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US20230002659A1 - Composition containing refrigerant, use of said composition, refrigerator having said composition, and method for operating said refrigerator - Google Patents

Composition containing refrigerant, use of said composition, refrigerator having said composition, and method for operating said refrigerator Download PDF

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Publication number
US20230002659A1
US20230002659A1 US17/887,125 US202217887125A US2023002659A1 US 20230002659 A1 US20230002659 A1 US 20230002659A1 US 202217887125 A US202217887125 A US 202217887125A US 2023002659 A1 US2023002659 A1 US 2023002659A1
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United States
Prior art keywords
mass
refrigerant
hfo
point
r1234yf
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US17/887,125
Inventor
Mitsushi Itano
Daisuke Karube
Yuuki YOTSUMOTO
Kazuhiro Takahashi
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Daikin Industries Ltd
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Daikin Industries Ltd
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Publication date
Priority claimed from PCT/JP2018/038748 external-priority patent/WO2019123806A1/en
Priority claimed from US16/913,639 external-priority patent/US11549041B2/en
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to US17/887,125 priority Critical patent/US20230002659A1/en
Publication of US20230002659A1 publication Critical patent/US20230002659A1/en
Pending legal-status Critical Current

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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
    • C09K2205/122—Halogenated 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures

Definitions

  • the present disclosure relates to a composition comprising a refrigerant, use of the composition, a refrigerating machine having the composition, and a method for operating the refrigerating machine.
  • R410A is currently used as an air conditioning refrigerant for home air conditioners etc.
  • R410A is a two-component mixed refrigerant of difluoromethane (CH 2 F 2 : HFC-32 or R32) and pentafluoroethane (C 2 HF 5 : HFC-125 or R125), and is a pseudo-azeotropic composition.
  • refrigerating capacity also referred to as “cooling capacity” or “capacity”
  • Class 2L lower flammability
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • a composition comprising a refrigerant
  • composition according to any one of Items 1 to 9, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.
  • composition according to any one of Items 1 to 10, for use as an alternative refrigerant for R410A for use as an alternative refrigerant for R410A.
  • composition according to any one of Items 1 to 10 as an alternative refrigerant for R410A.
  • a refrigerating machine comprising the composition according to any one of Items 1 to 10 as a working fluid.
  • a method for operating a refrigerating machine comprising the step of circulating the composition according to any one of Items 1 to 10 as a working fluid in a refrigerating machine.
  • the refrigerant according to the present disclosure has three types of performance; i.e., a refrigerating capacity that is equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the ASHRAE standard.
  • FIG. 1 is a schematic view of an apparatus used in measuring a burning velocity.
  • FIG. 2 is a view showing points A to C, E, G, and I to W; and line segments that connect points A to C, E, G, and I to W in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass %.
  • the present inventors conducted intensive studies to solve the above problem, and consequently found that a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (HFC-32 or R32), and 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or R1234yf) has the properties described above.
  • HFO-1132(E) trans-1,2-difluoroethylene
  • FC-32 or R32 difluoromethane
  • HFO-1234yf or R1234yf 2,3,3,3-tetrafluoro-1-propene
  • the present disclosure has been completed as a result of further research based on this finding.
  • the present disclosure includes the following embodiments.
  • refrigerant includes at least compounds that are specified in ISO 817 (International Organization for Standardization), and that are given a refrigerant number (ASHRAE number) representing the type of refrigerant with “R” at the beginning; and further includes refrigerants that have properties equivalent to those of such refrigerants, even though a refrigerant number is not yet given.
  • Refrigerants are broadly divided into fluorocarbon compounds and non-fluorocarbon compounds in terms of the structure of the compounds.
  • Fluorocarbon compounds include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC).
  • Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), and the like.
  • composition comprising a refrigerant at least includes (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further comprises other components and that can be mixed with at least a refrigeration oil to obtain a working fluid for a refrigerating machine, and (3) a working fluid for a refrigerating machine containing a refrigeration oil.
  • the composition (2) is referred to as a “refrigerant composition” so as to distinguish it from a refrigerant itself (including a mixture of refrigerants).
  • the working fluid for a refrigerating machine (3) is referred to as a “refrigeration oil-containing working fluid” so as to distinguish it from the “refrigerant composition.”
  • the first type of “alternative” means that equipment designed for operation using the first refrigerant can be operated using the second refrigerant under optimum conditions, optionally with changes of only a few parts (at least one of the following: refrigeration oil, gasket, packing, expansion valve, dryer, and other parts) and equipment adjustment.
  • this type of alternative means that the same equipment is operated with an alternative refrigerant.
  • Embodiments of this type of “alternative” include “drop-in alternative,” “nearly drop-in alternative,” and “retrofit,” in the order in which the extent of changes and adjustment necessary for replacing the first refrigerant with the second refrigerant is smaller.
  • alterative also includes a second type of “alternative,” which means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use with the first refrigerant by using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.
  • refrigerating machine refers to machines in general that draw heat from an object or space to make its temperature lower than the temperature of ambient air, and maintain a low temperature.
  • refrigerating machines refer to conversion machines that gain energy from the outside to do work, and that perform energy conversion, in order to transfer heat from where the temperature is lower to where the temperature is higher.
  • a refrigerant having a “WCF lower flammability” means that the most flammable composition (worst case of formulation for flammability: WCF) has a burning velocity of 10 cm/s or less according to the US ANSI/ASHRAE Standard 34-2013.
  • a refrigerant having “ASHRAE lower flammability” means that the burning velocity of WCF is less than 10 cm/s, that the most flammable fraction composition (worst case of fractionation for flammability: WCFF), which is specified by performing a leakage test during storage, shipping, or use based on ANSI/ASHRAE 34-2013 using WCF, has a burning velocity of 10 cm/s or less, and that flammability classification according to the US ANSI/ASHRAE Standard 34-2013 is determined to be classified as “Class 2L.”
  • the refrigerant according to the present disclosure is a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf).
  • the refrigerant according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant; i.e., a refrigerating capacity equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the ASHRAE standard.
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure is preferably a refrigerant wherein
  • the refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), R32, and R1234yf, as long as the above properties and effects are not impaired.
  • the refrigerant according to the present disclosure preferably comprises HFO-1132(E), R32, and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more based on the entire refrigerant.
  • additional refrigerants are not limited, and can be selected from a wide range of refrigerants.
  • the mixed refrigerant may comprise a single additional refrigerant, or two or more additional refrigerants.
  • the refrigerant according to the present disclosure can be preferably used as a working fluid in a refrigerating machine.
  • composition according to the present disclosure is suitable for use as an alternative refrigerant for R410A.
  • the refrigerant composition according to the present disclosure comprises at least the refrigerant according to the present disclosure, and can be used for the same use as the refrigerant according to the present disclosure. Moreover, the refrigerant composition according to the present disclosure can be further mixed with at least a refrigeration oil to thereby obtain a working fluid for a refrigerating machine.
  • the refrigerant composition according to the present disclosure further comprises at least one other component in addition to the refrigerant according to the present disclosure.
  • the refrigerant composition according to the present disclosure may comprise at least one of the following other components, if necessary.
  • the refrigerant composition according to the present disclosure when used as a working fluid in a refrigerating machine, it is generally used as a mixture with at least a refrigeration oil. Therefore, it is preferable that the refrigerant composition according to the present disclosure does not substantially comprise a refrigeration oil.
  • the content of the refrigeration oil based on the entire refrigerant composition is preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %.
  • the refrigerant composition according to the present disclosure may contain a small amount of water.
  • the water content of the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant.
  • a small amount of water contained in the refrigerant composition stabilizes double bonds in the molecules of unsaturated fluorocarbon compounds that can be present in the refrigerant, and makes it less likely that the unsaturated fluorocarbon compounds will be oxidized, thus increasing the stability of the refrigerant composition.
  • Tracer A tracer is added to the refrigerant composition according to the present disclosure at a detectable concentration such that when the refrigerant composition has been diluted, contaminated, or undergone other changes, the tracer can trace the changes.
  • the refrigerant composition according to the present disclosure may comprise a single tracer, or two or more tracers.
  • the tracer is not limited, and can be suitably selected from commonly used tracers. It is preferable that a compound that cannot be an impurity inevitably mixed into the refrigerant according to the present disclosure is selected as the tracer.
  • tracers examples include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N 2 O).
  • the tracer is particularly preferably a hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon, a fluorocarbon, a hydrochlorocarbon, a fluorocarbon, or a fluoroether.
  • the following compounds are preferable as the tracer.
  • FC-14 (tetrafluoromethane, CF 4 ) HCC-40 (chloromethane, CH 3 Cl) HFC-23 (trifluoromethane, CHF 3 ) HFC-41 (fluoromethane, CH 3 Cl) HFC-125 (pentafluoroethane, CF 3 CHF 2 ) HFC-134a (1,1,1,2-tetrafluoroethane, CF 3 CH 2 F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF 2 CHF 2 ) HFC-143a (1,1,1-trifluoroethane, CF 3 CH 3 ) HFC-143 (1,1,2-trifluoroethane, CHF 2 CH 2 F) HFC-152a (1,1-difluoroethane, CHF 2 CH 3 ) HFC-152 (1,2-difluoroethane, CH 2 FCH 2 F) HFC-161 (fluoroethane, CH 3 CH 2 F)
  • the tracer compound can be present in the refrigerant composition at a total concentration of about 10 parts per million by weight (ppm) to about 1000 ppm.
  • the tracer compound is preferably present in the refrigerant composition at a total concentration of about 30 ppm to about 500 ppm, and most preferably about 50 ppm to about 300 ppm.
  • the refrigerant composition according to the present disclosure may comprise a single ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.
