI/ASHRAE standard 34 and ISO 817. Class 2 and class 2L flammability may be manageable in refrigeration systems. Specific applications may have different requirements, with regards to flammability. [0061]
  • the compositions disclosed herein 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 estimated to be classified as class 2L flammability.
  • 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
  • any of the compositions of the above-mentioned embodiments further comprise at least one additional compound selected from HCFC-22, HCC-40, HFC-134a, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO- 1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye.
  • any of the compositions of the above-mentioned embodiments further comprise at least one additional compound comprising HFO-1234yf.
  • any of the compositions of the above-mentioned embodiments further comprise at least one additional compound comprising HFO-1243zf.
  • any of the compositions of the above-mentioned embodiments further comprise at least one additional compound comprising HFO-263fb.
  • Some of the compounds present in the 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 amounts 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 of any of the above- mentioned embodiments 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, HFC-134a, or CO2 will perform more consistently and be more stable with only minor amounts of oxygen or air present. Therefore, in another embodiment, the compositions of any of the above-mentioned embodiments 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 of any of the above-mentioned embodiments also contains 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 does include a stabilizer, it 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 of the above-mentioned embodiments 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 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 ,
  • compositions of any of the above-described embodiments 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. cyclic or ring structure saturated hydrocarbons, which may be paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds).
  • 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
  • compositions of any of the abovedescribed embodiments are combined with a PAG lubricant or a PVE lubricant or a POE lubricant for usage in an air-conditioning system or heat pump 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. If lubricant compatibility is an issue, a system may optionally include an oil separator in order to function more reliably.
  • 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.
  • Additional examples of additives which may be used are given in U.S. Pat. No. 5,976,399 (Schnur, 5:12-6:51 , hereby incorporated by reference).
  • 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.
  • Mouli et al. (WO 2008/027595 and WO 2009/042847) teaches the use of alkyl silanes as a stabilizer in refrigerant compositions containing fluoroolefins. 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 any of the abovedescribed embodiments 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.
  • Such methodologies are well known to those skilled in the art.
  • 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 (GO) techniques, for example gas chromatography (GO) with a flame ionization or electron-capture detector, or GO 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 (GO) techniques
  • degradation products of compositions of any of the above-described embodiments 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 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 air-conditioning and heating.
  • 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, wherein said cooling is provided by an air-conditioner or heat pump.
  • the air conditioner may be a residential, commercial, or industrial air-conditioning system. These may include, but are not limited to, window, ducted, ductless, packaged terminal, and those exterior to, but connected to the building, such as rooftop systems.
  • the present method may be particularly useful in high ambient temperature regions, due to the high critical temperature of blends containing HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC- 134a, or CO2.
  • a method of heating comprising evaporating a composition comprising HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 and thereafter condensing said composition in the vicinity of a body to be heated, wherein said heating is provided by a heat pump.
  • the heat pump is a residential, light commercial or industrial heat pump system.
  • These may include, but are not limited to, residential heat pumps that provide comfort air-conditioning and heating, hot water heat pumps for heating air (by secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high temperature heat pumps. Due to the high critical temperature of blends containing HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 it is possible to heat water to higher temperatures than propane or R-454C or R- 410A.
  • the method for producing cooling is particularly useful in regions where the ambient temperature can exceed at least 35°C.
  • R-22 is an ozone depleting substance in the Montreal Protocol to reduce ozone depletion. As such, R-22 has been mandated and legislated for phase out for manufacture for and use in air conditioning and refrigeration. There is interest in finding a refrigerant with the lowest possible direct GWP and also that performs well in hot climate (or high ambient) temperature regions.
  • the body to be cooled may be defined as any space, location, object, or body for which it is desirable to provide cooling. Examples include spaces, open or enclosed, that require cooling such as a residence, such as an apartment or apartment building, university dormitory, townhouse or other attached house, or a single-family home; or the body to be cooled may be any other building, such as an office building, supermarket, college or university classroom or administration buildings.
  • a method for producing air conditioning in high ambient temperatures comprises 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 CO 2 and thereafter condensing said composition.
  • the method is particularly useful in regions where ambient temperatures can exceed 35°C or more.
  • a method for replacing HCFC-22 in high ambient air conditioning apparatus comprising providing a composition comprising, consisting essentially of, or consisting of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 to said apparatus.
  • the method of replacing HCFC-22 is particularly useful in regions where ambient temperatures can exceed 35°C or more.
