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WO2025072113A1 - Appareil et procédés d'utilisation de z-1,2-difluoroéthylène - Google Patents

Appareil et procédés d'utilisation de z-1,2-difluoroéthylène Download PDF

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Publication number
WO2025072113A1
WO2025072113A1 PCT/US2024/048071 US2024048071W WO2025072113A1 WO 2025072113 A1 WO2025072113 A1 WO 2025072113A1 US 2024048071 W US2024048071 W US 2024048071W WO 2025072113 A1 WO2025072113 A1 WO 2025072113A1
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Prior art keywords
hfc
hfo
hcfc
hcfo
composition
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Inventor
Joshua Hughes
Luke David SIMONI
Siddarth SITAMRAJU
Konstantinos Kontomaris
Jason R. Juhasz
David Matthew Snyder
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Chemours Co FC LLC
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Chemours Co FC LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures

Definitions

  • the present invention is directed to a fluoroolefin compound that is useful as a refrigerant, methods and systems using the same, and systems containing the fluoroolefin, Z-1 ,2-difluoroethylene for use in cooling and heating applications.
  • 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 current invention solves certain problems associated with conventional refrigerants and provides HFO-1132(Z) refrigerant, which meets the evolving regulatory landscape.
  • Certain embodiments disclosed herein relate to a fluoropropene composition comprising Z-1 ,2-difluoroethylene (also called HFO-1132(Z), or R- 1132(Z)). This compound is shown herein to have advantageous properties for its use in refrigerant applications.
  • a method of cooling comprising evaporating a composition comprising HFO-1132(Z) 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.
  • a method of heating comprising evaporating a composition comprising HFO-1132(Z) and thereafter condensing said composition in the vicinity of a body to be heated, wherein said heating is provided by a heat pump.
  • the air-conditioner or heat pump is a residential, light commercial, or industrial air-conditioner or heat pump.
  • the heat pump is an automobile heat pump for thermal management of an electric or hybrid vehicle.
  • the heat pump is an automobile heat pump for heating and cooling the passenger compartment of an electric or hybrid vehicle.
  • systems for cooling or heating comprising a composition comprising HFO-1132(Z).
  • the systems for cooling or heating also comprises a lubricant.
  • the systems comprise an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.
  • said airconditioner or heat pump is a residential, light commercial, or industrial airconditioner or heat pump.
  • the system is an automobile heat pump for heating and cooling the passenger compartment of an electric or hybrid vehicle.
  • methods of replacing HFO-1234yf, R-454C, R-32, or propane in an air-conditioner or heat pump comprising providing a composition comprising HFO-1132(Z) as refrigerant to the air-conditioner or heat pump.
  • the composition provides COP greater than COP of HFO-1234yf, R-454C, R-32, or propane when operating under the same conditions.
  • compositions comprising HFO-1132(Z) as refrigerant in air conditioning and heat pumps.
  • the air conditioners are selected from residential, commercial, or industrial air conditioning system, window, ducted, ductless, packaged terminal, or rooftop systems.
  • heat pumps are selected from residential, commercial, or industrial heat pumps, hot water heat pumps, high temperature heat pumps, or automobile heat pumps.
  • composition further comprises at least one additional compound selected from the group consisting of HFO-1132(E), HCFC- 133, HCFC-133b, HCFC-123, HFC-152, HFC-143, HFC-41, HCFC-22, propylene, ethylene, acetylene, HCFC-142a, HFO-1123, HFO-1141, HFO-1132a, HCFO- 1131 E, HCFO-1131Z, HCFO-1122, and HCFO-1122a.
  • HFO-1132(E) HFO-1132(E), HCFC- 133, HCFC-133b, HCFC-123, HFC-152, HFC-143, HFC-41, HCFC-22, propylene, ethylene, acetylene, HCFC-142a, HFO-1123, HFO-1141, HFO-1132a, HCFO- 1131 E, HCFO-1131Z, HCFO-1122, and HCFO-1122a.
  • composition further comprises at least one additional compound and the total amount of additional compounds is greater than zero and less than 1 weight percent.