  • the ultraviolet fluorescent dye is not limited, and can be suitably selected from commonly used ultraviolet fluorescent dyes.
  • ultraviolet fluorescent dyes examples include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof.
  • the ultraviolet fluorescent dye is particularly preferably either naphthalimide or coumarin, or both.
  • the refrigerant composition according to the present disclosure may comprise a single stabilizer, or two or more stabilizers.
  • the stabilizer is not limited, and can be suitably selected from commonly used stabilizers.
  • stabilizers examples include nitro compounds, ethers, and amines.
  • nitro compounds include aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitro benzene and nitro styrene.
  • ethers examples include 1,4-dioxane.
  • amines examples include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.
  • stabilizers also include butylhydroxyxylene and benzotriazole.
  • the content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.
  • the refrigerant composition according to the present disclosure may comprise a single polymerization inhibitor, or two or more polymerization inhibitors.
  • the polymerization inhibitor is not limited, and can be suitably selected from commonly used polymerization inhibitors.
  • polymerization inhibitors examples include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.
  • the content of the polymerization inhibitor is not limited. Generally, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.
  • the refrigeration oil-containing working fluid according to the present disclosure comprises at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, for use as a working fluid in a refrigerating machine.
  • the refrigeration oil-containing working fluid according to the present disclosure is obtained by mixing a refrigeration oil used in a compressor of a refrigerating machine with the refrigerant or the refrigerant composition.
  • the refrigeration oil-containing working fluid generally comprises 10 to 50 mass % of refrigeration oil.
  • composition according to the present disclosure may comprise a single refrigeration oil, or two or more refrigeration oils.
  • the refrigeration oil is not limited, and can be suitably selected from commonly used refrigeration oils.
  • refrigeration oils that are superior in the action of increasing the miscibility with the mixture and the stability of the mixture, for example, are suitably selected as necessary.
  • the base oil of the refrigeration oil is preferably, for example, at least one member selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).
  • PAG polyalkylene glycols
  • POE polyol esters
  • PVE polyvinyl ethers
  • the refrigeration oil may further contain additives in addition to the base oil.
  • the additive may be at least one member selected from the group consisting of antioxidants, extreme-pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oil agents, and antifoaming agents.
  • a refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40° C. is preferable from the standpoint of lubrication.
  • the refrigeration oil-containing working fluid according to the present disclosure may further optionally contain at least one additive.
  • additives include compatibilizing agents described below.
  • the refrigeration oil-containing working fluid according to the present disclosure may comprise a single compatibilizing agent, or two or more compatibilizing agents.
  • the compatibilizing agent is not limited, and can be suitably selected from commonly used compatibilizing agents.
  • compatibilizing agents include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes.
  • the compatibilizing agent is particularly preferably a polyoxyalkylene glycol ether.
  • the method for operating a refrigerating machine according to the present disclosure is a method for operating a refrigerating machine using the refrigerant according to the present disclosure.
  • the method for operating a refrigerating machine according to the present disclosure comprises the step of circulating the refrigerant according to the present disclosure in a refrigerating machine.
  • composition of each mixed refrigerant of HFO-1132(E), R32, and R1234yf was defined as WCF.
  • a leak simulation was performed using the NIST Standard Reference Database REFLEAK Version 4.0 under the conditions of Equipment, Storage, Shipping, Leak, and Recharge according to the ASHRAE Standard 34-2013.
  • the most flammable fraction was defined as WCFF.
  • a burning velocity test was performed using the apparatus shown in FIG. 1 in the following manner.
  • the mixed refrigerants used had a purity of 99.5% or more, and were degassed by repeating a cycle of freezing, pumping, and thawing until no traces of air were observed on the vacuum gauge.
  • the burning velocity was measured by the closed method.
  • the initial temperature was ambient temperature.
  • Ignition was performed by generating an electric spark between the electrodes in the center of a sample cell.
  • the duration of the discharge was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J.
  • the spread of the flame was visualized using schlieren photographs.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two light transmission acrylic windows was used as the sample cell, and a xenon lamp was used as the light source.
  • Schlieren images of the flame were recorded by a high-speed digital video camera at a frame rate of 600 fps and stored on a PC. Tables 1 to 3 show the results.
  • Example 19 Item Unit M
  • Example 18 W WCF HFO-1132 (E) Mass % 52.6 39.2 32.4 R32 Mass % 0.0 5.0 10.0 R1234yf Mass % 47.4 55.8 57.6 Leak condition that Storage, Storage, Storage, results in WCFF Shipping, ⁇ 40° C., Shipping, ⁇ 40° C., Shipping, ⁇ 40° C., 0% release, on the 0% release, on the 0% release, on the gas phase side gas phase side gas phase side WCF HFO-1132 (E) Mass % 72.0 57.8 48.7 R32 Mass % 0.0 9.5 17.9 R1234yf Mass % 28.0 32.7 33.4 Burning Velocity (WCF) cm/s 8 or less 8 or less 8 or less Burning Velocity (WCFF) cm/s 10 10 10
  • Example 21 Item Unit Example 20 N
  • Example 22 WCF HFO-1132 (E) Mass % 29.3 27.7 24.6 R32 Mass % 14.5 18.2 27
  • Example 23 Example 25 Item Unit O
  • Example 24 P WCF HFO-1132 (E) Mass % 22.6 21.2 20.5 HFO-1123 Mass % 36.8 44.2 51.7 R1234yf Mass % 40.6 34.6 27.8 Leak condition that results in WCFF Storage, Storage, Storage, Shipping, ⁇ 40° C., Shipping, ⁇ 40° C., Shipping, ⁇ 40° C., 0% release, on 0% release, on 0% release, on the gas phase side the gas phase side the gas phase side WCFF HFO-1132 (E) Mass % 31.4 29.2 27.1 HFO-1123 Mass % 45.7 51.1 56.4 R1234yf Mass % 23.0 19.7 16.5 Burning Velocity (WCF) cm/s 8 or less 8 or less 8 or less Burning Velocity (WCFF) cm/s 10 10 10 10 10 10 10 10
  • Tables 4 to 32 show these values together with the GWP of each mixed refrigerant.
  • Example 1 A B A′ B′ A′′ B′′ HFO-1132 (E) Mass % R410A 81.6 0.0 63.1 0.0 48.2 0.0 R32 Mass % 18.4 18.1 36.9 36.7 51.8 51.5 R1234yf Mass % 0.0 81.9 0.0 63.3 0.0 48.5 GWP — 2088 125 125 250 250 350 350 COP Ratio % (relative 100 98.7 103.6 98.7 102.3 99.2 102.2 to R410A) Refrigerating % (relative 100 105.3 62.5 109.9 77.5 112.1 87.3 Capacity to R410A) Ratio
  • Example 23 Example 26 Item Unit O
  • Example 24 P S HFO-1132 (E) Mass % 22.6 21.2 20.5 21.9 R32 Mass % 36.8 44.2 51.7 39.7 R1234yf Mass % 40.6 34.6 27.8 38.4 GWP — 250 300 350 270 COP Ratio % (relative 100.4 100.5 100.6 100.4 to R410A) Refrigerating % (relative 91.0 95.0 99.1 92.5 Capacity to R410A) Ratio
  • Example 152 HFO-1132 (E) Mass % 25.0 28.0 R32 Mass % 49.0 49.0 R1234yf Mass % 26.0 23.0 GWP — 332 332 COP Ratio % (relative 100.3 100.1 to R410A) Refrigerating % (relative 99.8 101.3 Capacity to R410A) Ratio
  • point M (52.6, 0.0, 47.4), point M′ (39.2, 5.0, 55.8), point N (27.7, 18.2, 54.1), point V (11.0, 18.1, 70.9), and point G (39.6, 0.0, 60.4), or on these line segments (excluding the points on the line segment GM),
  • point Q (44.6, 23.0, 32.4), point R (25.5, 36.8, 37.7), point T (8.6, 51.6, 39.8), point L (28.9, 51.7, 19.4), and point K (35.6, 36.8, 27.6), or on these line segments,

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Abstract

An object is to provide a mixed refrigerant having three types of performance, i.e., a refrigerating capacity that is equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the ASHRAE standard. Provided is a composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf), wherein when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AC, CF, FD, and DA that connect the following 4 points: point A (71.1, 0.0, 28.9), point C (36.5, 18.2, 45.3), point F (47.6, 18.3, 34.1), and point D (72.0, 0.0, 28.0), or on these line segments; the line segment AC is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904); the line segment FD is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28); and the line segments CF and DA are straight lines.

Description

    TECHNICAL FIELD
  • The present disclosure relates to a composition comprising a refrigerant, use of the composition, a refrigerating machine having the composition, and a method for operating the refrigerating machine.
    • BACKGROUND ART
  • R410A is currently used as an air conditioning refrigerant for home air conditioners etc. R410A is a two-component mixed refrigerant of difluoromethane (CH2F2: HFC-32 or R32) and pentafluoroethane (C2HF5: HFC-125 or R125), and is a pseudo-azeotropic composition.
  • However, the global warming potential (GWP) of R410A is 2088. Due to growing concerns about global warming, R32, which has a GWP of 675, has been increasingly used.
  • For this reason, various low-GWP mixed refrigerants that can replace R410A have been proposed (PTL 1).
    • CITATION LIST Patent Literature
  • PTL 1: WO2015/186557
    • SUMMARY OF INVENTION Technical Problem
  • The present inventors performed independent examination, and conceived of the idea that no prior art had developed refrigerant compositions having three types of performance; i.e., a refrigerating capacity (also referred to as “cooling capacity” or “capacity”) that is equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the standard of the American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE). An object of the present disclosure is to solve this unique problem.
    • Solution to Problem
  • Item 1.