  • HCFC-124 has been used as the working fluid in such applications. HCFC-124 is also controlled under the Montreal protocol as an ozone depleting substance and more environmentally sustainable replacements are desirable.
  • a method for replacing HCFC-124 in industrial air conditioning apparatus comprising providing a composition comprising, consisting essentially of, or consisting of HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO 2 to said apparatus.
  • the method of replacing HCFC-124 is particularly useful in regions where ambient temperatures can exceed 35°C or more.
  • the method for producing cooling and method for replacing HCFC-22 or HCFC-124 are useful for systems operating in ambient temperatures of 40°C or higher.
  • the method for producing cooling is useful for systems operating in ambient temperatures of 45°C or higher.
  • the method for producing cooling is useful for systems operating in ambient temperatures of 50°C or higher.
  • the method for producing cooling is useful for systems operating in ambient temperatures of 55°C or higher.
  • the method for producing cooling is useful for systems operating in ambient temperatures of 60°C or higher.
  • the method for producing cooling is useful for systems operating in ambient temperatures from 35-50°C.
  • the method for producing cooling is useful for systems operating in ambient temperatures from 35-60°C.
  • the method for producing cooling is useful for systems operating in ambient temperatures from 40- 60°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 45-60°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 50-60°C.
  • a system for cooling or heating comprising a composition comprising HFO-1252zc, HFO-1234zeE, HFC-32, and at least one of HFC-134, HFC-134a, or CO2 and optionally a lubricant.
  • the system comprises an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • the air-conditioner or heat pump system may be a residential, light commercial, or industrial air-conditioner or heat pump. Various such systems are described previously herein.
  • the air-conditioner or heat pump 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.
  • airconditioner or heat pump system heat exchangers in particular, evaporators, are designed to provide some aspect of counter-current tendency. Therefore, provided herein is an air conditioning or heat pump 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.
  • compositions of the present invention can be used in systems with heat exchangers operating in cross-current mode.
  • an air-conditioner or heat pump 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, crosscurrent mode, or cross-current mode with counter-current tendency.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134, 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-410A (ASHRAE designation for a refrigerant containing 50 wt% H FC- 125 and 50 wt% H FC-32) under the conditions for a residential air-conditioner shown below.
  • Tables 1A and 1B provide the calculated results.
  • compositions comprising HFO-1252zc, HFO- 1234zeE, HFC-134, and HFC-32 provide higher COP (a measure of energy efficiency) than R-454C, and CAP (cooling capacity) within 20% of that for R-454C.
  • a composition range of 0.2% to 98.5% of R- 1252ZC, 0.2% to 98.5% of HFO-1234ZE(E), 0.2% to 26.0% of HFC-134, and 0.2% to 43.8% of HFC-32 will have a GWP less than 300, a maximum average glide of about 9.9 K, a cooling capacity range that has a deviation range of -48.1% to 22.3% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -2.4% to 5.4% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • a composition range of 0.2% to 98.5% of R-1252ZC, 0.2% to 98.5% of HFO-1234ZE(E), 0.2% to 12.9% of HFC-134, and 0.2% to 20.9% of HFC-32 will have a GWP less than 150, a maximum average glide of about 9.6 K, an ASHRAE flammability classification of 3, 2L and 2, a cooling capacity range has a deviation of -48.1% to -2.2% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of 1.5% to 5.0% 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 19.9% to 84.6% of R-1252ZC, 0.2% to 58.7% of HFO-1234ZE(E), 0.2% to 3.0% of HFC-134, and 14.9% to 20.9% of HFC-32 will have a GWP ⁇ 150, a maximum average heat exchanger glide of 9.4 K, an ASHRAE flammability classification of 2, 3 and 2L, the minimum and maximum cooling capacities are - 10.0% and -2.2% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 1.5% and 2.5% than that of R- 454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is -9.2% than that of R-454C, is 22.9 wt-% R-1252ZC, 55.7 wt-% HFO- 1234ZE(E), 0.5 wt-% HFC-134 and 20.9 wt-% HFC-32, where the COP for cooling is 2.4% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.3 K and its ASHRAE flammability classification is 2L.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.5% than that of R-454C, is 19.9 wt-% R-1252ZC, 58.7 wt-% HFO- 1234ZE(E), 0.5 wt-% HFC-134, and 20.9 wt-% HFC-32, where the CAP for cooling is -9.9% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.4 K and its ASHRAE flammability classification is 2L.
