WO2020256131A1 - Réfrigérateur comprenant du difluoroéthylène (hfo-1132) en tant que fluide thermodynamique - Google Patents

Réfrigérateur comprenant du difluoroéthylène (hfo-1132) en tant que fluide thermodynamique Download PDF

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Publication number
WO2020256131A1
WO2020256131A1 PCT/JP2020/024204 JP2020024204W WO2020256131A1 WO 2020256131 A1 WO2020256131 A1 WO 2020256131A1 JP 2020024204 W JP2020024204 W JP 2020024204W WO 2020256131 A1 WO2020256131 A1 WO 2020256131A1
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hfo
refrigerant
mass
point
r1234yf
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PCT/JP2020/024204
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English (en)
Japanese (ja)
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瞬 大久保
智行 後藤
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ダイキン工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/32—Cooling devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat

Definitions

  • This disclosure relates to a refrigerator containing difluoroethylene (HFO-1132) as a working fluid.
  • HFO-1132 difluoroethylene
  • the challenge is to improve the stability of HFO-1132 when it is mounted on a refrigerator and operated in a refrigerant containing difluoroethylene (HFO-1132).
  • Item 1 A refrigerator containing a refrigerant containing difluoroethylene (HFO-1132) as an operating medium, and having a processing unit for contacting the refrigerant with at least one selected from the group consisting of a desiccant, a deoxidizer and a powder remover. refrigerator.
  • Item 2. Item 2.
  • Item 3. Item 2.
  • Item 4. A method of removing oxygen from a composition containing difluoroethylene, which comprises a step of contacting the composition with an oxygen scavenger and / or a powder remover.
  • Item 5. Item 4. The method according to Item 4, wherein the composition comprises at least one difluoroethylene selected from the group consisting of HFO-1132 (E), HFO-1132 (Z) and HFO-1132a.
  • the refrigerant or composition is trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123) and 2,3,3,3-tetrafluoro-1-propen (R1234yf). including, Item 5.
  • the line segment DG is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402),
  • the line segment GH is It is represented by the coordinates (-0.0134z 2 -1.0825z + 56.692, 0.0134z 2 + 0.0825z + 43.308, z), and the line segments HO and OD are straight lines.
  • Item 5 The refrigerator or method according to Item 1.
  • the line segment LG is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402)
  • the line segment GH is It is represented by the coordinates (-0.0134z 2 -1.0825z + 56.692, 0.0134z 2 + 0.0825z + 43.308, z), and the line segments HI and IL are straight lines.
  • Item 5. The refrigerator or method according to Item 1.
  • the refrigerant or composition further contains difluoromethane (R32).
  • Item 5 The refrigerator or method according to Item 1.
  • HFO-1132 (E) when the mass% of HFO-1132 (E), HFO-1123 and R1234yf and R32 based on the sum of these is x, y and z and a, respectively, HFO-1132 (E). ), HFO-1123 and R1234yf have the coordinates (x, y, z) in the three-component composition diagram in which the sum is 100% by mass.
  • Point A (0.02a 2 -2.46a + 93.4, 0, -0.02a 2 + 2.46a + 6.6)
  • Point B' (-0.008a 2 -1.38a + 56, 0.018a 2 -0.53a + 26.3, -0.01a 2 + 1.91a + 17.7)
  • Point C (-0.016a 2 + 1.02a + 77.6, 0.016a 2 -1.02a + 22.4, 0)
  • point O (100.0, 0.0, 0.0) It is within the range of the figure surrounded by the straight line connecting the four points, or on the straight lines OA, AB'and B'C (however, points O and C are excluded).
  • the refrigerator or method according to Item 1. Item 11.
  • the refrigerant or composition contains the total of HFO-1132 (E) and HFO-1123 in an amount of 99.5% by mass or more based on the total amount of the refrigerant, and the refrigerant contains HFO-1132 (E) of the refrigerant.
  • Item 5. The refrigerator or method according to Item 1 to 5, which comprises 62.5% by mass to 72.5% by mass with respect to the whole.
  • the refrigerant or composition comprises HFO-1132 (E), R32 and R1234yf.
  • the sum of HFO-1132 (E), R32 and R1234yf is 100.
  • the coordinates (x, y, z) are 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) It is within the range of the figure surrounded by the line segments AC, CF, FD, and DA that connect the four points, or on the line segment.
  • the line segment AC is Represented in coordinates (0.0181y 2 -2.2288y + 71.096, y, -0.0181y 2 + 1.2288y + 28.904)
  • the line segment FD is It is represented by the coordinates (0.02y 2 -1.7y + 72, y, -0.02y 2 + 0.7y + 28), and the line segments CF and DA are straight lines.
  • Item 5. The refrigerator or method according to Item 1.
  • the refrigerant or composition comprises HFO-1132 (E), R32 and R1234yf.
  • the line segment AB is Represented in coordinates (0.0181y 2 -2.2288y + 71.096, y, -0.0181y 2 + 1.2288y + 28.904)
  • the line segment ED is The refrigerator or method represented by the coordinates (0.02y 2 -1.7y + 72, y, -0.02y 2 + 0.7y + 28) and according to Items 1 to 5.
  • Item 14 The refrigerant or composition comprises HFO-1132 (E), R32 and R1234yf.
  • the refrigerant or composition comprises HFO-1132 (E), R32 and R1234yf.
  • the coordinates (x, y, z) are 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) It is within the range of the figure surrounded by the line segment GH, HK and KG connecting the three points, or on the line segment, and the line segment GH is It is represented by the coordinates (0.02y 2 -2.4583y + 93.396, y, -0.02y 2 + 1.4583y + 6.604), and the line segments HK and KG are straight lines.
  • the refrigerant or composition comprises HFO-1132 (E), HFO-1123 and R32.
  • HFO-1132 (E), HFO-1123 and R32 In the above-mentioned refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R32 based on the sum of these is x, y and z, respectively, HFO-1132 (E), HFO-1123 and R32
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5), Point E'(41.8, 39.8, 18.4) and Point A'(81.6, 0.0, 18.4)
  • the line segment C'D' is Represented in coordinates (-0.0297z 2 -0.1915
  • the refrigerant or composition comprises HFO-1132 (E), HFO-1123 and R32.
  • HFO-1132 (E), HFO-1123 and R32 In the above-mentioned refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R32 based on the sum of these is x, y and z, respectively, HFO-1132 (E), HFO-1123 and R32
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point E (72.2, 9.4, 18.4) and point A'(81.6, 0.0, 18.4) Within the range of the figure surrounded by the line segments OC, CD, DE, EA'and A'O connecting the five points, respectively, or on the line segments CD, DE and EA'(excluding points C and A').
  • the line segment CDE is It is represented by the coordinates (-0.017z 2 + 0.0148z + 77.684, 0.017z 2 + 0.9852z + 22.316, z), and the line segments OC, EA'and A'O are straight lines.
  • Item 5. The refrigerator or method according to Item 1.
  • the refrigerant or composition comprises HFO-1132 (E), HFO-1123 and R32.
  • HFO-1132 (E), HFO-1123 and R32 In the above-mentioned refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R32 based on the sum of these is x, y and z, respectively, HFO-1132 (E), HFO-1123 and R32
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5) and point A (90.5, 0.0, 9.5) It is within the range of the figure surrounded by the line segments OC', C'D', D'A and AO connecting the five points, or on the line segments C'D'and D'A (however, the points C'and D'A.
  • the line segment C'D' is It is represented by the coordinates (-0.0297z 2 -0.1915z + 56.7, 0.0297z 2 + 1.1915z + 43.3, z), and the line segments OC', D'A and AO are straight lines.
  • Item 5. The refrigerator or method according to Item 1.
  • the refrigerant or composition comprises HFO-1132 (E), HFO-1123 and R32.
  • HFO-1132 (E), HFO-1123 and R32 In the above-mentioned refrigerant, when the mass% of HFO-1132 (E), HFO-1123 and R32 based on the sum of these is x, y and z, respectively, HFO-1132 (E), HFO-1123 and R32
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point A (90.5, 0.0, 9.5) Within the range of the figure surrounded by the line segments OC, CD, DA and AO connecting the five points, or on the line segments CD and DA (excluding points C and A).
  • the line segment CD is Represented in coordinates (-0.017z 2 + 0.0148z + 77.684, 0.017z 2 + 0.9852z + 22.316, z), and the line segments OC, DA and AO are straight lines.
  • Item 5. The refrigerator or method according to Item 1.
  • the refrigerant or composition is CO 2 , and trans-1,2-difluoroethylene (HFO-1132 (E)), difluoromethane (R32) and 2,3,3,3-tetrafluoro-1-propen (R1234yf).
  • Curve JK is Represented in coordinates (x, 0.0095x 2 -1.2222x + 67.676, -0.0095x 2 + 0.2222x + 32.324-w)
  • Curve KL Represented by coordinates (x, 0.0049x 2 -0.8842x + 61.488, -0.0049x 2 -0.1158x + 38.512), Item 5.
  • the refrigerant or composition is CO 2 , and trans-1,2-difluoroethylene (HFO-1132 (E)), difluoromethane (R32) and 2,3,3,3-tetrafluoro-1-propen (R1234yf).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • R32 difluoromethane
  • R1234yf 2,3,3,3-tetrafluoro-1-propen
  • ) Including CO 2 , and R32, HFO-1132 (E), and R1234yf, where the mass% based on the sum of these is w, and x, y, and z, respectively, of R32, HFO-1132 (E), and R1234yf.
  • the curve IJ is within the range of the figure surrounded by CI or on the line segment (except for the point on the straight line CI). Represented in coordinates (x, 0.0236x 2 -1.716x + 72, -0.0236x 2 + 0.716x + 28-w) Curve JK is Represented in coordinates (x, 0.0095x 2 -1.2222x + 67.676, -0.0095x 2 + 0.2222x + 32.324-w), Item 5.
  • the refrigerant or composition, CO 2 and comprises R32, HFO-1132 (E) and R1234yf, the CO 2, and R32, HFO-1132 (E) and R1234yf, mass% relative to the the sum of these
  • the coordinates (x, y, z) are ,
  • Point I (0.0, 72.0, 28.0-w)
  • Point J (18.3, 48.5, 33.2-w)
  • Point E (18.2, -1.1111w 2 -3.1667w + 31.9, 1.1111w 2 + 2.1667w + 49.9)
  • Curve IJ and curve JK connecting the four points of point C (0.0, -4.9167w + 58.317, 3.9167w + 41.683), and within or on the line segment surrounded by the straight line KF,
  • Item 24. The refrigerant or composition, CO 2, and comprises R32, HFO-1132 (E) and R1234yf, the CO 2, and R32, HFO-1132 (E) and R1234yf, mass% relative to the the sum of these
  • the sum of R32, HFO-1132 (E) and R1234yf is (100-w) mass%, where w and x, y and z are used, respectively, the coordinates (x, y, z) are ,
  • Point G -5.8333w 2 -3.1667w + 22.2, 7.0833w 2 -1.4167w + 26.2, -1.25w 2 + 3.5834w + 51.6
  • Point O (36.8, 0.8333w 2 + 1.8333w + 22.6, -0.8333w 2 -2.8333w + 40.6)
  • Point F (-0.0833w + 36.717, -4.0833w +
  • Curve MW is Coordinates (x, (0.0043w 2 -0.0359w + 0.1509) x 2 + (-0.0493w 2 + 0.4669w-3.6193) x-0.3004w 2 +2.419w + 55.53, 100-wxy) Represented by Curve WN Coordinates (x, (0.0055w 2 -0.0326w + 0.0665) x 2 + (-0.1571w 2 + 0.8981w-2.6274) x + 0.6555w 2 -2.2153w + 54.044, 100-wxy) Represented by Curve NO is Coordinates (x, (-0.00062w 2 + 0.0036w + 0.0037) x 2 + (0.0375w 2 -0.239w-0.4977) x-0.8575w 2 +6.4941w + 36.078, 100-wxy) Represented by When 1.3 ⁇ w ⁇ 4.0 Point M (0.0, -0.3004w 2 + 2.419w + 55.53,
  • Point C (0.0, 0.0667w 2 -4.9667w + 58.3, -0.0667w 2 + 3.9667w + 41.7) It is within the range of the figure surrounded by the curve MW, the curve WN and the curve NO, and the straight line OB', the straight line B'D, and the straight line DC and the straight line CM, respectively, or on the line segment (however, the straight line CM).
  • Curve MW is Coordinates (x, (0.00357w 2 -0.0391w + 0.1756) x 2 + (-0.0356w 2 + 0.4178w-3.6422) x-0.0667w 2 + 0.8333w + 58.103, 100-wxy) Represented by Curve WN Coordinates (x, (-0.002061w 2 + 0.0218w-0.0301) x 2 + (0.0556w 2 -0.5821w-0.1108) x-0.4158w 2 + 4.7352w + 43.383, 100-wxy)
  • Curve NO is Coordinates (x, (0.0082x 2 + (0.0022w 2 -0.0345w-0.7521) x-0.1307w 2 + 2.0247w + 42.327, 100-wxy) Represented by Item 5.
  • Item 25. The refrigerant or composition, CO 2, and comprises R32, HFO-1132 (E) and R1234yf, the CO 2, and R32, HFO-1132 (E) and R1234yf, mass% relative to the the sum of these
  • the sum of R32, HFO-1132 (E) and R1234yf is (100-w) mass%, where w and x, y and z are used, respectively, the coordinates (x, y, z) are ,
  • Point M (0.0, -0.3004w 2 + 2.419w + 55.53, 0.3004w 2 -3.419w + 44.47)
  • Point W (10.0, -0.3645w 2 + 3.5024w + 34.422, 0.3645w 2 -4.5024w + 55.578)
  • Point N (18.2, -0.3773w 2 + 3.319w + 28.26, 0.3773w 2
  • the refrigerant or composition Contains HFO-1132 (E)) and HFO-1234yf, For the total mass of HFO-1132 (E) and HFO-1234yf The content ratio of HFO-1132 (E) is 35.0 to 65.0% by mass, The content of HFO-1234yf is 65.0 to 35.0% by mass. Item 5.
  • the refrigerator or method according to Item 1. Item 27.
  • the content ratio of HFO-1132 (E) is 41.3 to 53.5% by mass, The content of HFO-1234yf is 58.7-46.5% by mass, Item 26.
  • the refrigerant or composition contains HFO-1132 (E) and HFO-1234yf.
  • the content ratio of HFO-1132 (E) is 40.5-49.2% by mass, The content of HFO-1234yf is 59.5 to 50.8% by mass.
  • the refrigerator or method according to Item 1. Item 29.
  • the refrigerant or composition contains HFO-1132 (E) and HFO-1234yf.
  • the content ratio of HFO-1132 (E) is 31.1 to 39.8% by mass, The content of HFO-1234yf is 68.9-60.2% by mass, Item 5.
  • the refrigerant or composition contains HFO-1132 (E) and HFO-1234yf.
  • HFO-1132 (E) and HFO-1234yf For the total mass of HFO-1132 (E) and HFO-1234yf
  • the content ratio of HFO-1132 (E) is 21.0 to 28.4% by mass
  • the content of HFO-1234yf is 79.0 to 71.6% by mass.
  • Item 5. The refrigerator or method according to Item 1.