  • A composition comprising a refrigerant,
      • the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane(R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf),
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments IJ, JN, NE, and EI that connect the following 4 points:
        point I (72.0, 0.0, 28.0),
        point J (48.5, 18.3, 33.2),
        point N (27.7, 18.2, 54.1), and
        point E (58.3, 0.0, 41.7)
        or on these line segments (excluding the points on the line segment EI;
      • the line segment IJ is represented by coordinates (0.0236y2−1.7616y+72.0, y, −0.0236y2+0.7616y+28.0);
      • the line segment NE is represented by coordinates (0.012y2−1.9003y+58.3, y, −0.012y2+0.9003y+41.7); and
      • the line segments JN and EI are straight lines.
  • Item 2.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments MM′, M′N, NV, VG, and GM that connect the following 5 points:
        point M (52.6, 0.0, 47.4),
        point M′ (39.2, 5.0, 55.8),
        point N (27.7, 18.2, 54.1),
        point V (11.0, 18.1, 70.9), and
        point G (39.6, 0.0, 60.4),
        or on these line segments (excluding the points on the line segment GM);
      • the line segment MM′ is represented by coordinates (0.132y2−3.34y+52.6, y, -0.132y2+2.34y+47.4);
      • the line segment M′N is represented by coordinates (0.0596y2−2.2541y+48.98, y, -0.0596y2+1.2541y+51.02);
      • the line segment VG is represented by coordinates (0.0123y2−1.8033y+39.6, y, -0.0123y2+0.8033y+60.4); and the line segments NV and GM are straight lines.
  • Item 3.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and
  • R1234yf,
  • wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ON, NU, and UO that connect the following 3 points:
        point O (22.6, 36.8, 40.6),
        point N (27.7, 18.2, 54.1), and
        point U (3.9, 36.7, 59.4),
        or on these line segments;
      • the line segment ON is represented by coordinates (0.0072y2−0.6701y+37.512, y, −0.0072y2−0.3299y+62.488);
      • the line segment NU is represented by coordinates (0.0083y2−1.7403y+56.635, y, −0.0083y2+0.7403y+43.365); and
      • the line segment UO is a straight line.
  • Item 4.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments QR, RT, TL, LK, and KQ that connect the following 5 points:
        point Q (44.6, 23.0, 32.4),
        point R (25.5, 36.8, 37.7),
        point T (8.6, 51.6, 39.8),
        point L (28.9, 51.7, 19.4), and
        point K (35.6, 36.8, 27.6),
        or on these line segments;
      • the line segment QR is represented by coordinates (0.0099y2−1.975y+84.765, y, −0.0099y2+0.975y+15.235);
      • the line segment RT is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874);
      • the line segment LK is represented by coordinates (0.0049y2−0.8842y+61.488, y, −0.0049y2−0.1158y+38.512);
      • the line segment KQ is represented by coordinates (0.0095y2−1.2222y+67.676, y, −0.0095y2+0.2222y+32.324); and
      • the line segment TL is a straight line.
  • Item 5.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PS, ST, and TP that connect the following 3 points:
        point P (20.5, 51.7, 27.8),
        point S (21.9, 39.7, 38.4), and
        point T (8.6, 51.6, 39.8),
        or on these line segments;
      • the line segment PS is represented by coordinates (0.0064y2−0.7103y+40.1, y, −0.0064y2−0.2897y+59.9);
      • the line segment ST is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874); and
      • the line segment TP is a straight line.
  • Item 6.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ac, cf, fd, and da that connect the following 4 points:
        point a (71.1, 0.0, 28.9),
        point c (36.5, 18.2, 45.3),
        point f (47.6, 18.3, 34.1), and
        point d (72.0, 0.0, 28.0),
        or on these line segments;
      • the line segment ac is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904);
      • the line segment fd is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28); and
      • the line segments cf and da are straight lines.
  • Item 7.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ab, be, ed, and da that connect the following 4 points:
        point a (71.1, 0.0, 28.9),
        point b (42.6, 14.5, 42.9),
        point e (51.4, 14.6, 34.0), and
        point d (72.0, 0.0, 28.0),
        or on these line segments;
      • the line segment ab is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904);
      • the line segment ed is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28); and
      • the line segments be and da are straight lines.
  • Item 8.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments gi, ij, and jg that connect the following 3 points:
        point g (77.5, 6.9, 15.6),
        point i (55.1, 18.3, 26.6), and
        point j (77.5. 18.4, 4.1),
        or on these line segments;
      • the line segment gi is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604); and
      • the line segments ij and jg are straight lines.
  • Item 9.
  • A composition comprising a refrigerant,
      • the refrigerant comprising HFO-1132(E), R32, and R1234yf,
        wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments gh, hi, and kg that connect the following 3 points:
        point g (77.5, 6.9, 15.6),
        point h (61.8, 14.6, 23.6), and
        point k (77.5, 14.6, 7.9),
        or on these line segments;
      • the line segment gh is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604); and
      • the line segments hk and kg are straight lines.
  • Item 10.
  • The composition according to any one of Items 1 to 9, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.
  • Item 11.
  • The composition according to any one of Items 1 to 10, for use as an alternative refrigerant for R410A.
  • Item 12.
  • Use of the composition according to any one of Items 1 to 10 as an alternative refrigerant for R410A.
  • Item 13.
  • A refrigerating machine comprising the composition according to any one of Items 1 to 10 as a working fluid.
  • Item 14.
  • A method for operating a refrigerating machine, comprising the step of circulating the composition according to any one of Items 1 to 10 as a working fluid in a refrigerating machine.
    • ADVANTAGEOUS EFFECTS OF INVENTION
  • The refrigerant according to the present disclosure has three types of performance; i.e., a refrigerating capacity that is equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the ASHRAE standard.
    • BRIEF DESCRIPTION OF DRAWING
  • FIG. 1 is a schematic view of an apparatus used in measuring a burning velocity.
  • FIG. 2 is a view showing points A to C, E, G, and I to W; and line segments that connect points A to C, E, G, and I to W in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass %.
    •  DESCRIPTION OF EMBODIMENTS
  • The present inventors conducted intensive studies to solve the above problem, and consequently found that a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (HFC-32 or R32), and 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or R1234yf) has the properties described above.
  • The present disclosure has been completed as a result of further research based on this finding. The present disclosure includes the following embodiments.
    • Definition of Terms
  • In the present specification, the term “refrigerant” includes at least compounds that are specified in ISO 817 (International Organization for Standardization), and that are given a refrigerant number (ASHRAE number) representing the type of refrigerant with “R” at the beginning; and further includes refrigerants that have properties equivalent to those of such refrigerants, even though a refrigerant number is not yet given. Refrigerants are broadly divided into fluorocarbon compounds and non-fluorocarbon compounds in terms of the structure of the compounds. Fluorocarbon compounds include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), and the like.
  • In the present specification, the phrase “composition comprising a refrigerant” at least includes (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further comprises other components and that can be mixed with at least a refrigeration oil to obtain a working fluid for a refrigerating machine, and (3) a working fluid for a refrigerating machine containing a refrigeration oil. In the present specification, of these three embodiments, the composition (2) is referred to as a “refrigerant composition” so as to distinguish it from a refrigerant itself (including a mixture of refrigerants). Further, the working fluid for a refrigerating machine (3) is referred to as a “refrigeration oil-containing working fluid” so as to distinguish it from the “refrigerant composition.”
  • In the present specification, when the term “alternative” is used in a context in which the first refrigerant is replaced with the second refrigerant, the first type of “alternative” means that equipment designed for operation using the first refrigerant can be operated using the second refrigerant under optimum conditions, optionally with changes of only a few parts (at least one of the following: refrigeration oil, gasket, packing, expansion valve, dryer, and other parts) and equipment adjustment. In other words, this type of alternative means that the same equipment is operated with an alternative refrigerant. Embodiments of this type of “alternative” include “drop-in alternative,” “nearly drop-in alternative,” and “retrofit,” in the order in which the extent of changes and adjustment necessary for replacing the first refrigerant with the second refrigerant is smaller.
  • The term “alternative” also includes a second type of “alternative,” which means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use with the first refrigerant by using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.
  • In the present specification, the term “refrigerating machine” refers to machines in general that draw heat from an object or space to make its temperature lower than the temperature of ambient air, and maintain a low temperature. In other words, refrigerating machines refer to conversion machines that gain energy from the outside to do work, and that perform energy conversion, in order to transfer heat from where the temperature is lower to where the temperature is higher.
  • In the present specification, a refrigerant having a “WCF lower flammability” means that the most flammable composition (worst case of formulation for flammability: WCF) has a burning velocity of 10 cm/s or less according to the US ANSI/ASHRAE Standard 34-2013. Further, in the present specification, a refrigerant having “ASHRAE lower flammability” means that the burning velocity of WCF is less than 10 cm/s, that the most flammable fraction composition (worst case of fractionation for flammability: WCFF), which is specified by performing a leakage test during storage, shipping, or use based on ANSI/ASHRAE 34-2013 using WCF, has a burning velocity of 10 cm/s or less, and that flammability classification according to the US ANSI/ASHRAE Standard 34-2013 is determined to be classified as “Class 2L.”
    • 1. Refrigerant
  • 1.1 Refrigerant Component
  • The refrigerant according to the present disclosure is a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf).