  • a composition range of 1.0% to 21.0% of R- 1252ZC, 64.0% to 92.0% of HFO-1234ZE(E), 1.0% to 11.0% of HFC-134, and 1.0% to 9.0% of HFC-32 will have a GWP ⁇ 150, an ASHRAE flammability rating of 2L, an average temperature glide of no more than 6.5, a cooling capacity of 40.0% to 48.9% of the cooling capacity of R-454C evaluated with the same conditions set, and a cooling COP of 108.6% to 109.3% of the cooling COP of R-454C evaluated with the same conditions set.
  • a composition range of 15.0% to 21.0% HFO-1252zc, 63.0% to 76.0% HFO-1252zeE, 1.0% to 8.0% HFC-134, and 7.0% to 9.0% HFC-32 will have a GWP ⁇ 150, an ASHRAE flammability rating of 2L, an average temperature glide of no more than 6.5, a cooling capacity of 49.1% to 53.0% of the cooling capacity of R-454C evaluated with the same conditions set, and a cooling COP of 108.6% to 108.7% of the cooling COP of R-454C evaluated with the same conditions set.
  • 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-410A (ASHRAE designation for a refrigerant containing 50 wt% H FC- 125 and 50 wt% HFC-32) under the conditions for a residential heat pump shown below.
  • Tables 2A and 2B provide the calculated results.
  • compositions comprising HFO-1252zc, HFO- 1234zeE, HFC-32, and CO2 provide higher COP (a measure of energy efficiency) higher than R-454C, and CAP (cooling capacity) within 20%, or even in some cases 15% of that for R-454C.
  • a composition range of 0.2% to 8.0% of CARBON DIOXIDE, 0.2% to 98.5% of R-1252ZC, 0.2% to 98.5% of HFO- 1234ZE(E), and 0.2% to 44.0% of HFC-32 will have a GWP less than 298, a maximum average glide of about 10.0 K, a heating capacity range that has a deviation range of -50.7% to 50.3% from the heating capacity of R-454C evaluated with the same conditions set, and the heating COP range has a deviation range from -3.6% to 2.3% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Table 2 lists example compositions within the GWP ⁇ 298 range that have ASHRAE flammability classifications of 2L, 2 and 3.
  • a composition range of 0.2% to 3.0% of CARBON DIOXIDE, 0.2% to 98.5% of R-1252ZC, 0.2% to 98.5% of HFO-1234ZE(E), and 0.2% to 22.0% of HFC-32 will have a GWP less than 149, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 2, 3 and 2L, a heating capacity range has a deviation of -50.7% to 2.0% from the heating capacity of R-454C evaluated with the same conditions set, and the heating COP range has a deviation of 0.1% to 2.3% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for heating mode within a composition range of 0.2% to 2.0% of CARBON DIOXIDE, 27.9% to 84.6% of R-1252ZC, 0.2% to 51.7% of HFO-1234ZE(E), and 11.0% to 22.0% of HFC-32 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 heating capacities are -10.0% and 2.0% than that of R-454C evaluated at the same conditions set, and the minimum and maximum heating COP efficiencies are 0.6% and 1.3% than that of R- 454C evaluated at the same conditions set.
  • composition for the even more preferred maximum heating capacity which is 1.5% than that of R-454C, is 1.0 wt-% CARBON DIOXIDE, 64.0 wt-% R- 1252ZC, 13.0 wt-% HFO-1234ZE(E) and 22.0 wt-% HFC-32, where the COP for heating is 0.6% 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.
  • compositions comprising HFO-1252zc, HFO- 1234zeE, HFC-134, HFC-32, and CO2 provide higher COP (a measure of energy efficiency) than R-454C, and CAP (cooling capacity) within 20%, or 15%, or even in some cases 12% of that for R-454C.
  • a composition range of 0.2% to 3.0% of CARBON DIOXIDE, 0.2% to 98.5% of R-1252ZC, 0.2% to 98.5% of HFO- 1234ZE(E), 0.2% to 26.0% of HFC-134, and 0.2% to 43.8% of HFC-32 will have a GWP less than 300, a maximum average glide of about 10.0 K, a heating capacity range that has a deviation range of -51.3% to 33.3% from the heating capacity of R- 454C evaluated with the same conditions set, and the heating COP range has a deviation range from -2.4% to 2.6% than that of the heating 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 2, 2L, 3 and 1.