  • Item 34. The refrigerator or method according to Item 33, wherein the refrigerant or composition comprises only HFO-1132 (E) and HFO-1234yf.
  • Item 35 The refrigerant or composition contains HFO-1132 (E) and HFO-1234yf.
  • HFO-1132 (E) and HFO-1234yf The content ratio of HFO-1132 (E) is 12.1 to 72.0% by mass.
  • the content of HFO-1234yf is 87.9 to 28.0% by mass.
  • Item 5. The refrigerator or method according to Item 1.
  • Item 36. Item 35.
  • the refrigerator or method according to Item 35, wherein the refrigerant or composition comprises only HFO-1132 (E) and HFO-1234yf.
  • Item 37 Item 35 or 36.
  • Item 37 The vehicle-mounted air-conditioning device according to Item 37, wherein the vehicle-mounted air-conditioning device is for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle.
  • the points and line segments that specify the refrigerant of the present disclosure are shown. is there.
  • the three-component composition diagram in which the total sum of R32, HFO-1132 (E) and R1234yf is 93% by mass (CO 2 content is 7% by mass) shows the points and line segments that define the refrigerant of the present disclosure. is there. It is a schematic diagram of the experimental apparatus for discriminating combustibility (combustible or non-combustible).
  • the present inventors have obtained a refrigerator containing a refrigerant containing HFO-1132 as an operating medium, and the refrigerant is used as a desiccant and / or an oxygen scavenger. It has been found that the above problem can be solved by a refrigerator having a processing unit to be contacted.
  • HFO-1132 refers to HFO-1132 (E)
  • HFO-1132a refers to the sum of HFO-1132 (E) and HFO-1132 (Z) and HFO-1132a.
  • refrigerant includes at least a compound having a refrigerant number (ASHRAE number) starting with R indicating the type of refrigerant defined by ISO817 (International Organization for Standardization), and further includes a refrigerant number. Even if it has not been attached yet, those having the same characteristics as a refrigerant are included.
  • Refrigerants are roughly classified into “fluorocarbon-based compounds” and “non-fluorocarbon-based compounds” in terms of compound structure.
  • Fluorocarbon-based compounds include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
  • non-fluorocarbon compound include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744) and ammonia (R717).
  • the term "refrigerator” refers to a general device that keeps a temperature lower than the surrounding outside air by removing heat from an object or space and maintains this low temperature.
  • a refrigerator is a conversion device that obtains energy from the outside to perform work and convert energy in order to transfer heat from the lower temperature side to the higher temperature side.
  • 1. Refrigerant containing HFO-1132
  • the refrigerant used in the present disclosure may be a refrigerant containing HFO-1132.
  • the refrigerant used in the present disclosure may be a refrigerant consisting only of HFO-1132.
  • HFO-1132 may be trans-1,2-difluoroethylene (HFO-1132 (E)) or cis-1,2-difluoroethylene (HFO-1132 (Z)). , A mixture thereof, but preferably trans-1,2-difluoroethylene (HFO-1132 (E)).
  • the refrigerant used in the present disclosure may be a mixed refrigerant containing HFO-1132 and an additional refrigerant.
  • R1234ze may be trans-1,3,3,3-tetrafluoro-1-propene (R1234ze (E)) or cis-1,3,3,3-tetrafluoro-1-propene (R1234ze). (Z)) or a mixture thereof.
  • the refrigerant used in the present disclosure may contain other additional refrigerants in addition to the above-mentioned specific additional refrigerants.
  • the refrigerant of the present disclosure may contain 99.5% by mass or more, 99.75% by mass or more, or 99.9% by mass of the total of HFO-1132 and the above-mentioned specific additional refrigerant with respect to the total refrigerant. It may contain more than%.
  • the refrigerant of the present disclosure may contain HFO-1132 in an amount of 99.5% by mass or more, 99.75% by mass or more, or 99.9% by mass or more with respect to the entire refrigerant.
  • Examples of the mixed refrigerant include those containing at least one selected from the above-mentioned additional refrigerant group.
  • Examples of the mixed refrigerant include a mixed refrigerant of HFO-1132 and HFO-1123, a mixed refrigerant of HFO-1132, HFO-1123 and R32, a mixed refrigerant of HFO-1132, HFO-1123 and R1234yf, and HFO-1132.
  • the stability of HFO-1132 is improved by providing a treatment unit for bringing the refrigerant into contact with a desiccant and / or a deoxidizer. Can be made to. It is understood that it is important to remove water and / or oxygen from the refrigerant containing HFO-1132 to obtain the above effects. Therefore, it is understood that the same effect will be obtained regardless of the type of additional refrigerant contained in the refrigerant. 2.
  • Refrigerants A to E Hereinafter, the refrigerants A to E, which are the refrigerants used in the present disclosure, will be described in detail.
  • Refrigerant A, Refrigerant B, Refrigerant C, Refrigerant D and Refrigerant E are independent of each other, and the alphabets indicating points and lines, the numbers of Examples and the numbers of Comparative Examples are all independent. It is assumed that the refrigerant A, the refrigerant B, the refrigerant C, the refrigerant D and the refrigerant E are independent of each other.
  • the first embodiment of the refrigerant A and the first embodiment of the refrigerant B show examples of different embodiments.
  • Refrigerants A of the present disclosure include trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123) and 2,3,3,3-tetrafluoro-1-propen (R1234yf). It is a mixed refrigerant containing.
  • the refrigerant A of the present disclosure has various characteristics desirable as an alternative refrigerant for R410A, such as having the same refrigerating capacity and coefficient of performance as R410A and having a sufficiently small GWP.
  • the refrigerant A of the present disclosure is a composition containing HFO-1132 (E) and R1234yf and, if necessary, HFO-1123, and may further satisfy the following requirements.
  • This refrigerant A also has the same refrigerating capacity and coefficient of performance as R410A, and has sufficiently small GWP, which are desirable characteristics as an alternative refrigerant for R410A.
  • the coordinates (x, y, z) are Point D (87.6, 0.0, 12.4), Point G (18.2, 55.1, 26.7), Point H (56.7, 43.3, 0.0) and Point O (100.0, 0.0, 0.0) Within the range of the figure surrounded by the line segments OD, DG, GH and HO connecting the four points, respectively, or on the line segments OD, DG and GH (however, points O and H are excluded).
  • the line segment DG is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402)
  • the line segment GH is It is represented by the coordinates (-0.0134z 2 -1.0825z + 56.692, 0.0134z 2 + 0.0825z + 43.308, z), and the line segments HO and OD are straight lines.
  • the refrigerant A of the present disclosure has a refrigerating capacity ratio based on R410A of 92.5% or more, and a COP ratio based on R410A of 92.5% or more.
  • the refrigerant A of the present disclosure is HFO-1132 (E), HFO-1123 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point L (72.5, 10.2, 17.3), Point G (18.2, 55.1, 26.7), Point H (56.7, 43.3, 0.0) and Point I (72.5, 27.5, 0.0) Within the range of the figure surrounded by the line segments LG, GH, HI and IL connecting the four points, or on the line segments LG, GH and IL (however, points H and I are excluded).
  • the line segment LG is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402),
  • the line segment GH is It is preferable that it is represented by coordinates (-0.0134z 2 -1.0825z + 56.692, 0.0134z 2 + 0.0825z + 43.308, z) and that the line segments HI and IL are straight lines.
  • Refrigerant A of the present disclosure not only has a refrigerating capacity ratio of 92.5% or more based on R410A and a COP ratio of 92.5% or more based on R410A when the above requirements are satisfied, and also has an ASHRAE standard. Shows slight flammability (2L class).
  • the refrigerant A of the present disclosure is HFO-1132 (E), HFO-1123 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point D (87.6, 0.0, 12.4), Point E (31.1, 42.9, 26.0), Point F (65.5, 34.5, 0.0) and Point O (100.0, 0.0, 0.0) Within the range of the figure surrounded by the line segments OD, DE, EF and FO connecting the four points, respectively, or on the line segments OD, DE and EF (however, points O and F are excluded).
  • the line segment DE is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402)
  • the line segment EF is It is preferable that it is represented by coordinates (-0.0064z 2 -1.1565z + 65.501, 0.0064z 2 + 0.1565z + 34.499, z) and the line segments FO and OD are straight lines.
  • the refrigerant A of the present disclosure has a refrigerating capacity ratio based on R410A of 93.5% or more, and a COP ratio based on R410A of 93.5% or more.
  • the refrigerant A of the present disclosure is HFO-1132 (E), HFO-1123 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point L (72.5, 10.2, 17.3), Point E (31.1, 42.9, 26.0), Point F (65.5, 34.5, 0.0) and Point I (72.5, 27.5, 0.0) Within the range of the figure surrounded by the line segments LE, EF, FI and IL connecting the four points, or on the line segments LE, EF and IL (however, points F and I are excluded).
  • the line segment LE is Represented in coordinates (0.0047y 2 -1.5177y + 87.598, y, -0.0047y 2 + 0.5177y + 12.402),
  • the line segment EF is It is preferable that it is represented by coordinates (-0.0134z 2 -1.0825z + 56.692, 0.0134z 2 + 0.0825z + 43.308, z) and that the line segments FI and IL are straight lines.
  • Refrigerant A of the present disclosure not only has a refrigerating capacity ratio of 93.5% or more based on R410A and a COP ratio of 93.5% or more based on R410A when the above requirements are satisfied, and also has an ASHRAE standard. Shows slight flammability (2L class).
  • the refrigerant A of the present disclosure is HFO-1132 (E), HFO-1123 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point A (93.4, 0.0, 6.6), Point B (55.6, 26.6, 17.8), Point C (77.6, 22.4, 0.0) and point O (100.0, 0.0, 0.0)
  • Point A (93.4, 0.0, 6.6
  • Point B (55.6, 26.6, 17.8)
  • Point C 77.6, 22.4, 0.0
  • point O 100.0, 0.0, 0.0
  • the line segment AB is Represented in coordinates (0.0052y 2 -1.5588y + 93.385, y, -0.0052y 2 +0.5588y + 6.615)
  • the line segment BC is It is preferable that it is represented by coordinates (-0.0032z 2 -1.1791z + 77.593, 0.0032z 2 + 0.1791z + 22.407, z) and the line segments CO and OA are straight lines.
  • the refrigerant A of the present disclosure has a refrigerating capacity ratio based on R410A of 95% or more, and a COP ratio based on R410A of 95% or more.
  • the refrigerant A of the present disclosure is HFO-1132 (E), HFO-1123 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point K (72.5, 14.1, 13.4), Point B (55.6, 26.6, 17.8) and point J (72.5, 23.2, 4.3) It is within the range of the figure surrounded by the line segment KB, BJ and JK connecting the three points, or on the line segment, and the line segment KB is Represented in coordinates (0.0052y 2 -1.5588y + 93.385, y, -0.0052y 2 +0.5588y + 6.615)
  • the line segment BJ is It is preferable that it is represented by coordinates (-0.0032z 2 -1.1791z + 77.593, 0.0032z 2 + 0.1791z + 22.407,
  • Refrigerant A of the present disclosure not only has a refrigerating capacity ratio based on R410A of 95% or more and a COP ratio based on R410A of 95% or more when the above requirements are satisfied, and also has an ASHRAE standard. Shows slight flammability (2L class).
  • the refrigerant A of the present disclosure may further contain difluoromethane (R32) in addition to HFO-1132 (E), HFO-1123 and R1234yf, as long as the above characteristics and effects are not impaired.
  • the content ratio of R32 to the whole of the refrigerant A of the present disclosure is not particularly limited and can be widely selected. For example, when the content ratio of R32 to the whole of the refrigerant A of the present disclosure is 21.8% by mass, the GWP of this mixed refrigerant is 150, so that the content ratio of R32 can be made lower than that.
  • the content ratio of R32 to the whole of the refrigerant A of the present disclosure may be, for example, 5% by mass or more.
  • the refrigerant A of the present disclosure contains R32 in addition to HFO-1132 (E), HFO-1123 and R1234yf
  • the sum of these of HFO-1132 (E), HFO-1123 and R1234yf and R32 is used as a reference.
  • FIGS. 3 to 9 In the three-component composition diagram (FIGS. 3 to 9) in which the total sum of HFO-1132 (E), HFO-1123 and R1234yf is 100% by mass, where x, y and z and a are the mass%.
  • point B' is based on R410A, where point B is the point where the refrigerating capacity ratio based on R410A is 95% and the COP ratio based on R410A is 95% in the three-component composition diagram. It is the intersection of the approximate straight line connecting the points where the COP ratio is 95% and the straight line AB.
  • the refrigerant A of the present disclosure has a refrigerating capacity ratio based on R410A of 95% or more, and a COP ratio based on R410A of 95% or more.
  • the refrigerant A of the present disclosure may contain other additional refrigerants in addition to HFO-1132 (E), HFO-1123 and R1234yf and R32, as long as the above characteristics and effects are not impaired. Good.
  • the refrigerant A of the present disclosure preferably contains the total of HFO-1132 (E), HFO-1123, R1234yf, and R32 in an amount of 99.5% by mass or more, preferably 99.75% by mass or more, based on the total amount of the refrigerant A. Is more preferable, and it is further preferable to contain 99.9% by mass or more.
  • the refrigerant A of the present disclosure may contain 99.5% by mass or more of the total of HFO-1132 (E), HFO-1123 and R1234yf with respect to the entire refrigerant A, and may contain 99.75% by mass or more. It may further contain 99.9% by mass or more.
  • the refrigerant A of the present disclosure may contain the total of HFO-1132 (E), HFO-1123, R1234yf and R32 in an amount of 99.5% by mass or more, and 99.75% by mass or more, based on the total amount of the refrigerant A. It may be 99.9% by mass or more.
  • the additional refrigerant is not particularly limited and can be widely selected.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • the refrigerant A of the present disclosure is suitable for use as an alternative refrigerant for R410A.
  • Example of Refrigerant A Hereinafter, an example of the refrigerant A will be described in more detail.
  • the refrigerant A of the present disclosure is not limited to these examples.
  • a mixed refrigerant was prepared by mixing HFO-1132 (E), HFO-1123, and R1234yf in mass% shown in Tables 1 to 5 based on the sum of these.
  • the COP ratio and refrigerating capacity ratio based on R410 were calculated.
  • the calculation conditions are as follows.
  • the coordinates (x, y, z) are Point D (87.6, 0.0, 12.4), Point E (31.1, 42.9, 26.0), Point F (65.5, 34.5, 0.0) and Point O (100.0, 0.0, 0.0)
  • Point D 87.6, 0.0, 12.4
  • Point E 31.1, 42.9, 26.0
  • Point F (65.5, 34.5, 0.0)
  • Point O 100.0, 0.0, 0.0
  • the refrigerating capacity ratio based on R410A is 93.5% or more
  • the COP ratio based on R410A is 93.5% or more.
  • the coordinates (x, y, z) are Point A (93.4, 0.0, 6.6), Point B (55.6, 26.6, 17.8), Point C (77.6, 22.4, 0.0) and point O (100.0, 0.0, 0.0) Within the range of the figure (Fig. 2) surrounded by the line segments OA, AB, BC and CO connecting the four points, or on the line segments OA, AB and BC (however, points O and C are excluded). , It can be seen that the refrigerating capacity ratio based on R410A is 95% or more, and the COP ratio based on R410A is 95% or more.