  • The refrigerant according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant; i.e., a refrigerating capacity equivalent to that of R410A, a sufficiently low GWP, and a lower flammability (Class 2L) according to the ASHRAE standard.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments IJ, JN, NE, and EI that connect the following 4 points:
        point I (72.0, 0.0, 28.0),
        point J (48.5, 18.3, 33.2),
        point N (27.7, 18.2, 54.1), and
        point E (58.3, 0.0, 41.7),
        or on these line segments (excluding the points on the line segment EI);
      • the line segment IJ is represented by coordinates (0.0236y2−1.7616y+72.0, y, −0.0236y2+0.7616y+28.0);
      • the line segment NE is represented by coordinates (0.012y2−1.9003y+58.3, y, −0.012y2+0.9003y+41.7); and
      • the line segments JN and EI are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to R410A, a GWP of 125 or less, and a WCF lower flammability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments MM′, M′N, NV, VG, and GM that connect the following 5 points:
        point M (52.6, 0.0, 47.4),
        point M′ (39.2, 5.0, 55.8),
        point N (27.7, 18.2, 54.1),
        point V (11.0, 18.1, 70.9), and
        point G (39.6, 0.0, 60.4),
        or on these line segments (excluding the points on the line segment GM);
      • the line segment MM′ is represented by coordinates (0.132y2−3.34y+52.6, y, −0.132y2+2.34y+47.4);
      • the line segment M′N is represented by coordinates (0.0596y2−2.2541y+48.98, y, −0.0596y2+1.2541y+51.02);
      • the line segment VG is represented by coordinates (0.0123y2−1.8033y+39.6, y, −0.0123y2+0.8033y+60.4); and
      • the line segments NV and GM are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 70% or more relative to R410A, a GWP of 125 or less, and an ASHRAE lower flammability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ON, NU, and UO that connect the following 3 points:
        point O (22.6, 36.8, 40.6),
        point N (27.7, 18.2, 54.1), and
        point U (3.9, 36.7, 59.4),
        or on these line segments;
      • the line segment ON is represented by coordinates (0.0072y2−0.6701y+37.512, y, −0.0072y2−0.3299y+62.488);
      • the line segment NU is represented by coordinates (0.0083y2−1.7403y+56.635, y, −0.0083y2+0.7403y+43.365); and
      • the line segment UO is a straight line. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to R410A, a GWP of 250 or less, and an ASHRAE lower flammability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments QR, RT, TL, LK, and KQ that connect the following 5 points:
        point Q (44.6, 23.0, 32.4),
        point R (25.5, 36.8, 37.7),
        point T (8.6, 51.6, 39.8),
        point L (28.9, 51.7, 19.4), and
        point K (35.6, 36.8, 27.6),
        or on these line segments;
      • the line segment QR is represented by coordinates (0.0099y2−1.975y+84.765, y, −0.0099y2+0.975y+15.235);
      • the line segment RT is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874);
      • the line segment LK is represented by coordinates (0.0049y2−0.8842y+61.488, y, −0.0049y2−0.1158y+38.512);
      • the line segment KQ is represented by coordinates (0.0095y2−1.2222y+67.676, y, −0.0095y2+0.2222y+32.324); and
      • the line segment TL is a straight line. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to R410A, a GWP of 350 or less, and a WCF lower flammability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PS, ST, and TP that connect the following 3 points:
        point P (20.5, 51.7, 27.8),
        point S (21.9, 39.7, 38.4), and
        point T (8.6, 51.6, 39.8),
        or on these line segments;
      • the line segment PS is represented by coordinates (0.0064y2−0.7103y+40.1, y, −0.0064y2−0.2897y+59.9);
      • the line segment ST is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874); and
      • the line segment TP is a straight line. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to R410A, a GWP of 350 or less, and an ASHRAE lower flammability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ac, cf, fd, and da that connect the following 4 points:
        point a (71.1, 0.0, 28.9),
        point c (36.5, 18.2, 45.3),
        point f (47.6, 18.3, 34.1), and
        point d (72.0, 0.0, 28.0),
        or on these line segments;
      • the line segment ac is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904);
      • the line segment fd is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28); and
      • the line segments cf and da are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to R410A, a GWP of 125 or less, and a lower flammability (Class 2L) according to the ASHRAE standard.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ab, be, ed, and da that connect the following 4 points:
        point a (71.1, 0.0, 28.9),
        point b (42.6, 14.5, 42.9),
        point e (51.4, 14.6, 34.0), and
        point d (72.0, 0.0, 28.0),
        or on these line segments;
      • the line segment ab is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904);
      • the line segment ed is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28); and
      • the line segments be and da are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to R410A, a GWP of 100 or less, and a lower flammability (Class 2L) according to the ASHRAE standard.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments gi, ij, and jg that connect the following 3 points:
        point g (77.5, 6.9, 15.6),
        point i (55.1, 18.3, 26.6), and
        point j (77.5. 18.4, 4.1),
        or on these line segments;
      • the line segment gi is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604); and
      • the line segments ij and jg are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to R410A and a GWP of 100 or less, undergoes fewer or no changes such as polymerization or decomposition, and also has excellent stability.
  • The refrigerant according to the present disclosure is preferably a refrigerant wherein
      • when the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments gh, hk, and kg that connect the following 3 points:
        point g (77.5, 6.9, 15.6),
        point h (61.8, 14.6, 23.6), and
        point k (77.5, 14.6, 7.9),
        or on these line segments;
      • the line segment gh is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604); and
      • the line segments hk and kg are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to R410A and a GWP of 100 or less, undergoes fewer or no changes such as polymerization or decomposition, and also has excellent stability.
  • The refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), R32, and R1234yf, as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure preferably comprises HFO-1132(E), R32, and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more based on the entire refrigerant.
  • Such additional refrigerants are not limited, and can be selected from a wide range of refrigerants. The mixed refrigerant may comprise a single additional refrigerant, or two or more additional refrigerants.
  • 1.2. Use
  • The refrigerant according to the present disclosure can be preferably used as a working fluid in a refrigerating machine.
  • The composition according to the present disclosure is suitable for use as an alternative refrigerant for R410A.
    • 2. Refrigerant Composition
  • The refrigerant composition according to the present disclosure comprises at least the refrigerant according to the present disclosure, and can be used for the same use as the refrigerant according to the present disclosure. Moreover, the refrigerant composition according to the present disclosure can be further mixed with at least a refrigeration oil to thereby obtain a working fluid for a refrigerating machine.
  • The refrigerant composition according to the present disclosure further comprises at least one other component in addition to the refrigerant according to the present disclosure. The refrigerant composition according to the present disclosure may comprise at least one of the following other components, if necessary. As described above, when the refrigerant composition according to the present disclosure is used as a working fluid in a refrigerating machine, it is generally used as a mixture with at least a refrigeration oil. Therefore, it is preferable that the refrigerant composition according to the present disclosure does not substantially comprise a refrigeration oil. Specifically, in the refrigerant composition according to the present disclosure, the content of the refrigeration oil based on the entire refrigerant composition is preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %.
  • 2.1. Water
  • The refrigerant composition according to the present disclosure may contain a small amount of water. The water content of the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant. A small amount of water contained in the refrigerant composition stabilizes double bonds in the molecules of unsaturated fluorocarbon compounds that can be present in the refrigerant, and makes it less likely that the unsaturated fluorocarbon compounds will be oxidized, thus increasing the stability of the refrigerant composition.
  • 2.2. Tracer A tracer is added to the refrigerant composition according to the present disclosure at a detectable concentration such that when the refrigerant composition has been diluted, contaminated, or undergone other changes, the tracer can trace the changes.
  • The refrigerant composition according to the present disclosure may comprise a single tracer, or two or more tracers.
  • The tracer is not limited, and can be suitably selected from commonly used tracers. It is preferable that a compound that cannot be an impurity inevitably mixed into the refrigerant according to the present disclosure is selected as the tracer.
  • Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). The tracer is particularly preferably a hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon, a fluorocarbon, a hydrochlorocarbon, a fluorocarbon, or a fluoroether.
  • Specifically, the following compounds are preferable as the tracer.
  • FC-14 (tetrafluoromethane, CF4)
    HCC-40 (chloromethane, CH3Cl)
    HFC-23 (trifluoromethane, CHF3)
    HFC-41 (fluoromethane, CH3Cl)
    HFC-125 (pentafluoroethane, CF3CHF2)
    HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)
    HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)
    HFC-143a (1,1,1-trifluoroethane, CF3CH3)
    HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)
    HFC-152a (1,1-difluoroethane, CHF2CH3)
    HFC-152 (1,2-difluoroethane, CH2FCH2F)
    HFC-161 (fluoroethane, CH3CH2F)
    HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)
    HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)
    HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)
    HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)
    HCFC-22 (chlorodifluoromethane, CHClF2)
    HCFC-31 (chlorofluoromethane, CH2ClF)
    CFC-1113 (chlorotrifluoroethylene, CF2=CClF)
    HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2)
    HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)
    HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)
    HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)
    HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)
  • The tracer compound can be present in the refrigerant composition at a total concentration of about 10 parts per million by weight (ppm) to about 1000 ppm. The tracer compound is preferably present in the refrigerant composition at a total concentration of about 30 ppm to about 500 ppm, and most preferably about 50 ppm to about 300 ppm.
  • 2.3. Ultraviolet Fluorescent Dye
  • The refrigerant composition according to the present disclosure may comprise a single ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.
  • The ultraviolet fluorescent dye is not limited, and can be suitably selected from commonly used ultraviolet fluorescent dyes.
  • Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. The ultraviolet fluorescent dye is particularly preferably either naphthalimide or coumarin, or both.
  • 2.4. Stabilizer
  • The refrigerant composition according to the present disclosure may comprise a single stabilizer, or two or more stabilizers.
  • The stabilizer is not limited, and can be suitably selected from commonly used stabilizers.
  • Examples of stabilizers include nitro compounds, ethers, and amines.
  • Examples of nitro compounds include aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitro benzene and nitro styrene.
  • Examples of ethers include 1,4-dioxane.
  • Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.
  • Examples of stabilizers also include butylhydroxyxylene and benzotriazole.
  • The content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.