  • the additional compounds comprise at least one selected from HFO-1132(E), HFO-1132a, HFC-152, HCFC-123, HCFC-142a, and HCFO-1122.
  • composition is determined to be class 2 for flammability, as defined in ANSI/ASHRAE Standard 34.
  • composition further comprises a lubricant.
  • lubricant is a polyalkylene glycol, polyol ester, poly-a-olefin, or polyvinyl ether.
  • the lubricant is polyol ester or polyvinyl ether.
  • 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.
  • 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.
  • composition comprises a stabilizer
  • 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.
  • the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-terbutyl-4- methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, d-limonene, a-terpinene, p- terpinene, a-pinene, p-pinene, or butylated hydroxytoluene.
  • the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-terbutyl-4- methylphenol, fluorinated epoxides, n-butyl g
  • the stabilizer is present in an amount from about 0.001 to 1 .0 weight percent based on the weight of the refrigerant.
  • composition comprises at least one tracer.
  • 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.
  • said at least one tracer is selected from the group consisting of HFC-23, HCFC-31 , HFC-41 , HFC-161 , HFC-143a, HFC-134a, HFC- 125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC- 338pcc, CFC-12, CFC-11 , CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO- 1141
  • compositions comprising HFO-1132(Z) as refrigerant in air-conditioning and heat pumps.
  • compositions comprising HFO-1132(Z) as refrigerant in residential, commercial, or industrial air conditioning systems including window, ducted, ductless, packaged terminal or rooftop systems.
  • compositions comprising HFO-1132(Z) in air-conditioning systems operating in ambient temperatures of 35°C or higher.
  • compositions comprising HFO-1132(Z) in residential, commercial, or industrial heat pumps, hot water heat pumps, high temperature heat pumps, or automobile heat pumps.
  • compositions comprising HFO-1132(Z) in automobile heat pumps for electric or hybrid vehicles.
  • compositions comprising HFO-1132(Z) in air conditioning systems or heat pumps that are secondary loop systems.
  • a method of improving heat transfer comprising matching the temperature profile of the refrigerant comprising, consisting of, or consisting essentially of HFO-1132Z to the temperature profile of the heat transfer fluid in a secondary loop system.
  • 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.
  • FIG. 1 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 2 illustrates a reversible cooling or heating loop system, according to an embodiment.
  • FIG. 3 illustrates a cooling or heating loop system, according to an embodiment.
  • FIG. 4 illustrates a cooling or heating loop system, according to an embodiment.
  • FIG. 5 illustrates a cooling or heating loop system, according to an embodiment.
  • FIG. 6 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 7 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 8 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 9 illustrates a cooling or heating system, according to an embodiment.
  • FIG. 10 illustrates an embodiment of a secondary loop cooling and heating system for electric and hybrid vehicles.
  • HFO-1132(Z) may potentially be a candidate to replace refrigerants such as HFO-1234yf, R-410A, R-454C or propane with low Global Warming Potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP), especially in applications where little or no temperature glide is required.
  • refrigerants such as HFO-1234yf, R-410A, R-454C or propane with low Global Warming Potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP), especially in applications where little or no temperature glide is required.
  • GWP Global Warming Potential
  • COP energy efficiency
  • HFO-1132(Z) would also be a potential alternative to propane in water heating heat pumps with improved energy efficiency and improved flammability properties.
  • the higher critical temperature of HFO-1132(Z) (121 °C) vs. R-454C (85.7 °C) and propane (96.7 °C) will allow for higher hot water delivery temperatures.
  • its higher critical temperature allows use of HFO- 1132(Z) in air-conditioning applications at high ambient temperatures, in regions such as the middle east, among others, where ambient temperature can reach higher than 35 °C.
  • a refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to vapor 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 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.
  • 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.
  • Z-1 ,2-difluoroethylene (HFO-1132(Z) or R-1132(Z)) may be prepared by dehydrochlorination of 1-chloro-1,2-difluoroethane (HCFC-142a) in either the gas phase or liquid phase as described in U.S. Patent Publication 2022-0017438A. The reaction will produce both the E- and Z- isomers of the compound, but they are separable by distillation.