  • R1234yf contributes to a decrease in flammability and suppression of alteration such as polymerization, and it is preferable to include this.
  • the combustion speed test was performed as follows using the device shown in FIG. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • a mixed refrigerant was prepared by mixing HFO-1132 (E), HFO-1123, R1234yf, and R32 in the mass% shown in Tables 6 to 12, respectively, based on the sum of these.
  • the R32 content ratio a (mass%) is 0% by mass, 5% by mass, 10% by mass, 14.3% by mass, 16.5% by mass, 19.2% by mass, and 21.8% by mass, respectively. Represents the composition of the case.
  • point B' is based on R410A, where point B is the point where the refrigerating capacity ratio based on R410A is 95% and the COP ratio based on R410A is 95% in the three-component composition diagram. This is the intersection of the straight line AB and the approximate straight line connecting the three points including the point C where the COP ratio is 95%.
  • Points A, B'and C were obtained by approximate calculation as follows.
  • Point A is that the HFO-1123 content ratio is 0% by mass and the refrigerating capacity ratio based on R410A is 95%.
  • point A three points were obtained for each of the following three ranges by calculation, and these approximate expressions were obtained.
  • Point C is that the R1234yf content ratio is 0% by mass and the COP ratio based on R410A is 95%.
  • point C three points were obtained for each of the following three ranges by calculation, and these approximate expressions were obtained.
  • the refrigerant B of the present disclosure is The total of HFO-1132 (E) and HFO-1123 is contained in an amount of 99.5% by mass or more based on the total amount of the refrigerant B, and HFO-1132 (E) is contained in an amount of 62.5% by mass to 72.5% by mass based on the total amount of the refrigerant B. Including, it is a mixed refrigerant.
  • the refrigerant B of the present disclosure has (1) a coefficient of performance equivalent to that of R410A, (2) has an equivalent refrigerating capacity as R410A, (3) has a sufficiently small GWP, and (4) has an ASHRAE standard. It has various characteristics that are desirable as an alternative refrigerant for R410A, such as being slightly flammable (2L class).
  • the refrigerant B of the present disclosure is particularly preferable as long as it is a mixed refrigerant containing 72.5% by mass or less of HFO-1132 (E), because it has a slight flammability (2L class) according to the ASHRAE standard.
  • the refrigerant B of the present disclosure is more preferably a mixed refrigerant containing 62.5% by mass or more of HFO-1132 (E).
  • the refrigerant B of the present disclosure has a better coefficient of performance ratio based on R410A, and the polymerization reaction of HFO-1132 (E) and / or HFO-1123 is further suppressed, and the stability is further improved. It will be excellent.
  • the refrigerant B of the present disclosure may contain other additional refrigerants in addition to HFO-1132 (E) and HFO-1123, as long as the above characteristics and effects are not impaired.
  • the refrigerant B of the present disclosure preferably contains the total of HFO-1132 (E) and HFO-1123 in an amount of 99.75% by mass or more, more preferably 99.9% by mass or more, based on the total amount of the refrigerant B. ..
  • the additional refrigerant is not particularly limited and can be widely selected.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • the refrigerant B of the present disclosure is suitable for use as a substitute refrigerant for HFC refrigerants such as R410A, R407C and R404A, and HCFC refrigerants such as R22.
  • HFC refrigerants such as R410A, R407C and R404A
  • HCFC refrigerants such as R22.
  • refrigerant B an example of the refrigerant B will be described in more detail.
  • the refrigerant B of the present disclosure is not limited to these examples.
  • a mixed refrigerant was prepared by mixing HFO-1132 (E) and HFO-1123 in mass% (mass%) shown in Tables 16 and 17, respectively, based on the sum of these.
  • the refrigerating capacity of a composition containing a mixture of R410A and HFO-1132 (E) and HFO-1123 was determined using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.
  • COP coefficient of performance
  • the combustion speed test was performed as follows using the device shown in FIG. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the refrigerant C of the present disclosure is a mixed refrigerant containing HFO-1132 (E), R32 and 2,3,3,3-tetrafluoro-1-propen (R1234yf).
  • the refrigerant C of the present disclosure has various characteristics desirable as an alternative refrigerant for R410A, such as having a cooling capacity equivalent to that of R410A, having a sufficiently small GWP, and being slightly flammable (2L class) according to the ASHRAE standard.
  • the refrigerant C of the present disclosure is of HFO-1132 (E), R32 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are 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) It is within the range of the figure surrounded by the line segments AC, CF, FD, and DA that connect the four points, or on the line segment.
  • the line segment AC is Represented in coordinates (0.0181y 2 -2.2288y + 71.096, y, -0.0181y 2 + 1.2288y + 28.904)
  • the line segment FD is It is preferable that it is represented by coordinates (0.02y 2 -1.7y + 72, y, -0.02y 2 + 0.7y + 28) and the line segments CF and DA are straight lines.
  • the refrigerant C of the present disclosure has a refrigerating capacity ratio of 85% or more based on R410A, a GWP of 125 or less, and is slightly flammable (2L class) according to the ASHRAE standard.
  • the refrigerant C of the present disclosure is of HFO-1132 (E), R32 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are 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) Within or on the line segment surrounded by the line segments AB, BE, ED, and DA connecting the four points, respectively.
  • the line segment AB is Represented in coordinates (0.0181y 2 -2.2288y + 71.096, y, -0.0181y 2 + 1.2288y + 28.904)
  • the line segment ED is It is preferable that it is represented by coordinates (0.02y 2 -1.7y + 72, y, -0.02y 2 + 0.7y + 28) and the line segments BE and DA are straight lines.
  • the refrigerant C of the present disclosure has a refrigerating capacity ratio of 85% or more based on R410A, a GWP of 100 or less, and is slightly flammable (2L class) according to the ASHRAE standard.
  • the refrigerant C of the present disclosure is of HFO-1132 (E), R32 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point G (77.5, 6.9, 15.6), Point I (55.1, 18.3, 26.6) and Point J (77.5.
  • the refrigerant C of the present disclosure has a refrigerating capacity ratio based on R410A of 95% or more, a GWP of 100 or less, is less likely to cause changes such as polymerization and decomposition, and has excellent stability. There is.
  • the refrigerant C of the present disclosure is of HFO-1132 (E), R32 and R1234yf, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are 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) It is within the range of the figure surrounded by the line segment GH, HK and KG connecting the three points, or on the line segment, and the line segment GH is It is preferable that it is represented by the coordinates (0.02y 2 -2.4583y + 93.396, y, -0.02y 2 + 1.4583y + 6.604) and the line segments HK and KG are straight lines.
  • the refrigerant C of the present disclosure has a refrigerating capacity ratio based on R410A of 95% or more, a GWP of 100 or less, is less likely to cause changes such as polymerization and decomposition, and has excellent stability. There is.
  • the refrigerant C of the present disclosure may contain other additional refrigerants in addition to HFO-1132 (E), R32 and R1234yf, as long as the above characteristics and effects are not impaired.
  • the refrigerant C of the present disclosure preferably contains the total of HFO-1132 (E), R32 and R1234yf in an amount of 99.5% by mass or more, more preferably 99.75% by mass or more, based on the total amount of the refrigerant C. It is more preferable to contain 99.9% by mass or more.
  • the additional refrigerant is not particularly limited and can be widely selected.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • the refrigerant C of the present disclosure is suitable for use as an alternative refrigerant for R410A.
  • Example of Refrigerant C Hereinafter, an example of the refrigerant C will be described in more detail.
  • the refrigerant C of the present disclosure is not limited to these examples.
  • the combustion speed test was performed as follows using the device shown in FIG. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • a mixed refrigerant was prepared by mixing HFO-1132 (E), R32 and R1234yf in mass% shown in Tables 19 to 23, respectively, based on the sum of these.
  • the coefficient of performance [Coefficient of Performance (COP)] ratio and the refrigerating capacity ratio based on R410 were determined. The calculation conditions are as follows.
  • the sum of HFO-1132 (E), R32 and R1234yf is In the three-component composition diagram of 100% by mass, the coordinates (x, y, z) are 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) If it is within the range of the line segment AC, CF, FD, and DA (Fig. 10) that connects the four points, or on the line segment, the refrigerating capacity ratio based on R410A is 85% or more. It can be seen that GWP is 125 or less and that it is slightly flammable (2L class) according to the ASHRAE standard.
  • the coordinates (x, y, z) are 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) If it is within the range of the line segment AB, BE, ED, and DA (Fig. 10) connecting the four points, or on the line segment, the refrigerating capacity ratio based on R410A is 85% or more. It can be seen that GWP is 100 or less and that it is slightly flammable (2L class) according to the ASHRAE standard.
  • the coordinates (x, y, z) are 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) If it is within the range of the line segment GI, IJ, and JK (Fig. 10) connecting the three points, or on the line segment, the refrigerating capacity ratio based on R410A is 95% or more, and the GWP is 125. It can be seen that the results are as follows, and changes such as polymerization and decomposition are unlikely to occur, and the stability is excellent.
  • the coordinates (x, y, z) are 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) If it is within the range of the line segment GH, HK and KG (Fig. 10) connecting the three points, or on the line segment, the refrigerating capacity ratio based on R410A is 95% or more, and GWP is 100. It can be seen that the results are as follows, and changes such as polymerization and decomposition are unlikely to occur, and the stability is excellent.
  • the refrigerant D of the present disclosure is a mixed refrigerant containing HFO-1132 (E), HFO-1123 and R32.
  • the refrigerant D of the present disclosure has various characteristics desirable as an alternative refrigerant for R410A, such as having a coefficient of performance equivalent to that of R410A and having a sufficiently small GWP.
  • the refrigerant D of the present disclosure is HFO-1132 (E), HFO-1123 and R32, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5), Point E'(41.8, 39.8, 18.4) and Point A'(81.6, 0.0, 18.4)
  • the refrigerant D of the present disclosure is HFO-1132 (E), HFO-1123 and R32, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point E (72.2, 9.4, 18.4) and point A'(81.6, 0.0, 18.4) Within the range of the figure surrounded by the line segments OC, CD, DE, EA'and A'O connecting the five points, respectively, or on the line segments CD, DE and EA'(excluding points C and A').
  • the line segment CDE is It is preferable that it is represented by coordinates (-0.017z 2 + 0.0148z + 77.684, 0.017z 2 + 0.9852z + 22.316, z) and that the line segments OC, EA'and A'O are straight lines.
  • the refrigerant D of the present disclosure has a COP ratio of 95% or more based on R410A and a GWP of 125 or less.
  • the refrigerant D of the present disclosure is HFO-1132 (E), HFO-1123 and R32, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5) and point A (90.5, 0.0, 9.5) It is within the range of the figure surrounded by the line segments OC', C'D', D'A and AO connecting the five points, or on the line segments C'D'and D'A (however, the points C'and D'A.
  • the line segment C'D' is It is preferable that it is represented by coordinates (-0.0297z 2 -0.1915z + 56.7, 0.0297z 2 + 1.1915z + 43.3, z) and that the line segments OC', D'A and AO are straight lines.
  • the refrigerant D of the present disclosure has a COP ratio of 93.5% or more based on R410A and a GWP of 65 or less.
  • the refrigerant D of the present disclosure is HFO-1132 (E), HFO-1123 and R32, where x, y and z are the mass% based on the sum of these, respectively.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point A (90.5, 0.0, 9.5) Within the range of the figure surrounded by the line segments OC, CD, DA and AO connecting the five points, or on the line segments CD and DA (excluding points C and A).
  • the line segment CD is It is preferable that it is represented by coordinates (-0.017z 2 + 0.0148z + 77.684, 0.017z 2 + 0.9852z + 22.316, z) and the line segments OC, DA and AO are straight lines.
  • the refrigerant D of the present disclosure has a COP ratio of 95% or more based on R410A and a GWP of 65 or less.
  • the refrigerant D of the present disclosure may contain other additional refrigerants in addition to HFO-1132 (E), HFO-1123 and R32, as long as the above characteristics and effects are not impaired.
  • the refrigerant D of the present disclosure preferably contains the total of HFO-1132 (E), HFO-1123, and R32 in an amount of 99.5% by mass or more, more preferably 99.75% by mass or more, based on the total amount of the refrigerant D. It is preferable, and it is more preferable to contain 99.9% by mass or more.
  • the additional refrigerant is not particularly limited and can be widely selected.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • the refrigerant D of the present disclosure is suitable for use as an alternative refrigerant for R410A.
  • Example of Refrigerant D Hereinafter, an example of the refrigerant D will be described in more detail.
  • the refrigerant D of the present disclosure is not limited to these examples.
  • a mixed refrigerant was prepared by mixing HFO-1132 (E), HFO-1123, and R32 in the mass% shown in Tables 24 to 26, respectively, based on the sum of these.
  • the COP ratio and refrigeration capacity [Refrigeration Capacity (sometimes referred to as Cooling Capacity or Capacity)] ratio based on R410 were calculated.
  • the calculation conditions are as follows.
  • HFO-1132 (E), HFO-1123 and R32 based on the sum of these is x, y and z, respectively, HFO-1132 (E), HFO-1123 and
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5), Point E'(41.8, 39.8, 18.4) and Point A'(81.6, 0.0, 18.4) Within the range of the line segment OC', C'D', D'E', E'A'and A'O (FIG.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point E (72.2, 9.4, 18.4) and point A'(81.6, 0.0, 18.4)
  • Point O 100.0, 0.0, 0.0
  • Point C 77.7, 22.3, 0.0
  • Point D 7.6.3, 14.2, 9.5
  • Point E 7.4, 18.4
  • point A' 81.6, 0.0, 18.4
  • the COP ratio based on R410A is 95% or more
  • the GWP is 125 or less.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C'(56.7, 43.3, 0.0), Point D'(52.2, 38.3, 9.5) and point A (90.5, 0.0, 9.5)
  • Point O (100.0, 0.0, 0.0)
  • Point C' (56.7, 43.3, 0.0)
  • Point D' (52.2, 38.3, 9.5)
  • point A (90.5, 0.0, 9.5)
  • COP ratio based on R410A is 92.5% or more
  • GWP is 65 or less.
  • the coordinates (x, y, z) are Point O (100.0, 0.0, 0.0), Point C (77.7, 22.3, 0.0), Point D (76.3, 14.2, 9.5), Point A (90.5, 0.0, 9.5) If it is within the range of the figure (Fig. 11) surrounded by the line segments OC, CD, DA and AO connecting the five points, or on the line segments CD and DA (excluding points C and A), R410A is used. It can be seen that the standard COP ratio is 95% or more and the GWP is 65 or less.
  • the refrigerant E of the present disclosure is a mixed refrigerant containing CO 2 and R32, HFO-1132 (E) and R1234yf.
  • the refrigerant E of the present disclosure has various characteristics desirable as an alternative refrigerant for R410A, such as having a cooling capacity equivalent to that of R410A, having a sufficiently small GWP, and being slightly flammable.
