Refrigerant-containing composition, use thereof, refrigerator having same, and method for operating said refrigerator

Abstract

The present disclosure provides a novel refrigerant mixture having a low GWP. Specifically, the present disclosure provides a refrigerant-containing composition, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), propane, and 1,1-difluoroethylene (HFO-1132a) and may further include difluoromethane (R32), the proportions of these compounds being limited so as to be in certain ranges.

Description

Refrigerant-containing composition, its use, refrigerator having same and method of operating the refrigerator

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to compositions containing refrigerants, uses thereof, refrigerators having same, and methods of operating such refrigerators.

[0002] As a working fluid for heat cycles that can replace R410A, a working fluid for heat cycles containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1).

[0003] International Publication No. 2015 / 141678

[0004] The present disclosure aims to provide a novel low GWP refrigerant mixture.

[0005] Item 1. A composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), propane, and 1,1-difluoroethylene (HFO-1132a), and may further contain difluoromethane (R32), and wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 75.0, 0.0, 25.0), Point R (0.0011a 2 -1.0794a+19.594, 0.0, -0.0011a 2 +0.0794a+80.406), point Q (0.0, -0.0011a 2 -0.5366a+10.186, 0.0011a 2Item 1. A composition that is within the area of ​​a figure surrounded by straight lines CD, DR, RQ, QB, BA, and AC that respectively connect the six points of point A (-0.4634a+89.814), point B (0.0, 44.2, -a+55.8), and point A (-a+55.7, 44.3, 0.0), or that is on said straight lines CD, DR, RQ, and BA (excluding points C, Q, B, and A). Item 2. A composition according to Item 1, which is a replacement composition for R410A. Item 3. A composition comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), propane, and HFO-1132a, and may further comprise R32; wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point F (-1.104a + 20.72, 0.0, 0.104a + 79.28), Point E (0.0, 0.0011a 2 -0.6234a+11.514, -0.0011a 2Item 3. A composition that is within the area surrounded by lines ID, DF, FE, EH, and HI that respectively connect the five points of point H (0.0, 21.9, -a+78.1) and point L (0.0, 21.9, -a+78.1), or that is on said lines ID, DF, FE, and HI (excluding points E and H). Item 4. The composition according to Item 3, which is a replacement composition for R1234yf. Item 5. A composition comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), propane, and HFO-1132a, and may further comprise R32; wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, when the coordinates (x, y, z) are 0 < a ≦ 5.0, the following points are present: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point M (0.136a 2 -1.74a+11.6, 0.0, -0.136a 2 +0.74a+88.4), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2 -0.4006a+93.406) and point H (0.0, 21.9, -a+78.1) When 5.0<a≦10.0, point I (-a+66.7, 22.1, 11.2), point D (-a+75.0, 0.0, 25.0), point M (-0.008a 2 -0.9a+11.0, 0.0, 0.008a 2 -0.1a+89.0), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2Item 6. A composition that is within the area surrounded by straight lines ID, DM, ML, LH, and HI connecting the five points of point A (0.0, 21.9, -a+78.1) and point B (0.0, 21.9, -a+78.1), or that is on said straight lines ID, DM, ML, and HI (excluding points L and H). Item 7. A refrigeration method comprising a step of operating a refrigeration cycle using the composition of any one of items 1, 3, and 5. Item 8. A refrigeration device comprising the composition of any one of items 1, 3, and 5 as a working fluid.

[0006] The refrigerants of the present disclosure have a low GWP.

[0007] FIG. 1 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 2 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 3 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 4 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 5 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 6 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 7 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 8 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 9 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 10 is a ternary diagram showing the composition of a refrigerant according to the present disclosure. FIG. 11 is a ternary diagram showing the composition of a refrigerant according to the present disclosure.

[0008] As a result of extensive research conducted by the present inventors to solve the above problems, they have found that various mixed refrigerants described below have the above properties.