  • 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
  • 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
  • the GWP of HFO-1132(Z) is estimated at ⁇ 1.
  • ODP Ozone depletion potential
  • HFCs Hydrofluorocarbons
  • HFO hydrofluoro-olefins
  • the composition comprising, consisting of, or consisting essentially of HFO-1132(Z) provides COP higher than HFO-1234yf, R- 410A, R-454C, and propane.
  • the composition comprising, consisting of, or consisting essentially of HFO-1132(Z) provides zero temperature glide.
  • the composition comprising, consisting of, or consisting essentially of HFO-1132(Z) provides low GWP estimated at ⁇ 1.
  • the composition comprising, consisting of, or consisting essentially of HFO-1132(Z) provides higher critical temperature than R-410A, R- 454C, and propane, allowing use in hot water heat pumps to deliver higher temperature water and to provide air-conditioning (cooling) in regions of the world with high ambient temperatures (35°C or higher).
  • HFO-1132(Z) has zero temperature glide in the heat exchangers (e.g., evaporators and condensers), as there is no fractionation or shifting of the composition during operation.
  • 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).
  • the estimated heat of combustion of this novel refrigerant is > 19,000 kJ/kg.
  • ASH RAE 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-1132(Z) is estimated as being class 2 flammability as defined by ANSI/ASHRAE standard 34 and ISO 817. Class 2 flammability may be manageable in air-conditioning and heat pumps. Specific applications may have different requirements, with regards to flammability. Systems using HFO-1132(Z) as refrigerant may be required to use a secondary loop system.
  • compositions comprising, consisting of, or consisting essentially of HFO-1132(Z) may further comprise additional compounds.
  • the additional compounds are present in an amount of greater than about 0 and less than 1 weight percent.
  • compositions comprising, consisting of, or consisting essentially of HFO-1132(Z) may further comprise at least one additional compound selected from HFO-1132(E) (E-1 ,2-difluoroethylene), HCFC-133 (1- chloro-1 ,1 ,2-trifluoroethane), HCFC-133b (2-chloro-1 ,1 ,1-trifluoroethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), HFC-152 (1 ,2-difluoroethane), HFC-143 (1,1 ,2- trifluoroethane), HFC-41 (fluoromethane), HCFC-22 (chlorodifluoromethane), propylene, ethylene, acetylene, HCFC-142a (1-chloro-1,2-difluoroethane), HFO- 1123 (trifluoroethylene), HFO-1141 (fluoro
  • compositions comprising, consisting of, or consisting essentially of HFO-1132(Z) may further comprise at least one additional compound selected from the group consisting of HFO-1132(E), HFO-1132a, HFC-152, HCFC-133, HCFC-123, HCFC-142a, and HCFO-1122.
  • the compositions comprising, consisting of, or consisting essentially of HFO-1132(Z) may further comprise at least one additional compound comprising HCFC-133.
  • the compositions comprising, consisting of, or consisting essentially of HFO-1132(Z) may further comprise at least one additional compound comprising HCFC-142a.
  • 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-1132(Z) 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-1132(Z) 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-1132(Z) 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-di- tertbutyl-4-methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, cyclic monoterpenes, terpenes, such as d-limonene, a-terpinene, p-terpinene, y-terpinene, a-pinene, or - pinene,
  • the refrigerant 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-1132(Z) 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 HFO-1132(Z) 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-1132(Z) further comprise at least one lubricant.
  • compositions further comprise a lubricant selected from the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, polyvinyl ether, and combinations thereof.
  • compositions further comprise a lubricant selected from the group consisting of polyol esters, polyvinyl ethers, or combinations thereof.
  • 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.
  • 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), polyalkylene glycols (PAGs), and polyvinyl ethers (PVEs).
  • POEs polyol esters
  • PAGs polyalkylene glycols
  • PVEs polyvinyl ethers
  • a POE polyol esters
  • PAGs polyalkylene glycols
  • PVEs polyvinyl ethers
  • PVEs polyvinyl ethers
  • compositions comprising, consisting of or consisting essentially of HFO-1132(Z) are combined with a PAG lubricant or a PVE lubricant or a POE lubricant for usage in an automotive A/C or heat pump system having an internal combustion engine or an electric or hybrid electric drive train.