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are Point I (0.0, 72.0, 28.0-w) Point J (18.3, 48.5, 33.2-w) Point K (36.8, 35.6, 27.6-w) Point L (51.7, 28.9, 19.4-w) Point B'' (-1.5278w 2 + 2.75w + 50.5, 0.0, 1.5278w 2 -3.75w + 49.5)
  • Point D (-2.9167w + 40.317, 0.0, 1.9167w + 59.683)
  • Point C (0.0, -4.9167w) +58.317, 3.9167w + 41.683)
  • Curve JK is Represented in coordinates (x, 0.0095x 2 -1.2222x + 67.676, -0.0095x 2 + 0.2222x + 32.324-w) Curve KL It is expressed in coordinates (x, 0.0049x 2 -0.8842x + 61.488, -0.0049x 2 -0.1158x + 38.512).
  • Refrigerant E of the present disclosure has a refrigerating capacity ratio of 80% or more based on R410A, GWP of 350 or less, and WCF slight combustion.
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are When 0 ⁇ w ⁇ 1.2
  • Point I (0.0, 72.0, 28.0-w)
  • Point J (18.3, 48.5, 33.2-w)
  • Point K (36.8, 35.6, 27.6-w)
  • Point F (-0.0833w + 36.717, -4.0833w + 5.1833, 3.1666w + 58.0997)
  • Curve IJ and curve JK connecting the five points of point C (0.0, -4.9167w + 58.317, 3.9167w + 41.683), and within or on the line segment surrounded by the straight line KF, straight line FC and straight line CI, respectively.
  • the curve IJ is within the range of the figure surrounded by CI or on the line segment (except for the point on the straight line CI). Represented in coordinates (x, 0.0236x 2 -1.716x + 72, -0.0236x 2 + 0.716x + 28-w) Curve JK is Anything represented by coordinates (x, 0.0095x 2 -1.2222x + 67.676, -0.0095x 2 + 0.2222x + 32.324-w) is preferable.
  • the refrigerant E of the present disclosure has a refrigerating capacity ratio of 80% or more based on R410A, a GWP of 250 or less, and a WCF slight combustion.
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are When 0 ⁇ w ⁇ 1.2
  • Point I (0.0, 72.0, 28.0-w)
  • Point J (18.3, 48.5, 33.2-w)
  • Point E (18.2, -1.1111w 2 -3.1667w + 31.9, 1.1111w 2 + 2.1667w + 49.9)
  • Point C (0.0, -4.9167w + 58.317, 3.9167w + 41.683) It is within the range of the figure surrounded by the curve IJ and the curve JK connecting the four points, and the straight line KF, the straight line FC and the straight line CI, or on the line segment (however,
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are When 0 ⁇ w ⁇ 0.6
  • Point G (-5.8333w 2 -3.1667w + 22.2, 7.0833w 2 + 1.4167w + 26.2, -1.25w 2 + 0.75w + 51.6)
  • Point O (36.8, 0.8333w 2 + 1.8333w + 22.6, -0.8333w 2 -2.8333w + 40.6)
  • Point P (51.7, 1.1111w 2 + 20.5, -1.1111w 2 -w + 27.8)
  • Point B'' (-1.5278w 2 + 2.75w + 50.5, 0.0, 1.5278w 2 -3.
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are When 0 ⁇ w ⁇ 0.6
  • Point G (-5.8333w 2 -3.1667w + 22.2, 7.0833w 2 -1.4167w + 26.2, -1.25w 2 + 3.5834w + 51.6)
  • Point O (36.8, 0.8333w 2 + 1.8333w + 22.6, -0.8333w 2 -2.8333w + 40.6)
  • Point F (-0.0833w + 36.717, -4.0833w + 5.1833, 3.1666w + 58.0997)
  • the curve GO connecting the three points of the above, and the curve GO within or on the line segment
  • Curve MW is Coordinates (x, (0.0043w 2 -0.0359w + 0.1509) x 2 + (-0.0493w 2 + 0.4669w-3.6193) x-0.3004w 2 +2.419w + 55.53, 100-wxy) Represented by Curve WN Coordinates (x, (0.0055w 2 -0.0326w + 0.0665) x 2 + (-0.1571w 2 + 0.8981w-2.6274) x + 0.6555w 2 -2.2153w + 54.044, 100-wxy) Represented by Curve NO is Coordinates (x, (-0.00062w 2 + 0.0036w + 0.0037) x 2 + (0.0375w 2 -0.239w-0.4977) x-0.8575w 2 +6.4941w + 36.078, 100-wxy) Represented by When 1.3 ⁇ w ⁇ 4.0 Point M (0.0, -0.3004w 2 + 2.419w + 55.53,
  • the curve MW is within the range of the figure surrounded by the straight line DC and the straight line CM or on the line segment (excluding the points on the straight line CM). Coordinates (x, (0.00357w 2 -0.0391w + 0.1756) x 2 + (-0.0356w 2 + 0.4178w-3.6422) x-0.0667w 2 + 0.8333w + 58.103, 100-wxy) Represented by Curve WN Coordinates (x, (-0.002061w 2 + 0.0218w-0.0301) x 2 + (0.0556w 2 -0.5821w-0.1108) x-0.4158w 2 + 4.7352w + 43.383, 100-wxy) Curve NO is Coordinates (x, (0.0082x 2 + (0.0022w 2 -0.0345w-0.7521) x-0.1307w 2 + 2.0247w + 42.327, 100-wxy) Anything represented by is preferable. When the above requirements are satisfied, the refriger
  • the refrigerant E of the present disclosure contains CO 2 and R32, HFO-1132 (E) and R1234yf, respectively, when the mass% based on the sum of these is w, and x, y and z, respectively.
  • the coordinates (x, y, z) are When 1.2 ⁇ w ⁇ 4.0
  • Point M (0.0, -0.3004w 2 + 2.419w + 55.53, 0.3004w 2 -3.419w + 44.47)
  • Point W (10.0, -0.3645w 2 + 3.5024w + 34.422, 0.3645w 2 -4.5024w + 55.578)
  • Point N (18.2, -0.3773w 2 + 3.319w + 28.26, 0.3773w 2 -4.319w + 53.54)
  • Point E (-0.0365w + 18.26, 0.0623w 2 -4.5381w + 31.856,
  • the curve MW is within the range or on the line segment (except for points on the straight line CM). Coordinates (x, (0.0043w 2 -0.0359w + 0.1509) x 2 + (-0.0493w 2 + 0.4669w-3.6193) x-0.3004w 2 +2.419w + 55.53, 100-wxy) Represented by Curve WN Coordinates (x, (0.0055w 2 -0.0326w + 0.0665) x 2 + (-0.1571w 2 + 0.8981w-2.6274) x + 0.6555w 2 -2.2153w + 54.044, 100-wxy) Represented by When 4.0 ⁇ w ⁇ 7.0 Point M (0.0, -0.0667w 2 + 0.8333w + 58.133, 0.0667w 2 -1.8333w + 41.867) Point W (10.0, -0.0667w 2 + 1.1w + 39.267, 0.0667w 2 -2.1w + 50.733) Point N
  • the curve MW is within the range or on the line segment (except for points on the straight line CM). Coordinates (x, (0.00357w 2 -0.0391w + 0.1756) x 2 + (-0.0356w 2 + 0.4178w-3.6422) x-0.0667w 2 + 0.8333w + 58.103, 100-wxy) Represented by Curve WN Coordinates (x, (-0.002061w 2 + 0.0218w-0.0301) x 2 + (0.0556w 2 -0.5821w-0.1108) x-0.4158w 2 + 4.7352w + 43.383, 100-wxy) Anything represented by is preferable.
  • the refrigerant E of the present disclosure has a refrigerating capacity ratio of 80% or more based on R410A, a GWP of 125 or less, and ASHRAE slight combustion.
  • Refrigerant E of the present disclosure may contain CO 2 , as well as other additional refrigerants in addition to R32, HFO-1132 (E) and R1234yf, as long as the above characteristics and effects are not impaired. Good.
  • the refrigerant E of the present disclosure preferably contains CO 2 and the total of R32, HFO-1132 (E) and R1234yf in an amount of 99.5% by mass or more, preferably 99.75% by mass or more, based on the total amount of the refrigerant. More preferably, it contains 99.9% by mass or more.
  • the additional refrigerant is not particularly limited and can be widely selected.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • the refrigerant E of the present disclosure can be preferably used as a working fluid in a refrigerator.
  • compositions of the present disclosure are suitable for use as an alternative refrigerant for R410A.
  • Example of Refrigerant E Hereinafter, an example of the refrigerant E will be described in more detail.
  • the refrigerant D of the present disclosure is not limited to these examples.
  • Combustion rates were measured for CO 2 and for each of the mixed refrigerants R32, HFO-1132 (E) and R1234yf according to ANSI / ASHRAE34-2013 standards.
  • the compositions found are shown in Tables 27-29.
  • the combustion speed test was performed as follows using the device shown in FIG. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the WCFF concentration was obtained by performing a leak simulation using NIST Standard Reference Data Base Refleak Version 4.0 with the WCF concentration as the initial concentration.
  • a mixed refrigerant was prepared by mixing R32, HFO-1132 (E) and R1234yf in mass% shown in Tables 30 to 40, based on the sum of these. For each of the mixed refrigerants in Tables 30 to 37, the coefficient of performance [Coefficient of Performance (COP)] ratio and the refrigerating capacity ratio based on R410 were determined.
  • COP Coefficient of Performance
  • the refrigerating capacity of the composition containing a mixture of R410A and HFO-1132 (E), HFO-1123, and R1234yf was determined by using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). It was obtained by carrying out the theoretical calculation of the refrigeration cycle of the mixed refrigerant under the following conditions.
  • the straight line connecting points D and C is located approximately slightly to the left of the curve connecting the points where the refrigerating capacity ratio based on R410A is 80%. Therefore, when the coordinates (x, y, z) are on the left side of the straight line connecting the points D and C, it can be seen that the refrigerating capacity ratio of the mixed refrigerant based on R410A is 80% or more.
  • the coordinates of points C to G were determined by obtaining an approximate expression based on each point described in the above table. Specifically, the calculation was performed as shown in Tables 50 and 51.
  • the coordinates of the points on the curve MW and the curve WM were determined by obtaining an approximate expression based on each point described in the above table. Specifically, Table 53 (when 0% by mass ⁇ CO 2 concentration ⁇ 1.2% by mass), Table 54 (when 1.2% by mass ⁇ CO 2 concentration ⁇ 4.0% by mass), and Table 55 (when 4.0% by mass ⁇ CO 2 concentration). The calculation was performed as shown in (when ⁇ 7.0% by mass).
  • the coordinates of the points on the curve NO and the curve OP were determined by obtaining an approximate expression based on each point described in the above table. Specifically, Table 56 (when 0% by mass ⁇ CO 2 concentration ⁇ 1.2% by mass), Table 57 (when 1.2% by mass ⁇ CO 2 concentration ⁇ 4.0% by mass) and Table 58 (when 4.0% by mass ⁇ CO 2 concentration). The calculation was performed as shown in (when ⁇ 7.0% by mass).
  • Refrigerant 1-5 the refrigerants 1 to 5 which are the refrigerants used in the present disclosure will be described in detail.
  • the following descriptions of Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4 and Refrigerant 5 are independent of each other, and the alphabets indicating dots and lines, the numbers of Examples and the numbers of Comparative Examples are all independent. It is assumed that the refrigerant 1, the refrigerant 2, the refrigerant 3, the refrigerant 4, and the refrigerant 5 are independent of each other.
  • the first embodiment of the refrigerant 1 and the first embodiment of the refrigerant 2 show examples of different embodiments.
  • Refrigerant 1 The refrigerant of the present disclosure contains HFO-1132 (E) and HFO-1234yf in one embodiment, and contains HFO-1132 (E) with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the ratio is 35.0 to 65.0% by mass, and the content ratio of HFO-1234yf is 65.0 to 35.0% by mass.
  • This refrigerant may be referred to as "refrigerant 1".
  • the refrigerant 1 is used to operate a refrigeration cycle in which the evaporation temperature is -75 to -5 ° C.
  • Refrigerant 1 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has COP equal to or higher than R404A, and (3) equal to or higher than R404A. It has various characteristics of having the refrigerating capacity of.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf in the refrigerant 1 is 35.0% by mass or more, a refrigerating capacity equal to or higher than that of R404A can be obtained. .. Further, in the refrigerant 1, the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 65.0 mass% or less, so that the saturation temperature of the refrigerant 1 in the refrigeration cycle is 40 ° C. Saturation pressure can be maintained in a suitable range (particularly 2.10 Mpa or less).
  • Refrigerant 1 may have a refrigerating capacity of 95% or more for R404A, but is preferably 98% or more, more preferably 100% or more, further preferably 101% or more, and 102% or more. Is particularly preferable.
  • Refrigerant 1 has a GWP of 100 or less, so that the environmental load can be significantly suppressed as compared with other general-purpose refrigerants from the viewpoint of global warming.
  • the refrigerant 1 preferably has a high ratio of power consumed in the refrigeration cycle to R404A and refrigeration capacity (coefficient of performance (COP)).
  • COP coefficient of performance
  • the COP to R404A is 98% or more. Is more preferable, 100% or more is more preferable, and 102% or more is particularly preferable.
  • the content ratio of HFO-1132 (E) is 40.5 to 59.0% by mass and the content ratio of HFO-1234yf is 59.5 to 41.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is preferably%.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99% or more for R404A. Further, in this case, since the saturation pressure at the saturation temperature of 40 ° C. is 1.75 MPa or more and 2.00 MPa or less, the refrigerant 1 can be applied to a commercially available refrigerating apparatus for R404A without major design change.
  • the content ratio of HFO-1132 (E) is 41.3 to 59.0% by mass and the content ratio of HFO-1234yf is 58.7 to 41.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99.5% or more for R404A. Further, in this case, since the saturation pressure at the saturation temperature of 40 ° C. is 1.76 MPa or more and 2.00 MPa or less, the refrigerant 1 can be applied to a commercially available refrigerating apparatus for R404A without major design change.
  • the content ratio of HFO-1132 (E) is 41.3 to 55.0% by mass and the content ratio of HFO-1234yf is 58.7 to 45.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99.5% or more for R404A.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 53.5% by mass and the content ratio of HFO-1234yf is 58.7 to 46.5% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that it is%.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 51.0% by mass and the content ratio of HFO-1234yf is 58.7 to 49.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. % Is particularly preferable.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, and a refrigerating capacity of 99% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 49.2 mass% and the content ratio of HFO-1234yf is 58.7 to 50.8 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the saturation pressure at a saturation temperature of 40 ° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, still more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40 ° C. is in such a range, the refrigerant 1 can be applied to a commercially available refrigerating device for R404A without major design changes.
  • the saturation pressure at a saturation temperature of 40 ° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, still more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40 ° C. is in such a range, the refrigerant 1 can be applied to a commercially available refrigerating device for R404A without major design changes.
  • the discharge temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, from the viewpoint of extending the life of the members of the commercially available refrigeration apparatus for R404A. More preferably, it is 130 ° C. or lower, and particularly preferably 120 ° C. or lower.
  • Refrigerant 1 By using Refrigerant 1 to operate a refrigeration cycle in which the evaporation temperature is -75 to -5 ° C, there is an advantage that a refrigerating capacity equal to or higher than that of R404A can be obtained.
  • the evaporation temperature is preferably ⁇ 7.5 ° C. or lower, more preferably -10 ° C. or lower, still more preferably -35 ° C. or lower.