  • 2.5. Polymerization Inhibitor
  • The refrigerant composition according to the present disclosure may comprise a single polymerization inhibitor, or two or more polymerization inhibitors.
  • The polymerization inhibitor is not limited, and can be suitably selected from commonly used polymerization inhibitors.
  • Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.
  • The content of the polymerization inhibitor is not limited. Generally, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.
    • 3. Refrigeration Oil-Containing Working Fluid
  • The refrigeration oil-containing working fluid according to the present disclosure comprises at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, for use as a working fluid in a refrigerating machine. Specifically, the refrigeration oil-containing working fluid according to the present disclosure is obtained by mixing a refrigeration oil used in a compressor of a refrigerating machine with the refrigerant or the refrigerant composition. The refrigeration oil-containing working fluid generally comprises 10 to 50 mass % of refrigeration oil.
  • 3.1. Refrigeration Oil
  • The composition according to the present disclosure may comprise a single refrigeration oil, or two or more refrigeration oils.
  • The refrigeration oil is not limited, and can be suitably selected from commonly used refrigeration oils. In this case, refrigeration oils that are superior in the action of increasing the miscibility with the mixture and the stability of the mixture, for example, are suitably selected as necessary.
  • The base oil of the refrigeration oil is preferably, for example, at least one member selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).
  • The refrigeration oil may further contain additives in addition to the base oil. The additive may be at least one member selected from the group consisting of antioxidants, extreme-pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oil agents, and antifoaming agents.
  • A refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40° C. is preferable from the standpoint of lubrication.
  • The refrigeration oil-containing working fluid according to the present disclosure may further optionally contain at least one additive. Examples of additives include compatibilizing agents described below.
  • 3.2. Compatibilizing Agent
  • The refrigeration oil-containing working fluid according to the present disclosure may comprise a single compatibilizing agent, or two or more compatibilizing agents.
  • The compatibilizing agent is not limited, and can be suitably selected from commonly used compatibilizing agents.
  • Examples of compatibilizing agents include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. The compatibilizing agent is particularly preferably a polyoxyalkylene glycol ether.
    • 4. Method for Operating Refrigerating Machine
  • The method for operating a refrigerating machine according to the present disclosure is a method for operating a refrigerating machine using the refrigerant according to the present disclosure.
  • Specifically, the method for operating a refrigerating machine according to the present disclosure comprises the step of circulating the refrigerant according to the present disclosure in a refrigerating machine.
  • The embodiments are described above; however, it will be understood that various changes in forms and details can be made without departing from the spirit and scope of the claims.
    • EXAMPLES
  • The present disclosure is described in more detail below with reference to Examples. However, the present disclosure is not limited to the Examples.
  • The composition of each mixed refrigerant of HFO-1132(E), R32, and R1234yf was defined as WCF. A leak simulation was performed using the NIST Standard Reference Database REFLEAK Version 4.0 under the conditions of Equipment, Storage, Shipping, Leak, and Recharge according to the ASHRAE Standard 34-2013. The most flammable fraction was defined as WCFF.
  • A burning velocity test was performed using the apparatus shown in FIG. 1 in the following manner. First, the mixed refrigerants used had a purity of 99.5% or more, and were degassed by repeating a cycle of freezing, pumping, and thawing until no traces of air were observed on the vacuum gauge. The burning velocity was measured by the closed method. The initial temperature was ambient temperature. Ignition was performed by generating an electric spark between the electrodes in the center of a sample cell. The duration of the discharge was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The spread of the flame was visualized using schlieren photographs. A cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two light transmission acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of the flame were recorded by a high-speed digital video camera at a frame rate of 600 fps and stored on a PC. Tables 1 to 3 show the results.
  • TABLE 1
    Comparative
    Example 13 Example 12 Example 14 Example 16
    Item Unit I Example 11 J Example 13 K Example 15 L
    WCF HFO-1132 (E) Mass % 72 57.2 48.5 41.2 35.6 32 28.9
    R32 Mass % 0 10 18.3 27.6 36.8 44.2 51.7
    R1234yf Mass % 28 32.8 33.2 31.2 27.6 23.8 19.4
    Burning Velocity (WCF) cm/s 10 10 10 10 10 10 10
  • TABLE 2
    Comparative
    Example 14 Example 19
    Item Unit M Example 18 W
    WCF HFO-1132 (E) Mass % 52.6 39.2 32.4
    R32 Mass % 0.0 5.0 10.0
    R1234yf Mass % 47.4 55.8 57.6
    Leak condition that Storage, Storage, Storage,
    results in WCFF Shipping, −40° C., Shipping, −40° C., Shipping, −40° C.,
    0% release, on the 0% release, on the 0% release, on the
    gas phase side gas phase side gas phase side
    WCF HFO-1132 (E) Mass % 72.0 57.8 48.7
    R32 Mass % 0.0 9.5 17.9
    R1234yf Mass % 28.0 32.7 33.4
    Burning Velocity (WCF) cm/s 8 or less 8 or less 8 or less
    Burning Velocity (WCFF) cm/s 10 10 10  
    Example 21
    Item Unit Example 20 N Example 22
    WCF HFO-1132 (E) Mass % 29.3 27.7 24.6
    R32 Mass % 14.5 18.2 27.6
    R1234yf Mass % 56.2 54.1 47.8
    Leak condition that Storage, Storage, Storage,
    results in WCFF Shipping, −40° C., Shipping, −40° C., Shipping, −40° C.,
    0% release, on the 0% release, on the 0% release, on the
    gas phase side gas phase side gas phase side
    WCF HFO-1132 (E) Mass % 43.6 40.6 34.9
    R32 Mass % 24.2 28.7 38.1
    R1234yf Mass % 32.2 30.7 27.0
    Burning Velocity (WCF) cm/s 8 or less 8 or less 8 or less
    Burning Velocity (WCFF) cm/s 10   10   10  
  • TABLE 3
    Example 23 Example 25
    Item Unit O Example 24 P
    WCF HFO-1132 (E) Mass % 22.6 21.2 20.5
    HFO-1123 Mass % 36.8 44.2 51.7
    R1234yf Mass % 40.6 34.6 27.8
    Leak condition that results in WCFF Storage, Storage, Storage,
    Shipping, −40° C., Shipping, −40° C., Shipping, −40° C.,
    0% release, on 0% release, on 0% release, on
    the gas phase side the gas phase side the gas phase side
    WCFF HFO-1132 (E) Mass % 31.4 29.2 27.1
    HFO-1123 Mass % 45.7 51.1 56.4
    R1234yf Mass % 23.0 19.7 16.5
    Burning Velocity (WCF) cm/s 8 or less 8 or less 8 or less
    Burning Velocity (WCFF) cm/s 10   10   10  
  • The results indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in the ternary composition diagram shown in FIG. 2 in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are on the line segment that connects point I, point J, point K, and point L, or below these line segments, the refrigerant has a WCF lower flammability.
  • The results also indicate that when coordinates (x,y,z) in the ternary composition diagram shown in FIG. 2 are on the line segments that connect point M, point M′, point W, point J, point N, and point P, or below these line segments, the refrigerant has an ASHRAE lower flammability.
  • Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and R1234yf in amounts (mass %) shown in Tables 4 to 32 based on the sum of HFO-1132(E), R32, and R1234yf. The coefficient of performance (COP) ratio and the refrigerating capacity ratio relative to R410 of the mixed refrigerants shown in Tables 4 to 32 were determined. The conditions for calculation were as described below.
  • Evaporating temperature: 5° C.
  • Condensation temperature: 45° C.
  • Degree of superheating: 5 K
  • Degree of subcooling: 5 K
  • Compressor efficiency: 70%
  • Tables 4 to 32 show these values together with the GWP of each mixed refrigerant.