  • 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.
  • the inventive refrigerant composition 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.
  • Mouli et al. (WO 2008/027595 and WO 2009/042847) teach 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-134, HFC-227ea, HFC-236fa, CF 3 I, 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-1132(Z), and are free of or substantially free of Group A Fluorinated Substances, such as TFA.
  • the phrase "free of” as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas sample or liquid sample, and/or ion chromatography by analysis of a water sample after bubbling the thermal fluid through water.
  • the phrase "substantially free of” as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is > 0 wt.% and ⁇ _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)
  • GC gas chromatographic
  • degradation products of such compositions of the present invention which comprise, consist of, or consist essentially of HFO- 1132(Z) 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-1132(Z) 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-1132(Z) 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 HFO- 1132(Z).
  • a method of heating comprising evaporating a composition comprising HFO-1132(Z) 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, 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, high temperature heat pumps, and automobile heat pumps.
  • the heat pump is an automobile heat pump for electric or hybrid vehicles.
  • Electric or hybrid vehicles include automobiles with no internal combustion engine (ICE) or those that maintain an ICE but also use electric power and are therefore hybrid electric vehicles (HEV) or plug-in hybrid electric vehicles (PH EV) or mild hybrid electric vehicles (MHEV). Additionally, electric or hybrid vehicles include full electric vehicles (EV), such as battery electric vehicles (BEV). All of these electric or hybrid vehicles use at least one electric motor, wherein the electric motor provides some form of propulsion for the vehicles normally provided by the ICE found in gasoline/diesel powered vehicles.
  • ICE internal combustion engine
  • HEV hybrid electric vehicles
  • PH EV plug-in hybrid electric vehicles
  • MHEV
  • the high critical temperature of HFO-1132(Z) allows for heating water to higher temperatures than H FC-32, R-410A, propane, or R-454C while maintaining subcritical operating conditions.
  • 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 essentially of, or consisting of HFO-1132(Z) 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-1132(Z) 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-1132(Z) 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-1132(Z) 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, industrial, or automobile 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 system may be particularly useful in high ambient temperature regions (35°C or higher), due to the high critical temperature of HFO-1132 (Z).
  • 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, high temperature heat pumps, automobile heat pumps.
  • the heat pump is an automobile heat pump for electric or hybrid vehicles.
  • Electric or hybrid vehicles include automobiles with no internal combustion engine (ICE) or those that maintain an ICE but also use electric power and are therefore hybrid electric vehicles (HEV) or plug-in hybrid electric vehicles (PHEV) or mild hybrid electric vehicles (MHEV). Additionally, electric or hybrid vehicles include full electric vehicles (EV), such as battery electric vehicles (BEV). All of these electric or hybrid vehicles use at least one electric motor, wherein the electric motor provides some form of propulsion for the vehicles normally provided by the ICE found in gasoline/diesel powered vehicles.
  • ICE internal combustion engine
  • HEV hybrid electric vehicles
  • PHEV plug-in hybrid electric vehicles
  • MHEV mild hybrid electric vehicles
  • an automobile heat pump system comprising HFO- 1132(Z) as refrigerant, may be a secondary loop system.
  • a secondary loop system will isolate a flammable refrigerant from the passenger compartment, thus providing a higher level of safety.
  • a refrigeration system 100 having a refrigeration loop 110 comprises a first heat exchanger 120, a pressure regulator 130, a second heat exchanger 140, a compressor 150 and a four-way valve 160.
  • the first and second heat exchangers are of the air/refrigerant type.
  • the first heat exchanger 120 has passing through it the refrigerant of the loop 110 and the stream of air created by a fan.
  • the refrigerant set-in motion by the compressor 150 passes, via the valve 160, through the heat exchanger 120 which acts as a condenser, that is to say gives up heat energy to the outside, then through the pressure regulator 130 then through the heat exchanger 140 that is acting as an evaporator thus cooling the stream of air intended to be blown into the motor vehicle cabin interior or other body to be cooled.
  • the direction of flow of the refrigerant is reversed using the valve 160.