  • the evaporation temperature is preferably -65 ° C or higher, more preferably -60 ° C or higher, further preferably -55 ° C or higher, and particularly preferably -50 ° C or higher.
  • the evaporation temperature is preferably -65 ° C or higher and -5 ° C or lower, more preferably -60 ° C or higher and -5 ° C or lower, and further preferably -55 ° C or higher and -7.5 ° C or lower. , Especially preferably -50 ° C or higher and -10 ° C or lower.
  • the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, further preferably 0.04 MPa or more, and further preferably 0.05, from the viewpoint of improving the suction of the refrigerant into the compressor.
  • MPa or more is particularly preferable.
  • the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, further preferably 3.5 or more, and particularly preferably 4.0 or more, from the viewpoint of improving the efficiency of the refrigeration cycle.
  • the compression ratio is preferably 200 or less, more preferably 150 or less, further preferably 100 or less, and particularly preferably 50 or less, from the viewpoint of improving the efficiency of the refrigeration cycle.
  • Refrigerant 1 may contain HFO-1132 (E) and HFO-1234yf in the sum of these concentrations, usually 99.5% by mass or more.
  • the total amount of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 1 is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and further preferably 99.9% by mass or more. ..
  • Refrigerant 1 can contain other refrigerants in addition to HFO-1132 (E) and HFO-1234yf within a range that does not impair the above characteristics.
  • the content ratio of the other refrigerant in the entire refrigerant 1 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the other refrigerant is not particularly limited, and can be widely selected from known refrigerants widely used in this field.
  • the refrigerant 1 may contain another refrigerant alone, or may contain two or more other refrigerants.
  • the refrigerant 1 is composed of only HFO-1132 (E) and HFO-1234yf. In other words, it is particularly preferable that the total concentration of HFO-1132 (E) and HFO-1234yf in the refrigerant 1 as a whole is 100% by mass.
  • the content ratio of HFO-1132 (E) is usually 35.0 to 65.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is mass%, and the content ratio of HFO-1234yf is usually 65.0 to 35.0 mass%.
  • the refrigerant 1 has (1) a sufficiently small GWP (100 or less), (2) has a COP equal to or higher than that of R404A, and (3) has a COP equivalent to or higher than that of R404A. It has various characteristics of having the above refrigerating capacity.
  • the refrigerant 1 When the refrigerant 1 consists only of HFO-1132 (E) and HFO-1234yf, the content ratio of HFO-1132 (E) is 40.5 to 59.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content of HFO-1234yf is preferably 59.5 to 41.0% by mass.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99% or more for R404A. Further, in this case, since the saturation pressure at the saturation temperature of 40 ° C. is 1.75 MPa or more and 2.00 MPa or less, the refrigerant 1 can be applied to a commercially available refrigerating apparatus for R404A without major design change.
  • the content ratio of HFO-1132 (E) is 41.3 to 59.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferable that the content ratio of HFO-1234yf is 58.7 to 41.0% by mass.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99.5% or more for R404A. Further, in this case, since the saturation pressure at the saturation temperature of 40 ° C. is 1.76 MPa or more and 2.00 MPa or less, the refrigerant 1 can be applied to a commercially available refrigerating apparatus for R404A without major design change.
  • the content ratio of HFO-1132 (E) is 41.3 to 55.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably that the content ratio of HFO-1234yf is 58.7 to 45.0% by mass.
  • the refrigerant 1 has a GWP of 100 or less, a COP of 101% or more for R404A, and a refrigerating capacity of 99.5% or more for R404A.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 53.5 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that the content ratio of HFO-1234yf is 58.7 to 46.5% by mass.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 51.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that the content ratio of HFO-1234yf is 58.7 to 49.0% by mass.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, and a refrigerating capacity of 99% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 49.2 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. Most preferably, the content ratio of HFO-1234yf is 58.7 to 50.8% by mass.
  • Refrigerant 1 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • Refrigerant 2 The refrigerant of the present disclosure contains HFO-1132 (E) and HFO-1234yf in one embodiment, and contains HFO-1132 (E) with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the ratio is 40.5 to 49.2% by mass, and the content ratio of HFO-1234yf is 59.5 to 50.8% by mass.
  • This refrigerant may be referred to as "refrigerant 2".
  • Refrigerant 2 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has COP equal to or higher than R404A, and (3) equal to or higher than R404A. It has various characteristics such as having refrigerating capacity and (4) being slightly flammable (class 2L) according to the ASHRAE standard. Further, in this case, the refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf in the refrigerant 2 is 40.5% by mass or more, a refrigerating capacity equal to or higher than that of R404A can be obtained. .. Further, in the refrigerant 2, the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 49.2% by mass or less, so that the saturation temperature of the refrigerant 2 in the refrigeration cycle is 40 ° C. Saturation pressure can be maintained in a suitable range (particularly 2.10 Mpa or less).
  • the refrigerating capacity of the refrigerant 2 with respect to R404A may be 99% or more, but is preferably 100% or more, more preferably 101% or more, further preferably 102% or more, and 103% or more. Is particularly preferable.
  • Refrigerant 2 has a GWP of 100 or less, so that the environmental load can be significantly suppressed as compared with other general-purpose refrigerants from the viewpoint of global warming.
  • the refrigerant 2 preferably has a high ratio of power consumed in the refrigeration cycle to R404A and refrigeration capacity (coefficient of performance (COP)).
  • the COP to R404A is 98% or more. It is preferably 100% or more, more preferably 101% or more, and particularly preferably 102% or more.
  • the content ratio of HFO-1132 (E) is 41.3 to 49.2% by mass and the content ratio of HFO-1234yf is 58.7 to 50.8% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is preferably%.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 43.0 to 49.2 mass% and the content ratio of HFO-1234yf is 57.0 to 50.8 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 101% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 44.0 to 49.2% by mass and the content ratio of HFO-1234yf is 56.0 to 50.8% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 101% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 45.0 to 49.2% by mass and the content ratio of HFO-1234yf is 55.0 to 50.8% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that it is%.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 102% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 45.0 to 48.0% by mass and the content ratio of HFO-1234yf is 55.0 to 52.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. % Is particularly preferable.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102.5% or more for R404A, a refrigerating capacity of 102.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 45.0 to 47.0% by mass and the content ratio of HFO-1234yf is 55.0 to 53.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102.5% or more for R404A, a refrigerating capacity of 102.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.85 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the saturation pressure at a saturation temperature of 40 ° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, still more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40 ° C. is in such a range, the refrigerant 2 can be applied to a commercially available refrigerating device for R404A without major design changes.
  • the saturation pressure at a saturation temperature of 40 ° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, still more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40 ° C. is in such a range, the refrigerant 2 can be applied to a commercially available refrigerating device for R404A without major design changes.
  • the discharge temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, from the viewpoint of extending the life of the members of the commercially available refrigeration apparatus for R404A. More preferably, it is 130 ° C. or lower, and particularly preferably 120 ° C. or lower.
  • the refrigerant 2 is preferably used for operating a refrigeration cycle in which the evaporation temperature is ⁇ 75 to 15 ° C. from the viewpoint of obtaining a refrigerating capacity equal to or higher than that of R404A.
  • the evaporation temperature is preferably 15 ° C. or lower, more preferably 5 ° C. or lower, further preferably 0 ° C. or lower, and particularly preferably -5 ° C. or lower.
  • the evaporation temperature is preferably -65 ° C or higher, more preferably -60 ° C or higher, further preferably -55 ° C or higher, and particularly preferably -50 ° C or higher.
  • the evaporation temperature is preferably -65 ° C or higher and 15 ° C or lower, more preferably -60 ° C or higher and 5 ° C or lower, still more preferably -55 ° C or higher and 0 ° C or lower, particularly preferably. Is -50 ° C or higher and -5 ° C or lower.
  • the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, further preferably 0.04 MPa or more, and further preferably 0.05, from the viewpoint of improving the suction of the refrigerant into the compressor.
  • MPa or more is particularly preferable.
  • the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, further preferably 3.5 or more, and particularly preferably 4.0 or more, from the viewpoint of improving the efficiency of the refrigeration cycle.
  • Refrigerant 2 may contain HFO-1132 (E) and HFO-1234yf in the sum of these concentrations, usually 99.5% by mass or more. In the present disclosure, it is preferable that the total amount of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 2 is 99.7% by mass or more, more preferably 99.8% by mass or more, and further preferably 99.9% by mass or more. ..
  • Refrigerant 2 can contain other refrigerants in addition to HFO-1132 (E) and HFO-1234yf within a range that does not impair the above characteristics.
  • the content ratio of the other refrigerant in the entire refrigerant 2 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the other refrigerant is not particularly limited, and can be widely selected from known refrigerants widely used in this field.
  • the refrigerant 2 may contain other refrigerants alone, or may contain two or more other refrigerants.
  • the refrigerant 2 is composed of only HFO-1132 (E) and HFO-1234yf.
  • the refrigerant 2 preferably has a total concentration of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 2 of 100% by mass.
  • the content ratio of HFO-1132 (E) is usually 40.5 to 49.2 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is mass%, and the content ratio of HFO-1234yf is usually 59.5 to 50.8 mass%.
  • the refrigerant 2 has (1) a sufficiently small GWP (100 or less), (2) has a COP equal to or higher than that of R404A, and (3) has a COP equal to or higher than that of R404A. It has various characteristics such as having the refrigerating capacity of (4) and being slightly flammable (class 2L) according to the ASHRAE standard.
  • the refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 41.3 to 49.2 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content of HFO-1234yf is preferably 58.7 to 50.8% by mass.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 99.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 43.0 to 49.2 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably that the content ratio of HFO-1234yf is 57.0 to 50.8% by mass.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 101% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 44.0 to 49.2 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. %, And the content ratio of HFO-1234yf is more preferably 56.0 to 50.8% by mass.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 101% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 45.0 to 49.2 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that the content ratio of HFO-1234yf is 55.0 to 50.8% by mass.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102% or more for R404A, a refrigerating capacity of 102% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • the content ratio of HFO-1132 (E) is 45.0 to 48.0 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that the content ratio of HFO-1234yf is 55.0 to 52.0% by mass.
  • Refrigerant 2 has a GWP of 100 or less, a COP of 102.5% or more for R404A, a refrigerating capacity of 102.5% or more for R404A, and is slightly flammable (class 2L) according to the ASHRAE standard. It has various characteristics of being.
  • the refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40 ° C., and can be applied to a commercially available refrigerating apparatus for R404A without major design changes.
  • Refrigerant 3 The refrigerant of the present disclosure contains HFO-1132 (E) and HFO-1234yf in one embodiment, and contains HFO-1132 (E) with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the ratio is 31.1 to 39.8% by mass, and the content ratio of HFO-1234yf is 68.9 to 60.2% by mass.
  • This refrigerant may be referred to as "refrigerant 3".
  • the refrigerant 3 has (1) a sufficiently small GWP (100 or less), (2) has a COP equivalent to that of R134a, and (3) 150% or more as compared with R134a. It has various characteristics such as having a refrigerating capacity and (4) a discharge temperature of 90 ° C or less.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 31.1% by mass or more, so that the refrigerating capacity is 150% or more as compared with R134a. can get. Further, in the refrigerant 3, the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 39.8% by mass or less, so that the discharge temperature of the refrigerant 3 in the refrigeration cycle is 90. The temperature can be maintained below °C, and the life of the members of the refrigerating device for R134a can be secured for a long time.
  • the refrigerating capacity of the refrigerant 3 with respect to R134a may be 150% or more, but is preferably 151% or more, more preferably 152% or more, further preferably 153% or more, and further preferably 154% or more. Is particularly preferable.
  • the discharge temperature in the refrigeration cycle is preferably 90.0 ° C. or lower, more preferably 89.7 ° C. or lower, further preferably 89.4 ° C. or lower, and particularly preferably 89.0 ° C. or lower.
  • the GWP of the refrigerant 3 is 100 or less, the environmental load can be significantly suppressed as compared with other general-purpose refrigerants from the viewpoint of global warming.
  • the refrigerant 3 preferably has a high ratio of power consumed in the refrigeration cycle to R134a and refrigerating capacity (coefficient of performance (COP)).
  • COP coefficient of performance
  • the COP to R134a is 90% or more. It is preferably 91% or more, more preferably 91.5% or more, and particularly preferably 92% or more.
  • the content ratio of HFO-1132 (E) is usually 31.1 to 39.8% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is usually 68.9 to It is 60.2% by mass.
  • the refrigerant 3 has (1) a sufficiently small GWP (100 or less), (2) has a COP equivalent to that of R134a, and (3) 150% or more of that of R134a. It has various characteristics such as having a refrigerating capacity and (4) a discharge temperature of 90.0 ° C or less.
  • the content ratio of HFO-1132 (E) is 31.1 to 37.9 mass% and the content ratio of HFO-1234yf is 68.9 to 62.1 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is preferably%.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 150% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 32.0 to 37.9% by mass and the content ratio of HFO-1234yf is 68.0 to 62.1% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 151% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 33.0 to 37.9 mass% and the content ratio of HFO-1234yf is 67.0 to 62.1 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is even more preferable that it is%.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 152% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 34.0 to 37.9% by mass and the content ratio of HFO-1234yf is 66.0 to 62.1% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably%.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 153% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 35.0 to 37.9% by mass and the content ratio of HFO-1234yf is 65.0 to 62.1% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is particularly preferable that it is%.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 155% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the discharge temperature is preferably 90.0 ° C. or lower, more preferably 89.7 ° C. or lower, from the viewpoint of extending the life of the members of the commercially available refrigerating apparatus for R134a. More preferably, it is 89.4 ° C. or lower, and particularly preferably 89.0 ° C. or lower.
  • the critical temperature is the cooling water or cooling air for liquefying the refrigerant. It is necessary to be significantly higher than the temperature of. From this point of view, in the refrigeration cycle in which the refrigerant 3 of the present disclosure is used, the critical temperature is preferably 80 ° C. or higher, more preferably 81 ° C. or higher, still more preferably 81.5 ° C. or higher, and particularly 82 ° C. or higher.
  • the refrigerant 3 is usually used to operate a refrigeration cycle in which the evaporation temperature is ⁇ 75 to 15 ° C. from the viewpoint of obtaining a refrigerating capacity of 150% or more as compared with R134a.
  • the evaporation temperature is preferably 15 ° C. or lower, more preferably 5 ° C. or lower, still more preferably 0 ° C. or lower, and particularly preferably -5 ° C. or lower.
  • the evaporation temperature is preferably -65 ° C or higher, more preferably -60 ° C or higher, further preferably -55 ° C or higher, and particularly preferably -50 ° C or higher.
  • the evaporation temperature is preferably ⁇ 65 ° C. or higher and 15 ° C. or lower, more preferably -60 ° C. or higher and 5 ° C. or lower, further preferably -55 ° C. or higher and 0 ° C. or lower, particularly preferably. Is -50 ° C or higher and -5 ° C or lower.
  • the critical temperature of the refrigerant is preferably 80 ° C. or higher, more preferably 81 ° C. or higher, further preferably 81.5 ° C. or higher, and particularly preferably 82 ° C. or higher from the viewpoint of improving performance. ..
  • Refrigerant 3 may contain HFO-1132 (E) and HFO-1234yf in a sum of these concentrations, usually 99.5% by mass or more. In the present disclosure, it is preferable that the total amount of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 3 is 99.7% by mass or more, more preferably 99.8% by mass or more, and further preferably 99.9% by mass or more. ..