  • TABLE 4
    Comparative Comparative Comparative Comparative Comparative Comparative
    Comparative Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
    Item Unit Example 1 A B A′ B′ A″ B″
    HFO-1132 (E) Mass % R410A 81.6 0.0 63.1 0.0 48.2 0.0
    R32 Mass % 18.4 18.1 36.9 36.7 51.8 51.5
    R1234yf Mass % 0.0 81.9 0.0 63.3 0.0 48.5
    GWP — 2088 125 125 250 250 350 350
    COP Ratio % (relative 100 98.7 103.6 98.7 102.3 99.2 102.2
    to R410A)
    Refrigerating % (relative 100 105.3 62.5 109.9 77.5 112.1 87.3
    Capacity to R410A)
    Ratio
  • TABLE 5
    Comparative Comparative
    Example 8 Comparative Example 10 Example 2 Example 4
    Item Unit C Example 9 C′ Example 1 R Example 3 T
    HFO-1132 (E) Mass % 85.5 66.1 52.1 37.8 25.5 16.6 8.6
    R32 Mass % 0.0 10.0 18.2 27.6 36.8 44.2 51.6
    R1234yf Mass % 14.5 23.9 29.7 34.6 37.7 39.2 39.8
    GWP — 1 69 125 188 250 300 350
    COP Ratio % (relative 99.8 99.3 99.3 99.6 100.2 100.8 101.4
    to R410A)
    Refrigerating % (relative 92.5 92.5 92.5 92.5 92.5 92.5 92.5
    Capacity to R410A)
    Ratio
  • TABLE 6
    Comparative Comparative
    Example 11 Example 6 Example 8 Example 12 Example 10
    Item Unit E Example 5 N Example 7 U G Example 9 V
    HFO-1132 (E) Mass % 58.3 40.5 27.7 14.9 3.9 39.6 22.8 11.0
    R32 Mass % 0.0 10.0 18.2 27.6 36.7 0.0 10.0 18.1
    R1234yf Mass % 41.7 49.5 54.1 57.5 59.4 60.4 67.2 70.9
    GWP — 2 70 125 189 250 3 70 125
    COP Ratio % (relative 100.3 100.3 100.7 101.2 101.9 101.4 101.8 102.3
    to R410A)
    Refrigerating % (relative 80.0 80.0 80.0 80.0 80.0 70.0 70.0 70.0
    Capacity to R410A)
    Ratio
  • TABLE 7
    Comparative
    Example 13 Example 12 Example 14 Example 16 Example 17
    Item Unit I Example 11 J Example 13 K Example 15 L Q
    HFO-1132 (E) Mass % 72.0 57.2 48.5 41.2 35.6 32.0 28.9 44.6
    R32 Mass % 0.0 10.0 18.3 27.6 36.8 44.2 51.7 23.0
    R1234yf Mass % 28.0 32.8 33.2 31.2 27.6 23.8 19.4 32.4
    GWP — 2 69 125 188 250 300 350 157
    COP Ratio % (relative 99.9 99.5 99.4 99.5 99.6 99.8 100.1 99.4
    to R410A)
    Refrigerating % (relative 86.6 88.4 90.9 94.2 97.7 100.5 103.3 92.5
    Capacity to R410A)
    Ratio
  • TABLE 8
    Comparative
    Example 14 Example 19 Example 21
    Item Unit M Example 18 W Example 20 N Example 22
    HFO-1132 (E) Mass % 52.6 39.2 32.4 29.3 27.7 24.5
    R32 Mass % 0.0 5.0 10.0 14.5 18.2 27.6
    R1234yf Mass % 47.4 55.8 57.6 56.2 54.1 47.9
    GWP — 2 36 70 100 125 188
    COP Ratio % (relative 100.5 100.9 100.9 100.8 100.7 100.4
    to R410A)
    Refrigerating % (relative 77.1 74.8 75.6 77.8 80.0 85.5
    Capacity to R410A)
    Ratio
  • TABLE 9
    Example 23 Example 25 Example 26
    Item Unit O Example 24 P S
    HFO-1132 (E) Mass % 22.6 21.2 20.5 21.9
    R32 Mass % 36.8 44.2 51.7 39.7
    R1234yf Mass % 40.6 34.6 27.8 38.4
    GWP — 250 300 350 270
    COP Ratio % (relative 100.4 100.5 100.6 100.4
    to R410A)
    Refrigerating % (relative 91.0 95.0 99.1 92.5
    Capacity to R410A)
    Ratio
  • TABLE 10
    Comp. Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 15 Ex. 16 Ex. 17 Ex. 18 Example 27 Example 28 Ex. 19 Ex. 20
    HFO-1132 (E) Mass % 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0
    R32 Mass % 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
    R1234yf Mass % 85.0 75.0 65.0 55.0 45.0 35.0 25.0 15.0
    GWP — 37 37 37 36 36 36 35 35
    COP Ratio % (relative 103.4 102.6 101.6 100.8 100.2 99.8 99.6 99.4
    to R410A)
    Refrigerating % (relative 56.4 63.3 69.5 75.2 80.5 85.4 90.1 94.4
    Capacity to R410A)
    Ratio
  • TABLE 11
    Comp. Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 21 Ex. 22 Example 29 Ex. 23 Example 30 Ex. 24 Ex. 25 Ex. 26
    HFO-1132 (E) Mass % 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0
    R32 Mass % 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
    R1234yf Mass % 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
    GWP — 71 71 70 70 70 69 69 69
    COP Ratio % (relative 103.1 102.1 101.1 100.4 99.8 99.5 99.2 99.1
    to R410A)
    Refrigerating % (relative 61.8 68.3 74.3 79.7 84.9 89.7 94.2 98.4
    Capacity to R410A)
    Ratio
  • TABLE 12
    Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 27 Example 31 Ex. 28 Example 32 Example 33 Ex. 29 Ex. 30 Ex. 31
    HFO-1132 (E) Mass % 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0
    R32 Mass % 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
    R1234yf Mass % 75.0 65.0 55.0 45.0 35.0 25.0 15.0 5.0
    GWP — 104 104 104 103 103 103 103 102
    COP Ratio %(relative 102.7 101.6 100.7 100.0 99.5 99.2 99.0 98.9
    to R410A)
    Refrigerating %(relative 66.6 72.9 78.6 84.0 89.0 93.7 98.1 102.2
    Capacity to R410A)
    Ratio
  • TABLE 13
    Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Ex. 37 Ex. 38 Ex. 39
    HFO-1132 (E) Mass % 10.0 20.0 30.0 40.0 50.0 60.0 70.0 10.0
    R32 Mass % 20.0 20.0 20.0 20.0 20.0 20.0 20.0 25.0
    R1234yf Mass % 70.0 60.0 50.0 40.0 30.0 20.0 10.0 65.0
    GWP — 138 138 137 137 137 136 136 171
    COP Ratio % (relative 102.3 101.2 100.4 99.7 99.3 99.0 98.8 101.9
    to R410A)
    Refrigerating % (relative 71.0 77.1 82.7 88.0 92.9 97.5 101.7 75.0
    Capacity to R410A)
    Ratio
  • TABLE 14
    Comp. Comp. Comp. Comp. Comp. Comp.
    Item Unit Example 34 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 45 Example 35
    HFO-1132 (E) Mass % 20.0 30.0 40.0 50.0 60.0 70.0 10.0 20.0
    R32 Mass % 25.0 25.0 25.0 25.0 25.0 25.0 30.0 30.0
    R1234yf Mass % 55.0 45.0 35.0 25.0 15.0 5.0 60.0 50.0
    GWP — 171 171 171 170 170 170 205 205
    COP Ratio % (relative 100.9 100.1 99.6 99.2 98.9 98.7 101.6 100.7
    to R410A)
    Refrigerating % (relative 81.0 86.6 91.7 96.5 101.0 105.2 78.9 84.8
    Capacity to R410A)
    Ratio
  • TABLE 15
    Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 46 Ex. 47 Ex. 48 Ex. 49 Example 36 Example 37 Example 38 Ex. 50
    HFO-1132 (E) Mass % 30.0 40.0 50.0 60.0 10.0 20.0 30.0 40.0
    R32 Mass % 30.0 30.0 30.0 30.0 35.0 35.0 35.0 35.0
    R1234yf Mass % 40.0 30.0 20.0 10.0 55.0 45.0 35.0 25.0
    GWP — 204 204 204 204 239 238 238 238
    COP Ratio % (relative 100.0 99.5 99.1 98.8 101.4 100.6 99.9 99.4
    to R410A)
    Refrigerating % (relative 90.2 95.3 100.0 104.4 82.5 88.3 93.7 98.6
    Capacity to R410A)
    Ratio
  • TABLE 16
    Comp. Comp. Comp. Comp. Comp. Comp. Comp.
    Item Unit Ex. 51 Ex. 52 Ex. 53 Ex. 54 Example 39 Ex. 55 Ex. 56 Ex. 57
    HFO-1132 (E) Mass % 50.0 60.0 10.0 20.0 30.0 40.0 50.0 10.0
    R32 Mass % 35.0 35.0 40.0 40.0 40.0 40.0 40.0 45.0
    R1234yf Mass % 15.0 5.0 50.0 40.0 30.0 20.0 10.0 45.0
    GWP — 237 237 272 272 272 271 271 306
    COP Ratio % (relative 99.0 98.8 101.3 100.6 99.9 99.4 99.0 101.3
    to R410A)
    Refrigerating % (relative 103.2 107.5 86.0 91.7 96.9 101.8 106.3 89.3
    Capacity to R410A)
    Ratio
  • TABLE 17
    Example Example Comp. Comp. Comp. Example Comp. Comp.