  • the heat exchanger 140 acts as a condenser while the heat exchanger 120 acts as an evaporator.
  • the heat exchanger 140 can then be used to heat up the stream of air intended for the motor vehicle cabin or other body to be cooled.
  • Additional heat transfer loops may be connected to the heat pump system and absorb or reject heat at the heat exchangers 120 and/or 140 to allow transfer of heat away from the motor or battery, and therefore serve to provide thermal management of those components of the vehicle as well as cooling and heating for the passenger cabin.
  • a refrigeration system 300 having a refrigeration loop 310 comprises a first heat exchanger 320, a pressure regulator 330, a second heat exchanger 340, a compressor 350 and a four-way valve 360.
  • the first and second heat exchangers 320 and 340 are of the air/refrigerant type.
  • the way in which the heat exchangers 320 and 340 operate is the same as in the first embodiment depicted in FIG. 1.
  • Two fluid/liquid heat exchangers 370 and 380 are installed both on the refrigeration loop circuit 310 and on the engine cooling circuit or on a secondary glycol-water circuit. Installing fluid/liquid heat exchangers without going through an intermediate gaseous fluid (e.g. air) contributes to improving heat exchange by comparison with air/fluid heat exchangers.
  • an intermediate gaseous fluid e.g. air
  • the system for heating and cooling the passenger compartment of an electric vehicle further comprises a reheater operably connected between the compressor and the condenser for reduction of humidity in the passenger compartment during cooling mode.
  • a refrigeration system 400 having a refrigeration loop 410 comprises a first heat exchanger (condenser) 420, a pressure regulator 430, a second heat exchanger (evaporator) 440, a compressor 450, a three-way valve 460, and a third heat exchanger (for reheat) 470.
  • a first heat exchanger condenser
  • a pressure regulator 430 a second heat exchanger
  • a compressor 450 for reheat
  • three-way valve 460 for reheat
  • third heat exchanger for reheat
  • the exit stream from the third heat exchanger 470 discharges into the inlet of the first heat exchanger 420.
  • the refrigerant is condensed by the first heat exchanger 420 using an external fan 480 and ambient air as the heat sink.
  • the existing saturated or subcooled liquid is expanded in the pressure regulator 430 and the resulting lower pressure saturated mixture of refrigerant liquid and vapor enters the second heat exchanger 440.
  • the refrigerant evaporates in the second heat exchanger 440 through the use of a second fan 490 that is external to the refrigeration loop.
  • the air passing across the second heat exchanger 440 is cooled to below the air dew point temperature. This causes the moisture in the air to partially condense, thereby lowering the absolute humidity of the air.
  • the air then passes over the third heat exchanger 470, which transfers heat into the air, increasing the air temperature to above the dew point and lowering the relative humidity of the air, which is then supplied to the passenger compartment.
  • an air-conditioning (AC) and heat pump (HP) system 500 heating, cooling, or both can be accomplished in a vehicle cabin or for other vehicle loads.
  • the system 500 includes an AC circuit 510 and a HP circuit 520.
  • the HP control valve 530 upstream of the heat pump condenser 540 will be closed and the refrigerant will flow from the compressor 550 into the air-cooled AC condenser 560, through an AC expansion valve 570, and into the AC evaporator 580; providing cooling to the cabin. From the AC evaporator 580, the refrigerant will flow back to the compressor 550.
  • the AC control valve 535 upstream of the AC condenser 560 will be closed and the refrigerant will flow from the compressor 550 into the HP condenser 540 to provide heating to the cabin. From the HP condenser 540 the refrigerant will flow through the HP expansion valve 575 to the HP evaporator 585.
  • a separate humidity control mode could be accomplished by sending a portion of the compressor discharge gas into the AC circuit 510 and the remaining portion into the HP circuit 520.
  • a system 600 for heating, cooling, or both can be accomplished for a vehicle cabin or for other vehicle loads.
  • the system 600 includes an AC circuit 610 and a water-cooled/HP circuit 620.
  • the water loop control valve 630 upstream of the water-cooled condenser 640 will be closed and the refrigerant will flow from the compressor 650 into the AC condenser 660, through an AC expansion valve 670, and into the AC evaporator 680; providing cooling to the cabin.