  • composition for the even more preferred maximum heating capacity which is -0.1% than that of R-454C, is 1.0 wt-% CARBON DIOXIDE, 63.7 wt-% R- 1252ZC, 13.9 wt-% HFO-1234ZE(E), 0.5 wt-% HFC-134, and 20.9 wt-% HFC-32, where the COP for heating is 0.7% 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.
  • compositions of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, and HFC-134a provide GWP less than 150 and reasonable compressor discharge temperatures. Additionally, the compositions provide average temperature glide less than 10 K, or less than 9 K, or less than 8 K. And the compositions also provide capacity within 20% of that for R- 454C and COP at least 2%, or even 30 % or more higher than that for R-454C.
  • 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-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32) under the conditions for a residential air-conditioner shown below.
  • Tables 5A and 5B provide the calculated results.
  • compositions of the present invention containing HFO-1252zc, HFO-1234zeE, HFC-32, HFC-134, and CO 2 provide GWP less than 150 and reasonable compressor discharge temperatures. Additionally, the compositions provide average temperature glide less than 10 K, or less than 9 K. And the compositions also provide capacity within 20% of that for R-454C and COP at least 2%, or even 30 % or more higher than that for R-454C.
  • compositions may be lower in capacity than R-410A, but the improved COP (at least 7% higher, or even 8% higher than R-410A) may be worth a small redesign to allow use in systems similar to R-410A systems with the presently claimed lower capacity refrigerants.
  • 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-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32) under the conditions for a residential heat pump in both cooling and heating mode shown below.
  • Table 6a provides the calculated results for cooling mode while Table 6b provides the calculated results for heating mode.
  • a composition range of 1.0% to 96.0% of R- 1252ZC, 1.0% to 96.0% of HFO-1234ZE(E), 1.0% to 24.0% of HFC-134, 1.0% to 21.0% of HFC-134A, and 1.0% to 40.0% of HFC-32 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 -47.2% to 20.1% 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 4.7% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 6a 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 96.0% of R-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 will have a GWP less than 150, a maximum average glide of about 9.6 K, an ASHRAE flammability classification of 2L, 2 and 3, a cooling capacity range has a deviation of -47.2% to -5.2% 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 4.4% 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 36.0% to 82.0% of R-1252ZC, 1.0% to 44.0% 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 will have a GWP ⁇ 150, a maximum average heat exchanger glide of 8.2 K, an ASHRAE flammability classification of 3 and 2, the minimum and maximum cooling capacities are -10.0% and -5.2% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 2.2% and 2.6% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.4% than that of R-454C, is 53.0 wt-% R-1252ZC, 28.0 wt-% HFO-1234ZE(E), 2.0 wt-% HFC-134, 1.0 wt-% HFC-134A, and 16.0 wt-% HFC-32, where the CAP for cooling is -9.9% 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.
  • a composition range of 1.0% to 96.0% of R- 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 will have a GWP less than 300, a maximum average glide of about 10.0 K, a heating capacity range that has a deviation range of -50.1% to 19.7% from the heating capacity of R-454C evaluated with the same conditions set, and the heating COP range has a deviation range from -1.3% to 2.8% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Table 6b lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2L, 3, 1 and 2.
  • a composition range of 1.0% to 96.0% of R-1252ZC, 1.0% to 96.0% of HFO-1234ZE €, 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 will have a GWP less than 150, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 2, 3 and 2L, a heating capacity range has a deviation of -50.1% to -6.5% from the heating capacity of R-454C evaluated with the same conditions set, and the heating COP range has a deviation of 1.1% to 2.7% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for heating mode within a composition range of 45.0% to 81.0% of R-1252ZC, 1.0% to 35.0% of HFO-1234ZE €, 1.0% to 2.0% of HFC-134, 1.0% to 2.0% of HFC-134A, and 16.0% to 18.0% of HFC-32 will have a GWP ⁇ 150, a maximum average heat exchanger glide of 8.3 K, an ASHRAE flammability classification of 2 and 3, the minimum and maximum heating capacities are -10.0% and -6.5% than that of R-454C evaluated at the same conditions set, and the minimum and maximum heating COP efficiencies are 1.1% and 1.2% than that of R-454C evaluated at the same conditions set.