  • Refrigerant 3 can contain other refrigerants in addition to HFO-1132 (E) and HFO-1234yf within a range that does not impair the above characteristics.
  • the content ratio of the other refrigerant in the entire refrigerant 3 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the other refrigerant is not particularly limited, and can be widely selected from known refrigerants widely used in this field.
  • the refrigerant 3 may contain another refrigerant alone, or may contain two or more other refrigerants.
  • the refrigerant 3 is composed of only HFO-1132 (E) and HFO-1234yf.
  • the refrigerant 3 preferably has a total concentration of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 3 of 100% by mass.
  • the content ratio of HFO-1132 (E) is usually 31.1 to 39.8 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is mass%, and the content ratio of HFO-1234yf is usually 68.9 to 60.2 mass%.
  • the refrigerant 3 has (1) a sufficiently small GWP (100 or less), (2) has a COP equivalent to that of R134a, and (3) 150% or more of that of R134a. It has various characteristics such as having a refrigerating capacity and (4) a discharge temperature of 90 ° C or less.
  • the refrigerant 3 When the refrigerant 3 consists of only HFO-1132 (E) and HFO-1234yf, the content ratio of HFO-1132 (E) is 31.1 to 37.9 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content of HFO-1234yf is preferably 68.9 to 62.1% by mass.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 150% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the refrigerant 3 When the refrigerant 3 consists only of HFO-1132 (E) and HFO-1234yf, the content ratio of HFO-1132 (E) is 32.0 to 37.9 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferable that the content ratio of HFO-1234yf is 68.0 to 62.1% by mass.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 151% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 33.0 to 37.9 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably that the content ratio of HFO-1234yf is 67.0 to 62.1% by mass.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 152% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 34.0 to 37.9 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably that the content ratio of HFO-1234yf is 66.0 to 62.1% by mass.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 153% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • the content ratio of HFO-1132 (E) is 35.0 to 37.9 mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is more preferably that the content ratio of HFO-1234yf is 65.0 to 62.1% by mass.
  • the refrigerant 3 has the above-mentioned configuration, so that (1) GWP is sufficiently small (100 or less), (2) has a COP of 92% or more as compared with R134a, and (3) R134a. It has various characteristics such as having a refrigerating capacity of 155% or more, (4) a discharge temperature of 90.0 ° C or less, and (5) a critical temperature of 81 ° C or more.
  • Refrigerant 4 The refrigerant of the present disclosure contains HFO-1132 (E) and HFO-1234yf in one embodiment, and contains HFO-1132 (E) with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the ratio is 21.0 to 28.4% by mass, and the content ratio of HFO-1234yf is 79.0 to 71.6% by mass.
  • This refrigerant may be referred to as "refrigerant 4".
  • the refrigerant 4 has (1) a sufficiently small GWP (100 or less), (2) has a COP equivalent to that of R1234yf, and (3) 140% or more as compared with R1234yf. It has various characteristics such as having the refrigerating capacity of (4) and being slightly flammable (class 2L) according to the ASHRAE standard. Further, in this case, the refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 21.0% by mass or more, so that the refrigerating capacity is 140% or more as compared with R1234yf. can get. Further, in the refrigerant 4, the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 28.4% by mass or less, so that it is easy to secure a critical temperature of 83.5 ° C. or higher. Become.
  • the refrigerating capacity of the refrigerant 4 with respect to R1234yf may be 140% or more, but is preferably 142% or more, more preferably 143% or more, further preferably 145% or more, and 146% or more. Is particularly preferable.
  • the GWP of the refrigerant 4 is 100 or less, the environmental load can be significantly suppressed as compared with other general-purpose refrigerants from the viewpoint of global warming.
  • the refrigerant 4 preferably has a high ratio of power consumed in the refrigeration cycle to R1234yf and refrigerating capacity (coefficient of performance (COP)).
  • COP coefficient of performance
  • the COP to R1234yf is 95% or more. It is preferably 96% or more, more preferably 97% or more, and particularly preferably 98% or more.
  • the content ratio of HFO-1132 (E) is preferably 21.5 to 28.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is preferable. It is 78.5 to 72.0% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 65.0 ° C or less and a critical temperature of 83.5 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is more preferably 22.0 to 27.7% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is higher. It is preferably 78.0 to 72.3% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 65.0 ° C or less and a critical temperature of 83.5 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is more preferably 22.5 to 27.5% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is further increased. It is preferably 77.5 to 72.5% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is particularly preferably 23.0 to 27.2% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is particularly high. It is preferably 77.0 to 72.8% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 141% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is particularly preferably 23.5 to 27.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is Particularly preferably, it is 76.5 to 73.0% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 142% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is most preferably 24.0 to 26.7% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is the highest. It is preferably 76.0 to 73.3% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 144% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard. It has various characteristics such as a discharge temperature of 64.6 ° C or less and a critical temperature of 84.0 ° C or more.
  • the refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the saturation pressure at a saturation temperature of -10 ° C is usually 0.420 MPa or less, preferably 0.418 MPa or less, more preferably 0.417 MPa or less, still more preferably 0.415 MPa or less, and particularly preferably 0.413 MPa or less.
  • the refrigerant 4 can be applied to a commercially available refrigerating device for R1234yf without major design changes.
  • the saturation pressure at a saturation temperature of -10 ° C is usually 0.380 MPa or more, preferably 0.385 MPa or more, more preferably 0.390 MPa or more, still more preferably 0.400 MPa or more, and particularly preferably 0.410 MPa or more.
  • the refrigerant 4 can be applied to a commercially available refrigerating device for R1234yf without major design changes.
  • the discharge temperature is preferably 65 ° C. or lower, more preferably 64.8 ° C. or lower, from the viewpoint of extending the life of the members of the commercially available refrigeration apparatus for R1234yf. More preferably, it is 64.7 ° C or lower, and particularly preferably 64.5 ° C or lower.
  • the refrigerant 4 is preferably used for operating a refrigeration cycle in which the evaporation temperature is ⁇ 75 to 5 ° C. from the viewpoint of obtaining a refrigerating capacity of 140% or more as compared with R1234yf.
  • the evaporation temperature is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, still more preferably -5, from the viewpoint of obtaining a refrigerating capacity of 140% or more as compared with R1234yf. °C or less, particularly preferably -10 °C or less.
  • the evaporation temperature is preferably ⁇ 75 ° C. or higher, more preferably -60 ° C. or higher, still more preferably, from the viewpoint of obtaining a refrigerating capacity of 140% or higher as compared with R1234yf. -55 ° C or higher, particularly preferably -50 ° C or higher.
  • the evaporation temperature is preferably -65 ° C or higher and 0 ° C or lower, more preferably -60 ° C or higher, from the viewpoint of obtaining a refrigerating capacity of 140% or higher as compared with R1234yf. 5 ° C or lower, more preferably -55 ° C or higher and -7.5 ° C or lower, particularly preferably -50 ° C or higher and -10 ° C or lower.
  • the discharge temperature is preferably 65.0 ° C. or lower, more preferably 64.9 ° C. or lower, still more preferably 64.8 ° C. or lower, from the viewpoint of extending the life of the members of the commercially available refrigerating apparatus for R1234yf. , 64.7 ° C or lower is particularly preferable.
  • the critical temperature is the cooling water or cooling air for liquefying the refrigerant. It is necessary to be significantly higher than the temperature of. From this point of view, in the refrigeration cycle in which the refrigerant 4 of the present disclosure is used, the critical temperature is preferably 83.5 ° C. or higher, more preferably 83.8 ° C. or higher, further preferably 84.0 ° C. or higher, and particularly preferably 84.5 ° C. or higher.
  • Refrigerant 4 can contain other refrigerants in addition to HFO-1132 (E) and HFO-1234yf within a range that does not impair the above characteristics.
  • the content ratio of the other refrigerant in the entire refrigerant 4 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the other refrigerant is not particularly limited, and can be widely selected from known refrigerants widely used in this field.
  • the refrigerant 4 may contain other refrigerants alone, or may contain two or more other refrigerants.
  • the refrigerant 4 is composed of only HFO-1132 (E) and HFO-1234yf.
  • the refrigerant 4 preferably has a total concentration of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 4 of 100% by mass.
  • the content ratio of HFO-1132 (E) is usually 21.0 to 28.4 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is mass%, and the content ratio of HFO-1234yf is usually 79.0 to 71.6 mass%.
  • the refrigerant 4 has (1) a sufficiently small GWP (100 or less), (2) a COP equivalent to that of R1234yf, and (3) 140% as compared with R1234yf. It has various characteristics such as having the above refrigerating capacity and (4) being slightly flammable (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is preferably 21.5 to the total mass of HFO-1132 (E) and HFO-1234yf. It is 28.0% by mass, and the content ratio of HFO-1234yf is preferably 78.5 to 72.0% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 65.0 ° C or less and a critical temperature of 83.5 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is more preferably 22.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is ⁇ 27.7% by mass, and the content ratio of HFO-1234yf is more preferably 78.0 to 72.3% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 65.0 ° C or less and a critical temperature of 83.5 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is more preferably 22.5 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is ⁇ 27.5% by mass, and the content ratio of HFO-1234yf is more preferably 77.5 ⁇ 72.5% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 140% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is particularly preferably 23.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content is ⁇ 27.2% by mass, and the content of HFO-1234yf is particularly preferably 77.0 to 72.8% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 141% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is particularly preferable with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is 23.5 to 27.0% by mass, and the content ratio of HFO-1234yf is particularly preferably 76.5 to 73.0% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 142% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 64.8 ° C or less and a critical temperature of 83.8 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • the content ratio of HFO-1132 (E) is most preferably 24.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content is ⁇ 26.7% by mass, and the content of HFO-1234yf is most preferably 76.0 to 73.3% by mass.
  • the refrigerant 4 has a GWP of 100 or less, a COP of 98% or more for R1234yf, a refrigerating capacity of 144% or more for R1234yf, and a slight flammability (class 2L) according to the ASHRAE standard.
  • the refrigerant 4 has various characteristics such as a discharge temperature of 64.6 ° C or less and a critical temperature of 84.0 ° C or more. Further, in this case, the refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10 ° C., and can be applied to a commercially available refrigerating apparatus for R1234yf without major design changes.
  • Refrigerant 5 The refrigerant of the present disclosure contains HFO-1132 (E) and HFO-1234yf in one embodiment, and contains HFO-1132 (E) with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the ratio is 12.1 to 72.0% by mass, and the content ratio of HFO-1234yf is 87.9 to 28.0% by mass.
  • This refrigerant may be referred to as "refrigerant 5".
  • the refrigerant 5 is used in an in-vehicle air conditioner.
  • the refrigerant 5 has (1) a sufficiently small GWP (100 or less), (2) has a COP equivalent to that of R1234yf, and (3) 128% or more as compared with R1234yf. It has various characteristics such as having refrigerating capacity and (4) burning rate of less than 10.0 cm / s.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 12.1% by mass or more, which is advantageous when heating an electric vehicle using a heat pump.
  • a boiling point of -40 ° C or less can be secured.
  • a boiling point of -40 ° C or lower means that the saturation pressure is -40 ° C and the saturation pressure is atmospheric pressure or higher, and in the above application, the boiling point is preferably -40 ° C or lower, which is lower.
  • the content ratio of HFO-1132 (E) to the total mass of HFO-1132 (E) and HFO-1234yf is 72.0% by mass or less, so that it is safe when used in an in-vehicle air conditioner. It is possible to secure a combustion rate of less than 10.0 cm / s, which contributes to.
  • the refrigerating capacity with respect to R1234yf may be 128% or more, but preferably 130% or more, more preferably 140% or more, further preferably 150% or more, and 160% or more. Is particularly preferable.
  • Refrigerant 5 has a GWP of 5 or more and 100 or less, so that the environmental load can be significantly suppressed as compared with other general-purpose refrigerants from the viewpoint of global warming.
  • the ratio of the power consumed in the refrigeration cycle to R1234yf and the refrigerating capacity should be 100% or more.
  • the air-conditioning equipment is for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle.
  • the air conditioner for the refrigerant 5 is for an electric vehicle from the viewpoint of improving the mileage of the vehicle while heating the interior of the vehicle with a heat pump. That is, in the present disclosure, it is particularly preferable to use the refrigerant 5 in an electric vehicle.
  • the refrigerant 5 is used in an in-vehicle air conditioner.
  • the refrigerant 5 is preferably used in an air conditioner for a gasoline vehicle, an air conditioner for a hybrid vehicle, an air conditioner for an electric vehicle, or an air conditioner for a hydrogen vehicle.
  • it is particularly preferable that the refrigerant 5 is used in an air conditioner for an electric vehicle.
  • the boiling point of the refrigerant 5 is preferably -51.2 to -40.0 ° C, more preferably -50.0 to-. It is 42.0 ° C, more preferably -48.0 to -44.0 ° C.
  • the content ratio of HFO-1132 (E) is preferably 15.0 to 65.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is preferable. It is 85.0 to 35.0 mass%.
  • the content ratio of HFO-1132 (E) is more preferably 20.0 to 55.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is higher. It is preferably 80.0 to 45.0% by mass.
  • the content ratio of HFO-1132 (E) is more preferably 25.0 to 50.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is further increased. It is preferably 75.0 to 50.0% by mass.
  • the content ratio of HFO-1132 (E) is particularly preferably 30.0 to 45.0% by mass with respect to the total mass of HFO-1132 (E) and HFO-1234yf, and the content ratio of HFO-1234yf is particularly high. It is preferably 70.0 to 55.0% by mass.
  • the content ratio of HFO-1132 (E) is most preferably 35.0 to 40.0% by mass, and the content ratio of HFO-1234yf is the highest with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is preferably 65.0 to 60.0% by mass.
  • the combustion rate of the refrigerant 5 is preferably less than 10.0 cm / s, more preferably less than 5.0 cm / s, even more preferably less than 3.0 cm / s, at 2.0 cm / s. It is particularly preferable to have.
  • the refrigerant 5 is preferably used for operating a refrigeration cycle having an evaporation temperature of -40 to 10 ° C. from the viewpoint of obtaining a refrigerating capacity equal to or higher than that of R1234yf.
  • the discharge temperature is preferably 79 ° C. or lower, more preferably 75 ° C. or lower, still more preferably 70 ° C. or lower, and particularly preferably 67 ° C. or lower.
  • Refrigerant 5 may contain HFO-1132 (E) and HFO-1234yf in the sum of these concentrations, usually 99.5% by mass or more.
  • the total amount of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 5 is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and further preferably 99.9% by mass or more. ..
  • Refrigerant 5 can contain other refrigerants in addition to HFO-1132 (E) and HFO-1234yf within a range that does not impair the above characteristics.
  • the content ratio of the other refrigerant in the entire refrigerant 5 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the other refrigerant is not particularly limited, and can be widely selected from known refrigerants widely used in this field.
  • the refrigerant 5 may contain other refrigerants alone, or may contain two or more other refrigerants.
  • the refrigerant 5 is composed of only HFO-1132 (E) and HFO-1234yf.
  • the refrigerant 5 preferably has a total concentration of HFO-1132 (E) and HFO-1234yf in the entire refrigerant 5 of 100% by mass.