  • the AC control valve 635 upstream of the AC condenser 660 will be closed and the refrigerant will flow from the compressor 650 into the water-cooled condenser 640.
  • a heat transfer fluid (e.g., water or other heat transfer fluid) will take the heat generated in the water-cooled condenser 640 and transfer it to the cabin heater core 690; providing heat to the cabin.
  • the heat transfer fluid may return from the cabin heater core 690 to the water-cooled condenser 640.
  • the refrigerant will flow from the water-cooled condenser 640 through an HP expansion valve 675 into the HP evaporator 685 that cools a heat transfer fluid, which may be used to cool other components of the automobile and then back to the compressor 650.
  • there is one or more water/heat transfer fluid loop that may be used to heat and/or cool various other components of the vehicle.
  • a separate humidity control mode could be accomplished by sending a portion of the compressor discharge gas into the AC circuit 610 and the remaining portion into the water cooled/HP circuit 620.
  • the refrigerant circuit 700 in heating mode wherein specific conditions exist where both the vehicle cabin and other vehicle components require heat, operates as shown in FIG. 6.
  • discharge refrigerant vapor will take two paths.
  • One path is through the cabin condenser 740.
  • the cabin condenser 740 is a refrigerant-to-air heat exchanger typically of the fin-tube or microchannel type and can be single or multiple pass.
  • a first fan 745 in the vehicle ventilation ductwork will induce a flow of either 100% outside air or a mixture of outside air and return air from the vehicle cabin across this cabin condenser 740 and the refrigerant as it condenses will heat the air.
  • a physical bypass 735 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin evaporator 730.
  • the second path of refrigerant out of the compressor is through valve 770 and into a liquid/heat transfer fluid heat exchanger 720, which allows heat to be transferred from the warm refrigerant to the vehicle’s heat transfer fluid loop (not shown).
  • This vehicle heat transfer loop can then be used to manage other vehicle heat loads.
  • the heat transfer fluid of the heat transfer fluid loop may be water or a water/glycol solution.
  • the condensed refrigerant out of exchanger 720 then combines with the condenser 740 liquid refrigerant outlet and the combined stream flows through an expansion device 775, which will drop the pressure of the liquid refrigerant and generate a liquid-vapor mixture.
  • This liquid-vapor mixture then flows through the outdoor heat exchanger 780 (i.e. , evaporator in this setup).
  • the outdoor heat exchanger 780 will be a refrigerant-to-air heat exchanger typically of the fin-tube or microchannel type and can be single or multiple pass.
  • a second fan 785 will induce airflow across the outdoor heat exchanger 780 and allow the liquid-vapor refrigerant mixture to pick up heat from the ambient air and vaporize completely before it flows back to the compressor 750.
  • the refrigerant circuit 800 in heating mode when specific conditions exist where only cabin heating is required, operates as shown in FIG. 7. Starting at the compressor 850, discharge vapor will first flow through the cabin condenser 840. A first fan 845 in the vehicle ventilation ductwork will induce a flow of either 100% outside air or a mixture of outside air and return air from the vehicle cabin across this cabin condenser 840 and the refrigerant will exchange heat between the condenser 840 and the air. In this mode, a physical bypass 835 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin evaporator 830.
  • the refrigerant will condense in the cabin condenser 840 and flow to an expansion device 875 which will drop the pressure of the liquid refrigerant and generate a liquid-vapor mixture.
  • This liquid-vapor mixture flows through the outdoor heat exchanger 880 (i.e. , evaporator in this setup).
  • a second fan 885 will induce airflow across the outdoor heat exchanger 880 and allow the liquid-vapor refrigerant mixture to pick up heat from the ambient air and vaporize completely before it travels back to the compressor 850.
  • the refrigerant circuit 900 in cooling mode when specific conditions exist where both the vehicle cabin and the vehicle components require cooling, operates as shown in FIG. 8. Starting at the compressor 950, discharge refrigerant vapor will first flow through the cabin condenser 940, wherein there will be no heat transfer as in this mode, a physical bypass 945 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin condenser 940. Vapor refrigerant will pass through the cabin condenser 940 and flow through valve 975 and into the outdoor heat exchanger 980.