  • compositionn for the even more preferred maximum heating capacity which is-7.4% than that of R-454C, is 63.0 wt-% R-1252ZC, 17.0 wt-% HFO- 1234ZE €, 1.0 wt-% HFC-134, 1.0 wt-% HFC-134A, and 18.0 wt-% HFC-32, where the COP for heating is 1.1% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 7.8 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum heating COP efficiency which is 1.1% than that of R-454C, is 54.0 wt-% R-1252ZC, 27.0 wt-% HFO-1234ZE €, 1.0 wt-% HFC-134, 1.0 wt-% HFC-134A, and 17.0 wt-% HFC-32, where the CAP for heating is -9.9% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 7.8 K and its ASHRAE flammability classification is 2.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134a, 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-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32) under the conditions for a residential heat pump in both cooling and heating mode shown below.
  • Table 7a provides the calculated results for cooling mode while Table 7b provides the results for heating mode.
  • a composition range of 2.0% to 78.0% of CARBON DIOXIDE, 2.0% to 92.0% of R-1252ZC, 2.0% to 92.0% of HFO- 1234ZE(E), 2.0% to 22.0% of HFC-134A, and 2.0% to 40.0% of HFC-32 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 -37.7% to 218.6% from the cooling capacity of R- 454C evaluated with the same conditions set, and the cooling COP range has a deviation range from -35.0% to 3.2% than that of the cooling COP of R-454C evaluated with the same conditions set.
  • Table 7a lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2, 1, 3 and 2L.
  • a composition range of 2.0% to 78.0% of CARBON DIOXIDE, 2.0% to 92.0% of R-1252ZC, 2.0% to 92.0% of HFO-1234ZE(E), 2.0% to 10.0% of HFC-134A, and 2.0% to 18.0% of HFC-32 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 -37.7% to 213.4% from the cooling capacity of R-454C evaluated with the same conditions set, and the cooling COP range has a deviation of -35.0% to 3.1 % 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 CARBON DIOXIDE, 34.0% to 84.0% of R-1252ZC, 2.0% to 46.0% of HFO-1234ZE(E), 2.0% to 6.0% of HFC-134A, and 10.0% to 18.0% of HFC- 32 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 1.3% than that of R-454C evaluated at the same conditions set, and the minimum and maximum cooling COP efficiencies are 1.5% and 2.3% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum cooling capacity which is 0.6% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 62.0 wt-% R- 1252ZC, 16.0 wt-% HFO-1234ZE(E), 2.0 wt-% HFC-134A, and 18.0 wt-% HFC-32, where the COP for cooling is 1.5% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.5 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum cooling COP efficiency which is 2.1% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 46.0 wt-% R-1252ZC, 38.0 wt-% HFO-1234ZE(E), 2.0 wt-% HFC-134A, and 12.0 wt-% HFC-32, where the CAP for cooling is -9.9% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.3 K and its ASHRAE flammability classification is 2.
  • a composition range of 2.0% to 92.0% of CARBON DIOXIDE, 2.0% to 92.0% of R-1252ZC, 2.0% to 92.0% of HFO- 1234ZE(E), 2.0% to 22.0% of HFC-134A, and 2.0% to 40.0% of HFC-32 will have a GWP less than 300, a maximum average glide of about 10.0 K, a heating capacity range that has a deviation range of -40.4% to 348.8% from the heating capacity of R- 454C evaluated with the same conditions set, and the heating COP range has a deviation range from -22.6% to 1.4% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Table 7b lists example compositions within the GWP ⁇ 300 range that have ASHRAE flammability classifications of 2, 1, 2L and 3.
  • a composition range of 2.0% to 92.0% of CARBON DIOXIDE, 2.0% to 92.0% of R-1252ZC, 2.0% to 92.0% of HFO-1234ZE(E), 2.0% to 22.0% of HFC-134A, and 2.0% to 40.0% of HFC-32 will have a GWP less than 300, a maximum average glide of about 10.0 K, an ASHRAE flammability classification of 2, 1, 3 and 2L, a heating capacity range has a deviation of -40.4% to 348.8% from the heating capacity of R-454C evaluated with the same conditions set, and the heating COP range has a deviation of -22.6% to 1.4% than that of the heating COP of R-454C evaluated with the same conditions set.