  • the content ratio of HFO-1132 (E) is usually 12.1 to 72.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is mass%, and the content ratio of HFO-1234yf is usually 87.9 to 28.0 mass%.
  • the content ratio of HFO-1132 (E) is preferably 15.0 to 15.0 to the total mass of HFO-1132 (E) and HFO-1234yf. It is 65.0% by mass, and the content ratio of HFO-1234yf is preferably 85.0 to 35.0% by mass.
  • the content ratio of HFO-1132 (E) is more preferably 20.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is ⁇ 55.0% by mass, and the content ratio of HFO-1234yf is more preferably 80.0 to 45.0% by mass.
  • the content ratio of HFO-1132 (E) is more preferably 25.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is ⁇ 50.0% by mass, and the content ratio of HFO-1234yf is more preferably 75.0 to 50.0% by mass.
  • the content ratio of HFO-1132 (E) is particularly preferably 30.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf.
  • the content is ⁇ 45.0% by mass, and the content of HFO-1234yf is particularly preferably 70.0 to 55.0% by mass.
  • the content ratio of HFO-1132 (E) is most preferably 35.0 with respect to the total mass of HFO-1132 (E) and HFO-1234yf. It is ⁇ 40.0% by mass, and the content ratio of HFO-1234yf is most preferably 65.0 ⁇ 60.0% by mass.
  • composition containing the refrigerant of the present disclosure can be used as a working fluid of an existing refrigerant in 1) a freezing method including a step of operating a freezing cycle, 2) an operating method of a freezing device for operating a freezing cycle, and the like. It can be widely used for various purposes.
  • the refrigerant via the compressor is in a state of only the refrigerant, or the refrigerant composition or refrigerating machine oil described later. It means that the inside of the refrigerating apparatus is circulated in the state of the contained working fluid to convert energy.
  • the composition containing the refrigerant of the present disclosure is not particularly limited, but is suitable for use in a vapor compression refrigeration cycle.
  • the refrigerant is (1) compressed in a gaseous state with a compressor, (2) cooled by a condenser to change it into a liquid state with high pressure, and (3) the pressure is lowered by an expansion valve. Further, it consists of a series of cycles of (4) vaporizing at a low temperature in an evaporator and removing heat by the heat of vaporization. It can be classified into turbo (centrifugal), reciprocating, twin screw, single screw, scroll compressor and the like according to the method of compressing the gaseous refrigerant, and can be selected according to the heat capacity, compression ratio and size.
  • composition containing the refrigerant of the present disclosure is not particularly limited, but is suitable for the refrigerant used in a large chiller refrigerator, particularly a turbo (centrifugal) compressor.
  • the present disclosure includes the use of the refrigerants of the present disclosure (or compositions containing them) in freezing methods, the use of the refrigerants of the present disclosure (or compositions containing them) in operating methods such as freezing equipment, and the present disclosure.
  • a freezing device or the like having a refrigerant (or a composition containing them) is also included.
  • composition containing the refrigerant 1 of the present disclosure is used for operating a refrigeration cycle in which the evaporation temperature is -75 to -5 ° C.
  • composition containing the refrigerant 1 of the present disclosure for operating a refrigeration cycle in which the evaporation temperature is -75 to -5 ° C, there is an advantage that a refrigerating capacity equal to or higher than that of R404A can be obtained.
  • the evaporation temperature is preferably ⁇ 7.5 ° C. or lower, more preferably -10 ° C. or lower, still more preferably -35 ° C. or lower.
  • the evaporation temperature is preferably -65 ° C. or higher, more preferably -60 ° C. or higher, still more preferably -55 ° C. or higher, and particularly preferably -50 ° C. That is all.
  • composition containing the refrigerant 2 of the present disclosure is preferably used for operating a refrigeration cycle in which the evaporation temperature is ⁇ 75 to 5 ° C. from the viewpoint of obtaining a refrigerating capacity equal to or higher than that of R404A.
  • the evaporation temperature is preferably 0 ° C. or lower, more preferably -5 ° C. or lower, still more preferably -7.5 ° C. or lower, and particularly preferably -10 ° C. or lower. Is.
  • the evaporation temperature is preferably -65 ° C. or higher, more preferably -60 ° C. or higher, still more preferably -55 ° C. or higher, and particularly preferably -50 ° C. That is all.
  • composition containing the refrigerant 3 of the present disclosure is preferably used for operating a refrigeration cycle in which the evaporation temperature is ⁇ 75 to 15 ° C. from the viewpoint of obtaining a refrigerating capacity equal to or higher than that of R134a.
  • the evaporation temperature is preferably 15 ° C. or lower, more preferably 5 ° C. or lower, still more preferably 0 ° C. or lower, and particularly preferably -5 ° C. or lower. ..
  • the evaporation temperature is preferably ⁇ 65 ° C. or higher, more preferably -60 ° C. or higher, further preferably -55 ° C. or higher, and particularly preferably -50 ° C. That is all.
  • the evaporation temperature is preferably ⁇ 65 ° C. or higher and 15 ° C. or lower, more preferably -60 ° C. or higher and 5 ° C. or lower, and further preferably -55 ° C. or higher and 0. °C or less, particularly preferably -50 °C or more and -5 °C or less.
  • composition containing the refrigerant 4 of the present disclosure is preferably used for operating a refrigeration cycle having an evaporation temperature of ⁇ 75 to 20 ° C. from the viewpoint of obtaining a refrigerating capacity of 140% or more as compared with R1234yf. ..
  • the evaporation temperature is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, from the viewpoint of obtaining a refrigerating capacity of 140% or more as compared with R1234yf. It is more preferably 0 ° C. or lower, and particularly preferably -10 ° C. or lower.
  • the evaporation temperature is preferably ⁇ 75 ° C. or higher, more preferably -60 ° C. from the viewpoint of obtaining a refrigerating capacity of 140% or more as compared with R1234yf. Above, more preferably -55 ° C. or higher, particularly preferably -50 ° C. or higher.
  • Refrigerant devices to which the refrigerant 1, refrigerant 2, refrigerant 3 and refrigerant 4 (or compositions containing them) of the present disclosure can be applied include, for example, air conditioners, refrigerators, freezers, water coolers, ice makers, refrigerator showcases, and freezers. Showcases, refrigerating units, refrigerators for refrigerating and refrigerating warehouses, in-vehicle air conditioners, turborefrigerants or screw refrigerators are preferred. Among these, in-vehicle air conditioners are more preferable.
  • in-vehicle air-conditioning equipment gasoline-powered vehicle air-conditioning equipment, hybrid vehicle air-conditioning equipment, electric vehicle air-conditioning equipment, and hydrogen vehicle air-conditioning equipment are more preferable.
  • the in-vehicle air conditioners the electric vehicle air conditioners are particularly preferable.
  • compositions containing the refrigerants 1 or 2 of the present disclosure include R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, Suitable for use as an alternative refrigerant for R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507 or R513A.
  • compositions containing Refrigerant 1 or 2 of the present disclosure are more suitable for use as an alternative refrigerant for R22, R404A, R407F, R407H, R448A, R449A, R454C, R455A or R465A. Further, since the composition containing the refrigerant 1 or 2 of the present disclosure has a refrigerating capacity equivalent to that of the currently widely used R404A and has a sufficiently small GWP, it can be used as an alternative refrigerant for the R404A. Especially suitable.
  • the composition containing the refrigerant 3 of the present disclosure is suitable for use as an alternative refrigerant for R134a, R1234yf or CO 2 .
  • the composition containing the refrigerant 3 of the present disclosure is more suitable for use as an alternative refrigerant for R134a.
  • the composition containing the refrigerant 3 of the present disclosure has a refrigerating capacity of 150% or more as compared with the currently widely used R134a, and has a performance that the GWP is sufficiently small, so that it can be used as an alternative refrigerant for R134a. Especially suitable for use in.
  • compositions containing the refrigerant 4 of the present disclosure include R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, Suitable for use as an alternative refrigerant for R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze.
  • composition containing the refrigerant 4 of the present disclosure is more suitable for use as an alternative refrigerant for R12, R134a, R404A, R407C, R449C, R454C, R1234yf or R1234ze. Further, the composition containing the refrigerant 4 of the present disclosure has a refrigerating capacity of 140% or more as compared with the currently widely used R1234yf, and has a performance that the GWP is sufficiently small, so that it can be used as an alternative refrigerant for R1234yf. Especially suitable for use in.
  • compositions containing the refrigerant 5 of the present disclosure include R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, Suitable for use as an alternative refrigerant for R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze.
  • composition containing the refrigerant 5 of the present disclosure is more suitable for use as an alternative refrigerant for R12, R134a or R1234yf. Further, the composition containing the refrigerant 5 of the present disclosure has a refrigerating capacity of 140% or more as compared with the currently widely used R1234yf, and has a performance that the GWP is sufficiently small, so that it can be used as an alternative refrigerant for R1234yf. Especially suitable for use in.
  • the composition containing the refrigerant 5 of the present disclosure is preferably used for in-vehicle air conditioning equipment.
  • the vehicle-mounted air-conditioning equipment is a gasoline vehicle air-conditioning equipment, a hybrid vehicle air-conditioning equipment, an electric vehicle air-conditioning equipment, or a hydrogen vehicle air-conditioning equipment.
  • the in-vehicle air conditioner is an electric vehicle air conditioner. That is, in the present disclosure, it is particularly preferable to use the composition containing the refrigerant 5 in an electric vehicle.
  • Test Example 1-1 The GWP of the mixed refrigerants shown in Examples 1-1 to 1-13, Comparative Examples 1-1 to 1-2 and Reference Example 1-1 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • the COP, refrigerating capacity, discharge temperature, saturation pressure, condensation pressure and evaporation pressure at a saturation temperature of 40 ° C for these mixed refrigerants are available from the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). It was obtained by carrying out the refrigeration cycle theoretical calculation of the mixed refrigerant under the following conditions. Evaporation temperature -50 ° C Condensation temperature 40 ° C Superheat temperature 20K Supercooling temperature 0K Compressor efficiency 70%
  • Evaporation temperature -50 ° C means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration system is -50 ° C.
  • condensation temperature 40 ° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigerating apparatus is 40 ° C.
  • Test Example 1-1 The results of Test Example 1-1 are shown in Table 59.
  • Table 59 shows examples and comparative examples of the refrigerant 1 of the present disclosure.
  • the "COP ratio” and the “refrigerating capacity ratio” indicate the ratio (%) to R404A.
  • “saturation pressure (40 ° C.)” indicates a saturation pressure at a saturation temperature of 40 ° C.
  • the “discharge temperature (° C.)” indicates the temperature at which the temperature becomes the highest in the refrigeration cycle in the theoretical calculation of the refrigeration cycle of the mixed refrigerant.
  • COP (refrigeration capacity or heating capacity) / power consumption
  • Compression ratio condensation pressure (Mpa) / evaporation pressure (Mpa)
  • the flammability of the mixed refrigerant was determined by using the mixed composition of the mixed refrigerant as the WCF concentration and measuring the combustion rate according to the ANSI / ASHRAE34-2013 standard. If the combustion speed is 0 cm / s to 10 cm / s, it is "Class 2 L (slight combustion)", and if the combustion speed is over 10 cm / s, it is “Class 2 (weak fuel)", and there is no flame propagation. The one was "Class 1 (non-combustible)”. In Table 59, "ASHRAE flammability classification" indicates the result based on this criterion.
  • the combustion speed test was conducted as follows. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the combustion range of the mixed refrigerant was measured using a measuring device (see FIG. 20) based on ASTM E681-09.
  • a spherical glass flask with an internal volume of 12 liters is used so that the state of combustion can be visually observed and recorded, and the glass flask releases gas from the upper lid when excessive pressure is generated due to combustion. It was to so.
  • the ignition method was generated by electric discharge from an electrode held at a height of 1/3 from the bottom.
  • Test Example 1-2 The GWP of the mixed refrigerants shown in Examples 1-14 to 1-26, Comparative Examples 1-3 to 1-4 and Reference Example 1-2 (R404A) were evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 60 shows the results of Test Example 1-2.
  • Table 60 shows examples and comparative examples of the refrigerant 1 of the present disclosure.
  • the meaning of each term is the same as that of Test Example 1-1.
  • the coefficient of performance (COP) and compression ratio were determined in the same manner as in Test Example 1-1.
  • the flammability of the mixed refrigerant was determined in the same manner as in Test Example 1-1.
  • the combustion rate test was carried out in the same manner as in Test Example 1-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 1-1.
  • Test Example 1-3 The GWP of the mixed refrigerants shown in Examples 1-27 to 1-39, Comparative Examples 1-5 to 1-6 and Reference Example 1-3 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 61 shows the results of Test Example 1-3.
  • Table 61 shows examples and comparative examples of the refrigerant 1 of the present disclosure. In Table 61, the meaning of each term is the same as that of Test Example 1-1.
  • the coefficient of performance (COP) and compression ratio were determined in the same manner as in Test Example 1-1.
  • the flammability of the mixed refrigerant was determined in the same manner as in Test Example 1-1.
  • the combustion rate test was carried out in the same manner as in Test Example 1-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 1-1.
  • Test Example 1-4 The GWP of the mixed refrigerants shown in Comparative Examples 1-7 to 1-21 and Reference Example 1-4 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report.
  • Table 62 shows the results of Test Example 1-4.
  • Table 62 shows a comparative example of the refrigerant 1 of the present disclosure. In Table 62, the meaning of each term is the same as that of Test Example 1-1.
  • the coefficient of performance (COP) and compression ratio were determined in the same manner as in Test Example 1-1.
  • the flammability of the mixed refrigerant was determined in the same manner as in Test Example 1-1.
  • the combustion rate test was carried out in the same manner as in Test Example 1-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 1-1.
  • Test Example 1-5 The GWP of the mixed refrigerants shown in Comparative Examples 1-22 to 1-36 and Reference Example 1-5 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report.
  • Table 63 shows the results of Test Example 1-5.
  • Table 63 shows a comparative example of the refrigerant 1 of the present disclosure. In Table 63, the meaning of each term is the same as that of Test Example 1-1.
  • the coefficient of performance (COP) and compression ratio were determined in the same manner as in Test Example 1-1.
  • the flammability of the mixed refrigerant was determined in the same manner as in Test Example 1-1.
  • the combustion rate test was carried out in the same manner as in Test Example 1-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 1-1.
  • Test Example 2-1 The GWP of the mixed refrigerants shown in Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-9 and Reference Example 2-1 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • the COP, refrigerating capacity, discharge temperature, saturation pressure, condensation pressure and evaporation pressure at a saturation temperature of 40 ° C for these mixed refrigerants are available from the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). It was obtained by carrying out the refrigeration cycle theoretical calculation of the mixed refrigerant under the following conditions. Evaporation temperature -50 ° C Condensation temperature 40 ° C Superheat temperature 20K Supercooling temperature 0K Compressor efficiency 70%
  • Evaporation temperature -50 ° C means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration system is -50 ° C.
  • condensation temperature 40 ° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigerating apparatus is 40 ° C.
  • Table 64 shows examples and comparative examples of the refrigerant 2 of the present disclosure.
  • the "COP ratio” and the “refrigerating capacity ratio” indicate the ratio (%) to R404A.