  • the outdoor heat exchanger 980 acts as a condenser as a first fan 985 induces flow across the heat exchanger and the hot refrigerant vapor exchanges heat and condenses to a liquid. A portion of this liquid refrigerant will leave the outdoor heat exchanger 980 and enter the internal heat exchanger 990. Liquid refrigerant will be subcooled in the internal heat exchanger 990 and then flow to an expansion device 910 and into the cabin evaporator 930. This air-to-refrigerant cabin evaporator 930 will be of the fin-tube or microchannel type of heat exchanger and can be single or multiple pass.
  • a second fan (or cabin blower fan) 935 will induce a flow of either 100% outside air or a mixture of outside air and return air from the cabin across the coil of the cabin evaporator 930 where heat will be exchanged between the air and refrigerant.
  • the refrigerant will vaporize and travel back to the internal heat exchanger 990 where it will be further superheated until it finally re-enters the compressor 950.
  • the remaining portion of refrigerant exiting the condenser 980 will flow through expansion valve 915 and into the liquid/heat transfer fluid heat exchanger 920 wherein vehicle component heat is transferred via a heat transfer fluid loop (not shown) into the refrigerant. This vehicle heat transfer loop can then be used to manage other vehicle heat loads.
  • the refrigerant vaporizes in heat exchanger 920 and joins the refrigerant exiting internal heat exchanger 990 at the suction of the compressor 950.
  • the refrigerant circuit 1000 in cooling mode when specific conditions exist where only vehicle cabin cooling is required, operates as shown in FIG. 9. Starting at the compressor 1050, discharge refrigerant vapor will first flow through the cabin condenser 1040, wherein there will be no heat transfer, as in this mode, a physical bypass 1045 within the vehicle ventilation ductwork will prevent any air from flowing over the cabin condenser 1040. Vapor refrigerant will pass through the cabin condenser 1040 and flow through a valve 1075 to the outdoor heat exchanger 1080.
  • the outdoor heat exchanger 1080 acts as a condenser as a first fan 1085 induces flow across the heat exchanger 1080 and the hot refrigerant vapor exchanges heat and condenses to a liquid.
  • This liquid refrigerant will leave the outdoor heat exchanger 1080 and enter the internal heat exchanger 1090.
  • Liquid refrigerant will be subcooled in the internal heat exchanger 1090 and then flow to an expansion device 1010 and into the cabin evaporator 1030.
  • a second fan (or cabin blower fan) 1035 will induce a flow of either 100% outside air or a mixture of outside air and return air from the cabin across the cabin evaporator 1030 where heat will be exchanged between the air and refrigerant.
  • the refrigerant will vaporize and flow back to the internal heat exchanger 1090 where it will be further superheated until it finally returns to the compressor 1050.
  • FIG. 10 illustrates an electric vehicle heat pump with secondary loops.
  • the purpose of the secondary loops are to separate the refrigerant from the “users” or various vehicle heat exchangers used to cool/heat the cabin air, the power electronics, and the battery to enable the use of refrigerants with a higher flammability than historic refrigerants used for vehicles.
  • the heat pump itself consists of a compressor (1), a condenser (2), an expansion valve (3), and an evaporator (4).
  • the concept here is that the refrigerant loop is close coupled, contained within the “engine compartment,” and does not require reversing capability.
  • Two separate heat transfer fluid i.e.
  • the first heat transfer fluid loop is contained within the “engine compartment” and utilizes an air-to-liquid heat exchanger (5) and circulation pump (6) to discharge heat from the condenser (2) in air-conditioning mode or provide heat to the evaporator (4) in heat pump mode or a combination of both. Air flows over the heat exchanger (5) via an external fan.
  • the second heat transfer fluid loop consists of a pump (7) and heat exchanger (8). For simplicity, one heat exchanger is shown, when in reality, several heat exchangers could be employed providing heating/cooling to the cabin air, the power electronics, and the battery. Control valves (9), (10), (11), and (12) are used to depict the flexibility of such a system to provide heating, cooling, or both to any given heat exchanger via communication with the heat pump condenser (2) and evaporator (4).