  • Preferred blend composition ranges for heating mode within a composition range of 2.0% to 4.0% of CARBON DIOXIDE, 28.0% to 82.0% of R-1252ZC, 2.0% to 40.0% of HFO-1234ZE(E), 2.0% to 20.0% of HFC-134A, and 4.0% to 28.0% of HFC- 32 will have a GWP ⁇ 300, a maximum average heat exchanger glide of 10.0 K, an ASHRAE flammability classification of 2 and 3, the minimum and maximum heating capacities are -10.0% and 10.0% than that of R-454C evaluated at the same conditions set, and the minimum and maximum heating COP efficiencies are -0.4% and 0.9% than that of R-454C evaluated at the same conditions set.
  • composition for the even more preferred maximum heating capacity which is 10.0% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 52.0 wt-% R- 1252ZC, 14.0 wt-% HFO-1234ZE(E), 6.0 wt-% HFC-134A, and 26.0 wt-% HFC-32, where the COP for heating is -0.3% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.3 K and its ASHRAE flammability classification is 2.
  • composition for the even more preferred maximum heating COP efficiency which is 0.8% than that of R-454C, is 2.0 wt-% CARBON DIOXIDE, 58.0 wt-% R-1252ZC, 26.0 wt-% HFO-1234ZE(E), 2.0 wt-% HFC-134A, and 12.0 wt-% HFC-32, where the CAP for heating is -9.5% than that for R-454C under the same cycle conditions, the maximum average heat exchanger glide is 9.5 K and its ASHRAE flammability classification is 2.
  • compositions containing HFO-1252zc, HFO- 1234zeE, HFC-134, and HFC-32 are compared to R-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32) under the conditions for a residential air-conditioner shown below.
  • Tables 8A and 8B provide the calculated results.
  • a composition range of 1.0% to 21.0% of R- 1252zc, 64.0% to 92.0% of HFO-1234ze(E), 1.0% to 11.0% of HFC-134, and 1.0% to 9.0% of HFC-32 will have a GWP ⁇ 150, an ASHRAE flammability rating of 2L, an average temperature glide of no more than 6.5, a cooling capacity of 40.0% to 48.9% of the cooling capacity of R-410A evaluated with the same conditions set, and a cooling COP of 108.6% to 109.3% of the cooling COP of R-410A evaluated with the same conditions set.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'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-134a ou CO2. Les compositions ont un faible GWP et sont utiles dans des procédés de refroidissement et de chauffage, de systèmes ou d'appareils de climatisation et de pompe à chaleur, et des procédés de remplacement de fluides frigorigènes actuels.
PCT/US2025/011628 2024-03-14 2025-01-15 Compositions comprenant du difluoropropène, du tétrafluoropropène et du difluorométhane et leurs utilisations Pending WO2025193321A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463565051P 2024-03-14 2024-03-14
US63/565,051 2024-03-14

Publications (1)

Publication Number Publication Date
WO2025193321A1 true WO2025193321A1 (fr) 2025-09-18

Family

ID=94605810

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2025/011628 Pending WO2025193321A1 (fr) 2024-03-14 2025-01-15 Compositions comprenant du difluoropropène, du tétrafluoropropène et du difluorométhane et leurs utilisations

Country Status (1)

Country Link
WO (1) WO2025193321A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755316A (en) 1987-10-23 1988-07-05 Allied-Signal Inc. Refrigeration lubricants
US5152926A (en) 1989-06-02 1992-10-06 Union Carbide Chemicals & Plastics Technology Corporation Refrigerant lubricant compositions
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
CA2557873A1 (fr) 2004-04-29 2005-11-10 Honeywell International Inc. Compositions contenant des olefines substituees par du fluor
US20060116310A1 (en) 2004-04-16 2006-06-01 Honeywell International Inc. Compositions of HFC-152a and CF3I
US20070290164A1 (en) 2004-09-14 2007-12-20 Idemitsu Kosan Co., Ltd. Refrigerator Oil Composition
WO2008027595A1 (fr) 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Agents stabilisants d'alkylsilane pour fluoroléfines
WO2009018117A1 (fr) 2007-07-27 2009-02-05 E. I. Du Pont De Nemours And Company Compositions contenant des fluoro-oléfines, et leurs utilisations