  • “saturation pressure (40 ° C.)” indicates a saturation pressure at a saturation temperature of 40 ° C.
  • the “discharge temperature (° C.)” indicates the temperature at which the temperature becomes the highest in the refrigeration cycle in the theoretical calculation of the refrigeration cycle of the mixed refrigerant.
  • COP (refrigeration capacity or heating capacity) / power consumption
  • Compression ratio condensation pressure (Mpa) / evaporation pressure (Mpa)
  • the flammability of the mixed refrigerant was determined by using the mixed composition of the mixed refrigerant as the WCF concentration and measuring the combustion rate according to the ANSI / ASHRAE34-2013 standard. If the combustion speed is 0 cm / s to 10 cm / s, it is "Class 2 L (slight combustion)", and if the combustion speed is over 10 cm / s, it is “Class 2 (weak fuel)", and there is no flame propagation. The one was "Class 1 (non-combustible)”. In Table 64, "ASHRAE flammability classification" indicates the result based on this criterion.
  • the combustion speed test was conducted as follows. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the combustion range of the mixed refrigerant was measured using a measuring device (see FIG. 20) based on ASTM E681-09.
  • a spherical glass flask with an internal volume of 12 liters is used so that the state of combustion can be visually observed and recorded, and the glass flask releases gas from the upper lid when excessive pressure is generated due to combustion. It was to so.
  • the ignition method was generated by electric discharge from an electrode held at a height of 1/3 from the bottom.
  • Test Example 2-2 The GWP of the mixed refrigerants shown in Examples 2-7 to 2-12, Comparative Examples 2-10 to 2-18 and Reference Example 2-2 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 65 shows the results of Test Example 2-2.
  • Table 65 shows examples and comparative examples of the refrigerant 2 of the present disclosure.
  • the meaning of each term is the same as that of Test Example 2-1.
  • the flammability of the mixed refrigerant was judged in the same manner as in Test Example 2-1.
  • the combustion rate test was carried out in the same manner as in Test Example 2-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 2-1.
  • Test Example 2-3 The GWP of the mixed refrigerants shown in Examples 2-13 to 2-18, Comparative Examples 2-19 to 2-27 and Reference Example 2-3 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 66 shows the results of Test Example 2-3.
  • Table 66 shows examples and comparative examples of the refrigerant 2 of the present disclosure. In Table 66, the meaning of each term is the same as that of Test Example 2-1.
  • the flammability of the mixed refrigerant was judged in the same manner as in Test Example 2-1.
  • the combustion rate test was carried out in the same manner as in Test Example 2-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 2-1.
  • Test Example 2-4 The GWP of the mixed refrigerants shown in Examples 2-19 to 2-24, Comparative Examples 2-28 to 2-36 and Reference Example 2-4 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 67 shows the results of Test Example 2-4.
  • Table 67 shows examples and comparative examples of the refrigerant 2 of the present disclosure. In Table 67, the meaning of each term is the same as that of Test Example 2-1.
  • the flammability of the mixed refrigerant was judged in the same manner as in Test Example 2-1.
  • the combustion rate test was carried out in the same manner as in Test Example 2-1.
  • the combustion range of the mixed refrigerant was measured by the same method and test conditions as in Test Example 2-1 using a measuring device based on ASTM E681-09 (see FIG. 20).
  • Test Example 2-5 The GWP of the mixed refrigerants shown in Examples 2-25 to 2-30, Comparative Examples 2-37 to 2-45 and Reference Example 2-5 (R404A) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • Table 68 shows the results of Test Example 2-5.
  • Table 68 shows examples and comparative examples of the refrigerant 2 of the present disclosure. In Table 68, the meaning of each term is the same as that of Test Example 2-1.
  • the flammability of the mixed refrigerant was judged in the same manner as in Test Example 2-1.
  • the combustion rate test was carried out in the same manner as in Test Example 2-1.
  • the combustion range of the mixed refrigerant was measured using a measuring device based on ASTM E681-09 (see FIG. 20) under the same method and test conditions as in Test Example 2-1.
  • Test Example 3 The GWP of the mixed refrigerants shown in Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-5, Reference Example 3-1 (R134a) and Reference Example 3-2 (R404A) are IPCC Fourth Assessment Report. Evaluated based on the values in the report.
  • the COP, refrigerating capacity, discharge temperature, saturation pressure, condensation pressure and evaporation pressure at a saturation temperature of 45 ° C for these mixed refrigerants are available from the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). It was obtained by carrying out the refrigeration cycle theoretical calculation of the mixed refrigerant under the following conditions. Evaporation temperature -10 ° C Condensation temperature 45 ° C Superheat temperature 20K Supercooling temperature 0K Compressor efficiency 70%
  • Evaporation temperature -10 ° C means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration system is -10 ° C. Further, the “condensation temperature 45 ° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigerating apparatus is 45 ° C.
  • Table 69 shows examples and comparative examples of the refrigerant 3 of the present disclosure.
  • the "COP ratio” and the “refrigerating capacity ratio” indicate the ratio (%) with respect to R134a.
  • saturation pressure (45 ° C.) indicates the saturation pressure at a saturation temperature of 45 ° C.
  • discharge temperature (° C.) indicates the temperature at which the temperature becomes the highest in the refrigeration cycle in the theoretical calculation of the refrigeration cycle of the mixed refrigerant.
  • COP (refrigeration capacity or heating capacity) / power consumption
  • the critical temperature was determined by performing calculations using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).
  • the flammability of the mixed refrigerant was determined by using the mixed composition of the mixed refrigerant as the WCF concentration and measuring the combustion rate according to the ANSI / ASHRAE34-2013 standard. If the combustion speed is 0 cm / s to 10 cm / s, it is "Class 2 L (slight combustion)", and if the combustion speed is over 10 cm / s, it is “Class 2 (weak fuel)", and there is no flame propagation. The one was "Class 1 (non-combustible)”. In Table 69, "ASHRAE flammability classification" indicates the result based on this criterion.
  • the combustion speed test was conducted as follows. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the combustion range of the mixed refrigerant was measured using a measuring device (see FIG. 20) based on ASTM E681-09.
  • a spherical glass flask with an internal volume of 12 liters is used so that the state of combustion can be visually observed and recorded, and the glass flask releases gas from the upper lid when excessive pressure is generated due to combustion. It was to so.
  • the ignition method was generated by electric discharge from an electrode held at a height of 1/3 from the bottom.
  • Test Example 4 The GWP of the mixed refrigerants shown in Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-5 were evaluated based on the values in the IPCC Fourth Assessment Report.
  • the COP, refrigerating capacity, discharge temperature and saturation pressure of these mixed refrigerants at -10 ° C are determined using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions. It was obtained by carrying out the refrigeration cycle theoretical calculation of the mixed refrigerant in. Evaporation temperature 5 ° C Condensation temperature 45 ° C Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70%
  • Evaporation temperature 5 ° C means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration system is 5 ° C.
  • condensation temperature 45 ° C means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigerating apparatus is 45 ° C.
  • Table 70 shows the results of Test Example 4.
  • Table 70 shows examples and comparative examples of the refrigerant 4 of the present disclosure.
  • COP ratio and “refrigerating capacity ratio” indicate the ratio (%) to R1234yf.
  • saturation pressure (-10 ° C.) indicates a saturation pressure at a saturation temperature of ⁇ 10 ° C. as a representative value of the evaporation temperature under refrigeration conditions.
  • discharge temperature (° C.) indicates the temperature at which the temperature becomes the highest in the refrigeration cycle in the theoretical calculation of the refrigeration cycle of the mixed refrigerant.
  • COP (refrigeration capacity or heating capacity) / power consumption
  • the critical temperature was determined by performing calculations using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).
  • the flammability of the mixed refrigerant was determined by using the mixed composition of the mixed refrigerant as the WCF concentration and measuring the combustion rate according to the ANSI / ASHRAE34-2013 standard. If the combustion speed is 0 cm / s to 10 cm / s, it is "Class 2 L (slight combustion)", and if the combustion speed is over 10 cm / s, it is “Class 2 (weak fuel)", and there is no flame propagation. The thing was “class 1 (non-combustible)”. In Table 70, "ASHRAE flammability classification" indicates the result based on this criterion.
  • the combustion speed test was conducted as follows. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closure method. The initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J. A schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the combustion range of the mixed refrigerant was measured using a measuring device (see FIG. 20) based on ASTM E681-09.
  • a spherical glass flask with an internal volume of 12 liters is used so that the state of combustion can be visually observed and recorded, and the glass flask releases gas from the upper lid when excessive pressure is generated due to combustion. It was to so.
  • the ignition method was generated by electric discharge from an electrode held at a height of 1/3 from the bottom.
  • Test Example 5 The GWP of the mixed refrigerants shown in Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-3 and Reference Example 5-1 (R134a) was evaluated based on the values in the IPCC Fourth Assessment Report. ..
  • the COP, refrigerating capacity, boiling point and discharge temperature of these mixed refrigerants are determined using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions. Obtained by performing the calculation. Evaporation temperature -30 ° C Condensation temperature 30 ° C Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70%
  • Evaporation temperature -30 ° C means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration system is -30 ° C.
  • condensation temperature 30 ° C means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigerating apparatus is 30 ° C.
  • Table 71 shows examples and comparative examples of the refrigerant 5 of the present disclosure.
  • COP ratio and “refrigeration capacity ratio” indicate the ratio (%) to R1234yf.
  • discharge temperature indicates the temperature at which the temperature becomes the highest in the refrigeration cycle in the theoretical calculation of the refrigeration cycle of the mixed refrigerant.
  • boiling point indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa).
  • power consumption (%) of power indicates the electric energy used to drive the electric vehicle, and is expressed as a ratio to the power consumption when the refrigerant is HFO-1234yf.
  • heating power consumption (%) indicates the electric energy used by the electric vehicle to operate the heating, and is expressed as a ratio to the power consumption when the refrigerant is HFO-1234yf.
  • mileage means 100% of the mileage of an electric vehicle equipped with a secondary battery having a certain electric capacity when the vehicle runs without heating (heating power consumption is 0). It represents the relative ratio (%) of the mileage that can be traveled when traveling with heating.
  • COP (refrigeration capacity or heating capacity) / power consumption
  • the flammability of the mixed refrigerant was determined by measuring the combustion rate according to the ANSI / ASHRAE34-2013 standard, using the mixed composition of the mixed refrigerant as the WCF concentration.
  • the combustion rate was measured as follows. First, the mixed refrigerant used had a purity of 99.5% or higher, and was degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge.
  • the burning rate was measured by the closure method.
  • the initial temperature was the ambient temperature. Ignition was performed by creating an electrical spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0-9.9 ms and the ignition energy was typically about 0.1-1.0 J.
  • a schlieren photograph was used to visualize the spread of the flame.
  • a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows for passing light was used as a sample cell, and a xenon lamp was used as a light source.
  • a schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the electric heater method was used for heating for the refrigerant having a boiling point exceeding -40 ° C
  • the heat pump method was used for heating for the refrigerant having a boiling point of -40 ° C or less.
  • the heating COP means "heating efficiency”.
  • the heating COP is calculated by performing the refrigeration cycle theoretical calculation of the mixed refrigerant under the following conditions. It was. Evaporation temperature -30 ° C Condensation temperature 30 ° C Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70%
  • Mileage (battery capacity) / (power consumption of power + power consumption of heating)
  • the present disclosure is a refrigerator containing a refrigerant containing HFO-1132 as an operating medium, and a processing unit that brings the refrigerant into contact with a desiccant and / or a deoxidizer. With respect to the refrigerator having.
  • the refrigerator of the present disclosure preferably has a compressor, a condenser, a depressurizing mechanism and an evaporator. It is preferable that these are connected in a ring shape by piping to form a refrigeration cycle.
  • the refrigerant can be brought into contact with the desiccant and / or oxygen scavenger, the concentration of water and / or oxygen in the refrigeration cycle can be reduced, and the decomposition of HFO-1132 can be performed. Is suppressed, and the generation of sludge is suppressed.
  • the processing unit may be provided at any place.
  • the condenser and the depressurizing mechanism are provided.
  • the working medium is a liquid, with water and / or oxygen in contact with the desiccant and / or oxygen scavenger than in contact with the gas. This is because can be removed more efficiently.
  • a wide range of known desiccants can be used. Examples thereof include, but are not limited to, anhydrous calcium sulfide, calcium chloride, barium oxide, phosphorus pentoxide, activated alumina, silica gel, molecular sieve and the like.
  • oxygen scavengers can be used.
  • iron powder 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, epoxidized cyclohexylcarbinol, di (alkylphenyl) carbodiimide, ⁇ -pinene, ⁇ -pinene, zinc dithiophosphate, organic sulfur compounds, 2, 6-di-tert-butyl-4-ethylphenol, 2,2-methylenebis (4-methyl-6-tert-butylphenol), phenyl- ⁇ -naphthylamine, N, N-diphenyl-p-phenylenediamine, N, N -Disalicylidene-1,2-diaminopropane and the like can be mentioned.
  • a wide range of known powder removers can be used. Examples include, but are not limited to, strainers, meshes, filters and the like.
  • HFO-1132 (E) The stability of HFO-1132 (E) was tested in the presence of specific concentrations of water and oxygen.
  • 1 g of refrigerant, 1 g of refrigerating machine oil, and iron, copper, and aluminum as catalysts are sealed in a glass container adjusted to a specific water concentration and air concentration, sealed, and stored at 175 ° C. for 14 days. It was evaluated by evaluating and measuring the hue (ASTM color) and the total acid value.
  • ASTM color the hue
  • Commercially available refrigerating machine oil was used.
  • the hue evaluation method was as follows.
  • the total acid value measurement method was as follows.
  • the measurement was calculated by collecting a sample in a predetermined glass container, dissolving it in a solvent (toluene / 2-propanol / water (5/5 / 0.05Vol ratio)), and neutralizing and titrating it.
  • the acid value was measured by titration with a burette, neutralized with potassium hydroxide 2-propanol standard solution, and expressed in mg of potassium hydroxide.

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Abstract

L'invention concerne un fluide frigorigène comprenant du difluoroéthylène (HFO-1132), la stabilité du HFO-1132 une fois utilisé dans un réfrigérateur et mis en fonction étant améliorée. L'invention concerne également un réfrigérateur comprenant un fluide frigorigène qui comprend du difluoroéthylène (HFO-1132) en tant que fluide thermodynamique, le réfrigérateur comprenant une unité de traitement pour amener le fluide frigorigène en contact avec au moins un agent choisi dans le groupe constitué par des déshydratants, des désoxydants et des décapants en poudre.
PCT/JP2020/024204 2019-06-19 2020-06-19 Réfrigérateur comprenant du difluoroéthylène (hfo-1132) en tant que fluide thermodynamique WO2020256131A1 (fr)

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US11525076B2 (en) 2019-01-30 2022-12-13 Daikin Industries, Ltd. Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device
WO2023287695A1 (fr) * 2021-07-12 2023-01-19 The Chemours Company Fc, Llc Compositions de fluoroéthylène stabilisées et leurs procédés de stockage et d'utilisation
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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WO2023287695A1 (fr) * 2021-07-12 2023-01-19 The Chemours Company Fc, Llc Compositions de fluoroéthylène stabilisées et leurs procédés de stockage et d'utilisation

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