  • an automobile heat pump system may include a positive temperature coefficient (PTC) heater.
  • the PTC heater may be needed for use of the automobile heat pump in hybrid vehicles, such as HEV, PHEV, MHEV, to provide heating to the passenger compartment of an automobile. Additionally, the PTC heater may be needed when the ambient temperature is below about -20 °C, or below about -30 °C. In another embodiment, no PTC heater may be needed in some systems, so the system may not include a PTC heater.
  • the high critical temperature of HFO-1132(Z) allows for heating water to higher temperatures than H FC-32, R-410A, propane, or R-454C while maintaining subcritical operation. Thus, the heat pump system comprising HFO-1132(Z) is useful as high temperature heat pump and hot water heat pump systems.
  • the system comprising HFO-1132(Z) is useful in regions where the ambient temperature can exceed at least 35°C. Thus, providing cooling in high temperature regions of the world.
  • a method for replacing HFO- 1234yf, R-454C, R-32, or propane in an air-conditioner or heat pump comprising providing a composition comprising HFO-1132(Z) as refrigerant to the air-conditioner or heat pump.
  • compositions comprising HFO-1132(Z) provide COP greater than any of HFO-1234yf, R-454C, R-32, or propane with GWP lower than R-454C or R-32. Additionally, HFO-11132(Z) has a lower compressor discharge temperature than R- 32, making it desirable as a replacement for R-32.
  • compositions comprising HFO- 1132(Z) as refrigerant in air-conditioning and heat pump systems. Many embodiments of this use are described herein above.
  • HFO-1132(Z) provides the highest COP (a measure of energy efficiency) as compared to R-410A, R-454C, R-32, propane, or HFO-1234ze(E). Additionally, HFO-1132(Z) has zero glide, and lower pressures than propane and R-32, and lower discharge temperature than R-32. Further, with its high critical point, it can also serve well for air conditioning in high ambient temperature conditions, as well as provide heating at higher temperatures in heat pumps while maintaining subcritical operation.
  • thermodynamic modeling program was used to calculate the expected performance of the refrigerant comprising HFO-1132(Z) compared to HFO-1234yf alone. Fourteen different sets of conditions were modeled, the conditions being specified by the Society of Automotive Engineers (SAE) for characterization of refrigerant performance in an automobile heat pump system. Physical properties for the components were taken from NIST REFPROP Version 10.
  • Compressor isentropic efficiency 70%
  • Compressor volumetric efficiency 95 %
  • HFO-1132(Z) surprisingly provides volumetric capacity over 26% higher, and COP 49% higher than for HFO-1234yf alone. Furthermore, the above data demonstrate that HFO-1132(Z) surprisingly provides average volumetric capacity over 2% higher, and average COP over 7% higher than for HFO-134a alone. Furthermore, HFO-1132(Z) has over 9% higher COP and boiling point closer to HFC-134a than propane alone.
  • the performance data in Table 3 show that HFO-1132(Z) can easily be used to provide more than adequate cooling and heating to a passenger cabin of an electric or hybrid vehicle.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Air-Conditioning For Vehicles (AREA)

Abstract

La présente divulgation concerne l'utilisation de Z-1,2-difluoroéthylène (HFO-1132(Z)) dans des procédés de refroidissement et de chauffage, et des systèmes de refroidissement et de chauffage. En particulier, la composition est utile dans des pompes à chaleur et climatisation, y compris des pompes à chaleur d'automobile pour véhicules électriques et hybrides. Les propriétés du HFO-1132(Z) le rendent particulièrement utile dans des pompes à chaleur à haute température, des pompes à chaleur à eau chaude et la climatisation dans des régions à température ambiante élevée.
PCT/US2024/048071 2023-09-29 2024-09-24 Appareil et procédés d'utilisation de z-1,2-difluoroéthylène Pending WO2025072113A1 (fr)

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EP3919843A1 (fr) * 2019-01-30 2021-12-08 Daikin Industries, Ltd. Dispositif de conditionnement d'air en boîte

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