WO2009042847A1 (fr) 2007-09-28 2009-04-02 E. I. Du Pont De Nemours And Company Compositions stabilisatrices à base d'un liquide ionique
WO2009047535A2 (fr) * 2007-10-12 2009-04-16 Ineos Fluor Holdings Limited Compositions de transfert de chaleur
US20120126187A1 (en) * 2009-04-16 2012-05-24 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8535555B2 (en) 2006-09-01 2013-09-17 E I Du Pont De Nemours And Company Epoxide and fluorinated epoxide stabilizers for fluoroolefins
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 (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755316A (en) 1987-10-23 1988-07-05 Allied-Signal Inc. Refrigeration lubricants
US5152926A (en) 1989-06-02 1992-10-06 Union Carbide Chemicals & Plastics Technology Corporation Refrigerant lubricant compositions
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US20060116310A1 (en) 2004-04-16 2006-06-01 Honeywell International Inc. Compositions of HFC-152a and CF3I
CA2557873A1 (fr) 2004-04-29 2005-11-10 Honeywell International Inc. Compositions contenant des olefines substituees par du fluor
US20070290164A1 (en) 2004-09-14 2007-12-20 Idemitsu Kosan Co., Ltd. Refrigerator Oil Composition
WO2008027595A1 (fr) 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Agents stabilisants d'alkylsilane pour fluoroléfines
US8535555B2 (en) 2006-09-01 2013-09-17 E I Du Pont De Nemours And Company Epoxide and fluorinated epoxide stabilizers for fluoroolefins
WO2009018117A1 (fr) 2007-07-27 2009-02-05 E. I. Du Pont De Nemours And Company Compositions contenant des fluoro-oléfines, et leurs utilisations
WO2009042847A1 (fr) 2007-09-28 2009-04-02 E. I. Du Pont De Nemours And Company Compositions stabilisatrices à base d'un liquide ionique
WO2009047535A2 (fr) * 2007-10-12 2009-04-16 Ineos Fluor Holdings Limited Compositions de transfert de chaleur
US20120126187A1 (en) * 2009-04-16 2012-05-24 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
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

Similar Documents

Publication Publication Date Title
US12473477B2 (en) Refrigerant-containing composition, heat transfer medium, and heat cycle system
US9902888B2 (en) Compositions comprising difluoromethane, pentafluoroethane, tetrafluoropropene, and tetrafluoroethane and uses thereof
JP2024023869A (ja) 安定化されたフルオロオレフィン組成物、並びにその生成、保管、及び使用方法
CN104745148B (zh) 包含氟代烯烃的组合物及其用途
JP7321257B2 (ja) ジフルオロメタン、テトラフルオロプロペン、及び二酸化炭素を含有する組成物、並びにその使用
US12428586B2 (en) Compositions containing tetrafluoropropene, tetrafluoroethane and pentafluoropropene and uses thereof
WO2025019190A1 (fr) Compositions à faible prp comprenant du hfo-1252zc et leurs utilisations
WO2025193321A1 (fr) Compositions comprenant du difluoropropène, du tétrafluoropropène et du difluorométhane et leurs utilisations
WO2025193323A1 (fr) Compositions de mélange contenant du difluoropropène
WO2025019187A1 (fr) Compositions comprenant du difluoropropène et leurs utilisations
WO2025019186A1 (fr) Procédés et appareil utilisant du difluoropropène
WO2025019189A1 (fr) Compositions de mélange contenant du difluoropropène
WO2025072110A1 (fr) Mélanges à faible prg comprenant du 1,2-difluoroéthylène et leurs utilisations
WO2025193322A1 (fr) Compositions à faible gwp comprenant du hfo-1252 zc et leurs utilisations
WO2025159947A1 (fr) Compositions à faible gwp comprenant du hfo-1252zc et leurs utilisations
WO2025072107A1 (fr) Compositions à faible prp comprenant hfo-1132z et leurs utilisations
KR20230082649A (ko) 냉매 압축기 시스템용 냉매 조성물
WO2025072113A1 (fr) Appareil et procédés d'utilisation de z-1,2-difluoroéthylène
WO2025072112A1 (fr) Compositions à faible gwp comprenant du hfo-1132 et leurs utilisations
TW202540026A (zh) 包含二氟丙烯、四氟丙烯、及二氟甲烷之組成物及其用途
TW202540025A (zh) 含有二氟丙烯之摻合組成物
WO2025096365A1 (fr) Compositions comprenant du tétrafluoropropène et leurs utilisations
TW202539987A (zh) 包含ｈｆｏ－１２５２ｚｃ之低ｇｗｐ組成物及其用途
TWI906576B (zh) 含二氟甲烷、四氟丙烯和二氧化碳之組合物及其用途
US20230374361A1 (en) Refrigerant compositions for refrigerant compressor systems

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: 25705417

Country of ref document: EP

Kind code of ref document: A1