    Item Unit 40 41 Ex. 58 Ex. 59 Ex. 60 42 Ex. 61 Ex. 62
    HFO-1132 (E) Mass % 20.0 30.0 40.0 50.0 10.0 20.0 30.0 40.0
    R32 Mass % 45.0 45.0 45.0 45.0 50.0 50.0 50.0 50.0
    R1234yf Mass % 35.0 25.0 15.0 5.0 40.0 30.0 20.0 10.0
    GWP — 305 305 305 304 339 339 339 338
    COP Ratio % (relative 100.6 100.0 99.5 99.1 101.3 100.6 100.0 99.5
    to R410A)
    Refrigerating % (relative 94.9 100.0 104.7 109.2 92.4 97.8 102.9 107.5
    Capacity to R410A)
    Ratio
  • TABLE 18
    Comp. Comp. Comp. Comp. Example Example Example Example
    Item Unit Ex. 63 Ex. 64 Ex. 65 Ex. 66 43 44 45 46
    HFO-1132 (E) Mass % 10.0 20.0 30.0 40.0 56.0 59.0 62.0 65.0
    R32 Mass % 55.0 55.0 55.0 55.0 3.0 3.0 3.0 3.0
    R1234yf Mass % 35.0 25.0 15.0 5.0 41.0 38.0 35.0 32.0
    GWP — 373 372 372 372 22 22 22 22
    COP Ratio % (relative 101.4 100.7 100.1 99.6 100.1 100.0 99.9 99.8
    to R410A)
    Refrigerating % (relative 95.3 100.6 105.6 110.2 81.7 83.2 84.6 86.0
    Capacity to R410A)
    Ratio
  • TABLE 19
    Example Example Example Example Example Example Example Example
    Item Unit 47 48 49 50 51 52 53 54
    HFO-1132 (E) Mass % 49.0 52.0 55.0 58.0 61.0 43.0 46.0 49.0
    R32 Mass % 6.0 6.0 6.0 6.0 6.0 9.0 9.0 9.0
    R1234yf Mass % 45.0 42.0 39.0 36.0 33.0 48.0 45.0 42.0
    GWP — 43 43 43 43 42 63 63 63
    COP Ratio % (relative 100.2 100.0 99.9 99.8 90.7 100.3 100.1 99.9
    to R410A)
    Refrigerating % (relative 80.9 82.4 83.9 85.4 86.8 80.4 82.0 83.5
    Capacity to R410A)
    Ratio
  • TABLE 20
    Example Example Example Example Example Example Example Example
    Item Unit 55 56 57 58 59 60 61 62
    HFO-1132 (E) Mass % 52.0 55.0 58.0 38.0 41.0 44.0 47.0 50.0
    R32 Mass % 9.0 9.0 9.0 12.0 12.0 12.0 12.0 12.0
    R1234yf Mass % 39.0 36.0 33.0 50.0 47.0 44.0 41.0 38.0
    GWP — 63 63 63 83 83 83 83 83
    COP Ratio % (relative 99.8 99.7 99.6 100.3 100.1 100.0 99.8 99.7
    to R410A)
    Refrigerating % (relative 85.0 86.5 87.9 80.4 82.0 83.5 85.1 86.6
    Capacity to R410A)
    Ratio
  • TABLE 21
    Example Example Example Example Example Example Example Example
    Item Unit 63 64 65 66 67 68 69 70
    HFO-1132 (E) Mass % 53.0 33.0 36.0 39.0 42.0 45.0 48.0 51.0
    R32 Mass % 12.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
    R1234yf Mass % 35.0 52.0 49.0 46.0 43.0 40.0 37.0 34.0
    GWP — 83 104 104 103 103 103 103 103
    COP Ratio % (relative 99.6 100.5 100.3 100.1 99.9 99.7 99.6 99.5
    to R410A)
    Refrigerating % (relative 88.0 80.3 81.9 83.5 85.0 86.5 88.0 89.5
    Capacity to R410A)
    Ratio
  • TABLE 22
    Example Example Example Example Example Example Example Example
    Item Unit 71 72 73 74 75 76 77 78
    HFO-1132 (E) Mass % 29.0 32.0 35.0 38.0 41.0 44.0 47.0 36.0
    R32 Mass % 18.0 18.0 18.0 18.0 18.0 18.0 18.0 3.0
    R1234yf Mass % 51.0 50.0 47.0 44.0 41.0 38.0 35.0 61.0
    GWP — 124 124 124 124 124 123 123 23
    COP Ratio % (relative 100.6 100.3 100.1 99.9 99.8 99.8 99.5 101.3
    to R410A)
    Refrigerating % (relative 80.6 82.2 83.8 85.4 86.9 88.4 89.9 71.0
    Capacity to R410A)
    Ratio
  • TABLE 23
    Example Example Example Example Example Example Example Example
    Item Unit 79 80 81 82 83 84 85 86
    HFO-1132 (E) Mass % 39.0 42.0 30.0 33.0 36.0 26.0 29.0 32.0
    R32 Mass % 3.0 3.0 6.0 6.0 6.0 9.0 9.0 9.0
    R1234yf Mass % 58.0 55.0 64.0 61.0 58.0 65.0 62.0 59.0
    GWP — 23 23 43 43 43 64 64 63
    COP Ratio % (relative 101.1 100.9 101.5 101.3 101.0 101.6 101.3 101.1
    to R410A)
    Refrigerating % (relative 72.7 74.4 70.5 72.2 73.9 71.0 72.8 74.5
    Capacity to R410A)
    Ratio
  • TABLE 24
    Example Example Example Example Example Example Example Example
    Item Unit 87 88 89 90 91 92 93 94
    HFO-1132 (E) Mass % 21.0 24.0 27.0 30.0 16.0 19.0 22.0 25.0
    R32 Mass % 12.0 12.0 12.0 12.0 15.0 15.0 15.0 15.0
    R1234yf Mass % 67.0 64.0 61.0 58.0 69.0 66.0 63.0 60.0
    GWP — 84 84 84 84 104 104 104 104
    COP Ratio % (relative 101.8 101.5 101.2 101.0 102.1 101.8 101.4 101.2
    to R410A)
    Refrigerating % (relative 70.8 72.6 74.3 76.0 70.4 72.3 74.0 75.8
    Capacity to R410A)
    Ratio
  • TABLE 25
    Example Example Example Example Example Example Example Example
    Item Unit 95 96 97 98 99 100 101 102
    HFO-1132 (E) Mass % 28.0 12.0 15.0 18.0 21.0 24.0 27.0 25.0
    R32 Mass % 15.0 18.0 18.0 18.0 18.0 18.0 18.0 21.0
    R1234yf Mass % 57.0 70.0 67.0 64.0 61.0 58.0 55.0 54.0
    GWP — 104 124 124 124 124 124 124 144
    COP Ratio % (relative 100.9 102.2 101.9 101.6 101.3 101.0 100.7 100.7
    to R410A)
    Refrigerating % (relative 77.5 70.5 72.4 74.2 76.0 77.7 79.4 80.7
    Capacity to R410A)
    Ratio
  • TABLE 26
    Example Example Example Example Example Example Example Example
    Item Unit 103 104 105 106 107 108 109 110
    HFO-1132 (E) Mass % 21.0 24.0 17.0 20.0 23.0 13.0 16.0 19.0
    R32 Mass % 24.0 24.0 27.0 27.0 27.0 30.0 30.0 30.0
    R1234yf Mass % 65.0 52.0 56.0 53.0 50.0 57.0 54.0 51.0
    GWP — 164 164 185 185 184 205 205 205
    COP Ratio % (relative 100.9 100.6 101.1 100.8 100.6 101.3 101.0 100.8
    to R410A)
    Refrigerating % (relative 80.8 82.5 80.8 82.5 84.2 80.7 82.5 84.2
    Capacity to R410A)
    Ratio
  • TABLE 27
    Example Example Example Example Example Example Example Example
    Item Unit 111 112 113 114 115 116 117 118
    HFO-1132 (E) Mass % 22.0 9.0 12.0 15.0 18.0 21.0 8.0 12.0
    R32 Mass % 30.0 33.0 33.0 33.0 33.0 33.0 36.0 36.0
    R1234yf Mass % 48.0 58.0 55.0 52.0 49.0 46.0 56.0 52.0
    GWP — 205 225 225 225 225 225 245 245
    COP Ratio % (relative 100.5 101.6 101.3 101.0 100.8 100.5 101.6 101.2
    to R410A)
    Refrigerating % (relative 85.9 80.5 82.3 84.1 85.8 87.5 82.0 84.4
    Capacity to R410A)
    Ratio
  • TABLE 28
    Example Example Example Example Example Example Example Example
    Item Unit 119 120 121 122 123 124 125 126
    HFO-1132 (E) Mass % 15.0 18.0 21.0 42.0 39.0 34.0 37.0 30.0
    R32 Mass % 36.0 36.0 36.0 25.0 28.0 31.0 31.0 34.0
    R1234yf Mass % 49.0 46.0 43.0 33.0 33.0 35.0 32.0 36.0
    GWP — 245 245 245 170 191 211 211 231
    COP Ratio % (relative 101.0 100.7 100.5 99.5 99.5 99.8 99.6 99.9
    to R410A)
    Refrigerating % (relative 86.2 87.9 89.6 92.7 93.4 93.0 94.5 93.0
    Capacity to R410A)
    Ratio
  • TABLE 29
    Example Example Example Example Example Example Example Example
    Item Unit 127 128 129 130 131 132 133 134
    HFO-1132 (E) Mass % 33.0 36.0 24.0 27.0 30.0 33.0 23.0 26.0
    R32 Mass % 34.0 34.0 37.0 37.0 37.0 37.0 40.0 40.0
    R1234yf Mass % 33.0 30.0 39.0 36.0 33.0 30.0 37.0 34.0
    GWP — 231 231 252 251 251 251 272 272
    COP Ratio % (relative 99.8 99.6 100.3 100.1 99.9 99.3 100.4 100.2
    to R410A)
    Refrigerating % (relative 94.5 96.0 91.9 93.4 95.0 96.5 93.3 94.9
    Capacity to R410A)
    Ratio
  • TABLE 30
    Example Example Example Example Example Example Example Example
    Item Unit 135 136 137 138 139 140 141 142
    HFO-1132 (E) Mass % 29.0 32.0 19.0 22.0 25.0 28.0 31.0 18.0
    R32 Mass % 40.0 40.0 43.0 43.0 43.0 43.0 43.0 46.0
    R1234yf Mass % 31.0 28.0 38.0 35.0 32.0 29.0 26.0 36.0
    GWP — 272 271 292 292 292 292 292 312
    COP Ratio % (relative 100.0 99.8 100.6 100.4 100.2 100.1 99.9 100.7
    to R410A)
    Refrigerating % (relative 96.4 97.9 93.1 94.7 96.2 97.8 99.3 94.4
    Capacity to R410A)
    Ratio
  • TABLE 31
    Example Example Example Example Example Example Example Example
    Item Unit 143 144 145 146 147 148 149 150
    HFO-1132 (E) Mass % 21.0 23.0 26.0 29.0 13.0 16.0 19.0 22.0
    R32 Mass % 46.0 46.0 46.0 46.0 49.0 49.0 49.0 49.0
    R1234yf Mass % 33.0 31.0 28.0 25.0 38.0 35.0 32.0 29.0
    GWP — 312 312 312 312 332 332 332 332
    COP Ratio % (relative 100.5 100.4 100.2 100.0 101.1 100.9 100.7 100.5
    to R410A)
    Refrigerating % (relative 96.0 97.0 98.6 100.1 93.5 95.1 96.7 98.3
    Capacity to R410A)
    Ratio
  • TABLE 32
    Item Unit Example 151 Example 152
    HFO-1132 (E) Mass % 25.0 28.0
    R32 Mass % 49.0 49.0
    R1234yf Mass % 26.0 23.0
    GWP — 332 332
    COP Ratio % (relative 100.3 100.1
    to R410A)
    Refrigerating % (relative 99.8 101.3
    Capacity to R410A)
    Ratio
  • The results also indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments IJ, JN, NE, and EI that connect the following 4 points:
  • point I (72.0, 0.0, 28.0),
    point J (48.5, 18.3, 33.2),
    point N (27.7, 18.2, 54.1), and
    point E (58.3, 0.0, 41.7),
    or on these line segments (excluding the points on the line segment EI),
      • the line segment IJ is represented by coordinates (0.0236y2−1.7616y+72.0, y, −0.0236y2+0.7616y+28.0),
      • the line segment NE is represented by coordinates (0.012y2−1.9003y+58.3, y, −0.012y2+0.9003y+41.7), and
      • the line segments JN and EI are straight lines, the refrigerant has a refrigerating capacity ratio of 80% or more relative to R410A, a GWP of 125 or less, and a WCF lower flammability.
  • The results also indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments MM′, M′N, NV, VG, and GM that connect the following 5 points:
  • point M (52.6, 0.0, 47.4),
    point M′ (39.2, 5.0, 55.8),
    point N (27.7, 18.2, 54.1),
    point V (11.0, 18.1, 70.9), and
    point G (39.6, 0.0, 60.4),
    or on these line segments (excluding the points on the line segment GM),
      • the line segment MM′ is represented by coordinates (0.132y2−3.34y+52.6, y, −0.132y2+2.34y+47.4),
      • the line segment M′N is represented by coordinates (0.0596y2−2.2541y+48.98, y, −0.0596y2+1.2541y+51.02),
      • the line segment VG is represented by coordinates (0.0123y2−1.8033y+39.6, y, −0.0123y2+0.8033y+60.4), and
      • the line segments NV and GM are straight lines, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 70% or more relative to R410A, a GWP of 125 or less, and an ASHRAE lower flammability.
  • The results also indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments ON, NU, and UO that connect the following 3 points:
  • point O (22.6, 36.8, 40.6),
    point N (27.7, 18.2, 54.1), and
    point U (3.9, 36.7, 59.4),
    or on these line segments,
      • the line segment ON is represented by coordinates (0.0072y2−0.6701y+37.512, y, −0.0072y2−0.3299y+62.488),
      • the line segment NU is represented by coordinates (0.0083y2−1.7403y+56.635, y, −0.0083y2+0.7403y+43.365), and
      • the line segment UO is a straight line, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to R410A, a GWP of 250 or less, and an ASHRAE lower flammability.
  • The results also indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments QR, RT, TL, LK, and KQ that connect the following 5 points:
  • point Q (44.6, 23.0, 32.4),
    point R (25.5, 36.8, 37.7),
    point T (8.6, 51.6, 39.8),
    point L (28.9, 51.7, 19.4), and
    point K (35.6, 36.8, 27.6),
    or on these line segments,
      • the line segment QR is represented by coordinates (0.0099y2−1.975y+84.765, y, −0.0099y2+0.975y+15.235),
      • the line segment RT is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874),
      • the line segment LK is represented by coordinates (0.0049y2−0.8842y+61.488, y, −0.0049y2−0.1158y+38.512),
      • the line segment KQ is represented by coordinates (0.0095y2−1.2222y+67.676, y, −0.0095y2+0.2222y+32.324), and
      • the line segment TL is a straight line, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to R410A, a GWP of 350 or less, and a WCF lower flammability.
  • The results further indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PS, ST, and TP that connect the following 3 points:
  • point P (20.5, 51.7, 27.8),
    point S (21.9, 39.7, 38.4), and
    point T (8.6, 51.6, 39.8),
    or on these line segments,
      • the line segment PS is represented by coordinates (0.0064y2−0.7103y+40.1, y, −0.0064y2−0.2897y+59.9),
      • the line segment ST is represented by coordinates (0.0082y2−1.8683y+83.126, y, −0.0082y2+0.8683y+16.874), and
      • the line segment TP is a straight line, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to R410A, a GWP of 350 or less, and an ASHRAE lower flammability.
    DESCRIPTION OF THE REFERENCE NUMERALS
  • 1: Sample cell
    2: High-speed camera
    3: Xenon lamp
    4: Collimating lens
    5: Collimating lens
    6: Ring filter

Claims (9)

1. (canceled)
2. A composition comprising a refrigerant,
the refrigerant comprising HFO-1132(E), R32, and R1234yf,
wherein
when the mass % of HFO-1132(E), R32, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments MM′, M′N, NV, VG, and GM that connect the following 5 points:
point M (52.6, 0.0, 47.4),
point M′ (39.2, 5.0, 55.8),
point N (27.7, 18.2, 54.1),
point V (11.0, 18.1, 70.9), and
point G (39.6, 0.0, 60.4),
or on these line segments (excluding the points on the line segment GM);
the line segment MM′ is represented by coordinates (0.132y2−3.34y+52.6, y, −0.132y2+2.34y+47.4);
the line segment M′N is represented by coordinates (0.0596y2−2.2541y+48.98, y, −0.0596y2+1.2541y+51.02);
the line segment VG is represented by coordinates (0.0123y2−1.8033y+39.6, y, −0.0123y2+0.8033y+60.4); and
the line segments NV and GM are straight lines.
3. The composition according to claim 2, wherein the line segments MM′ and M′N are defined as illustrated in FIG. 2 of the drawings.
4-7. (canceled)
8. The composition according to claim 2, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.
9. The composition according to claim 2, for use as an alternative refrigerant for R410A.
10. Use of the composition according to claim 2 as an alternative refrigerant for R410A.
11. A refrigerating machine comprising the composition according to claim 2 as a working fluid.
12. A method for operating a refrigerating machine, comprising the step of circulating the composition according to claim 2 as a working fluid in a refrigerating machine.
US17/887,125 2017-12-18 2022-08-12 Composition containing refrigerant, use of said composition, refrigerator having said composition, and method for operating said refrigerator Pending US20230002659A1 (en)

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US202016955683A 2020-06-18 2020-06-18
US16/913,639 US11549041B2 (en) 2017-12-18 2020-06-26 Composition containing refrigerant, use of said composition, refrigerator having said composition, and method for operating said refrigerator
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US20200326109A1 (en) * 2017-12-18 2020-10-15 Daikin Industries, Ltd. Refrigeration apparatus
US20210355359A1 (en) * 2019-02-05 2021-11-18 Daikin Industries, Ltd. Refrigerant-containing composition, and refrigerating method, refrigerating device operating method, and refrigerating device using said composition
US20230029441A2 (en) * 2018-07-17 2023-01-26 Daikin Industries, Ltd. Refrigeration cycle device for vehicle
US11820933B2 (en) 2017-12-18 2023-11-21 Daikin Industries, Ltd. Refrigeration cycle apparatus
US11827833B2 (en) 2019-02-06 2023-11-28 Daikin Industries, Ltd. Refrigerant-containing composition, and refrigerating method, refrigerating device operating method, and refrigerating device using said composition
US11834601B2 (en) 2019-01-30 2023-12-05 Daikin Industries, Ltd. Composition containing refrigerant, refrigeration method using said composition, method for operating refrigeration device, and refrigeration device
US11840658B2 (en) 2019-01-30 2023-12-12 Daikin Industries, Ltd. Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device
US11912922B2 (en) 2018-07-17 2024-02-27 Daikin Industries, Ltd. Refrigerant cycle apparatus
US11939515B2 (en) 2018-07-17 2024-03-26 Daikin Industries, Ltd. Refrigerant-containing composition, heat transfer medium, and heat cycle system
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US11906207B2 (en) * 2017-12-18 2024-02-20 Daikin Industries, Ltd. Refrigeration apparatus
US12270575B2 (en) 2017-12-18 2025-04-08 Daikin Industries, Ltd. Warm-water generating apparatus
US20200326109A1 (en) * 2017-12-18 2020-10-15 Daikin Industries, Ltd. Refrigeration apparatus
US11820933B2 (en) 2017-12-18 2023-11-21 Daikin Industries, Ltd. Refrigeration cycle apparatus
US11912922B2 (en) 2018-07-17 2024-02-27 Daikin Industries, Ltd. Refrigerant cycle apparatus
US20230029441A2 (en) * 2018-07-17 2023-01-26 Daikin Industries, Ltd. Refrigeration cycle device for vehicle
US11920077B2 (en) * 2018-07-17 2024-03-05 Daikin Industries, Ltd. Refrigeration cycle device for vehicle
US11939515B2 (en) 2018-07-17 2024-03-26 Daikin Industries, Ltd. Refrigerant-containing composition, heat transfer medium, and heat cycle system
US11834601B2 (en) 2019-01-30 2023-12-05 Daikin Industries, Ltd. Composition containing refrigerant, refrigeration method using said composition, method for operating refrigeration device, and refrigeration device
US11840658B2 (en) 2019-01-30 2023-12-12 Daikin Industries, Ltd. Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device
US12221577B2 (en) 2019-01-30 2025-02-11 Daikin Industries, Ltd. Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device
US11834602B2 (en) * 2019-02-05 2023-12-05 Daikin Industries, Ltd. Refrigerant-containing composition, and refrigerating method, refrigerating device operating method, and refrigerating device using said composition
US20210355359A1 (en) * 2019-02-05 2021-11-18 Daikin Industries, Ltd. Refrigerant-containing composition, and refrigerating method, refrigerating device operating method, and refrigerating device using said composition
US11827833B2 (en) 2019-02-06 2023-11-28 Daikin Industries, Ltd. Refrigerant-containing composition, and refrigerating method, refrigerating device operating method, and refrigerating device using said composition

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