[0009] The present disclosure was completed as a result of further research based on these findings. The present disclosure includes the following embodiments. <Definition of Terms> In this specification, the term "refrigerant" includes at least compounds assigned a refrigerant number (ASHRAE number) beginning with the letter R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and also includes compounds that have equivalent refrigerant properties even if they have not yet been assigned a refrigerant number. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of compound structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0010] In this specification, the term "composition containing a refrigerant" includes at least (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further contains other components and can be used to obtain a working fluid for a refrigerant by mixing with at least a refrigerating machine oil, and (3) a working fluid for a refrigerant containing a refrigerating machine oil. In this specification, of these three aspects, the composition (2) is referred to as a "refrigerant composition" to distinguish it from the refrigerant itself (including a mixture of refrigerants). Furthermore, the working fluid for a refrigerant (3) is referred to as a "refrigerating machine oil-containing working fluid" to distinguish it from the "refrigerant composition."

[0011] As used herein, the term "substitution," when used in the context of "replacing" a first refrigerant with a second refrigerant, refers to a first type of equipment designed to operate using a first refrigerant, which can be operated under optimal conditions using a second refrigerant by simply changing a few components (at least one of refrigeration oil, gaskets, packing, expansion valves, dryers, and other components) and adjusting the equipment as necessary. In other words, this type refers to operating the same equipment by "substituting" a refrigerant. This type of "substitution" can be categorized into "drop-in substitution," "nearly drop-in substitution," and "retrofit," in order of decreasing degree of change or adjustment required when replacing with the second refrigerant.

[0012] The second category, where equipment designed to operate with a second refrigerant is installed and used for the same purpose as an existing use of a first refrigerant, is also included in the term "substitution." This category refers to "substituting" a refrigerant to serve the same purpose.

[0013] In this specification, the term "refrigerating machine" refers to a device that removes heat from an object or space, thereby lowering its temperature below that of the surrounding air, and maintaining that low temperature. In other words, a refrigerator is a conversion device that obtains energy from an external source, performs work, and converts it into energy in order to transfer heat from a low-temperature environment to a high-temperature environment.

[0014] In this specification, the term "vehicle air conditioner" refers to a type of refrigeration device used in automobiles such as gasoline vehicles, hybrid vehicles, electric vehicles, hydrogen vehicles, etc. The term "vehicle air conditioner" refers to a refrigeration device that has a refrigeration cycle in which heat is exchanged with a liquid refrigerant in an evaporator, the evaporated refrigerant gas is sucked into a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied in a condenser, and the refrigerant is further adiabatically expanded by passing through an expansion valve, and then supplied to the evaporator again as a liquid refrigerant.

[0015] Pressures described in this specification are in units of absolute pressure unless otherwise specified.

[0016] 1. Refrigerants Refrigerants disclosed herein include trans-1,2-difluoroethylene (HFO-1132(E), E-HFO-1132), propane, and 1,1-difluoroethylene (HFO-1132a), and may further include difluoromethane (R32).

[0017] The refrigerants of the present disclosure are low GWP refrigerant mixtures.

[0018] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on their total sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the total sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 75.0, 0.0, 25.0), Point R (0.0011a 2 -1.0794a+19.594, 0.0, -0.0011a 2 +0.0794a+80.406), point Q (0.0, -0.0011a 2 -0.5366a+10.186, 0.0011a 2 When the temperature is within the range of the figure enclosed by the lines CD, DR, RQ, QB, BA, and AC connecting the six points of point A (-0.4634a+89.814), point B (0.0, 44.2, -a+55.8), and point A (-a+55.7, 44.3, 0.0), or on the lines CD, DR, RQ, and BA (excluding points C, Q, B, and A), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R410A is 70% or more, and the GWP is 300 or less.

[0019] Therefore, the above refrigerant can be used as an alternative refrigerant to R410A.

[0020] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and propane, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point F (-1.104a + 20.72, 0.0, 0.104a + 79.28), Point E (0.0, 0.0011a 2 -0.6234a+11.514, -0.0011a 2 When the temperature is within the range of the figure enclosed by lines ID, DF, FE, EH, and HI connecting the five points (points E (-0.3766a+88.486) and point H (0.0, 21.9, -a+78.1)) or on the lines ID, DF, FE, and HI (excluding points E and H), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R1234yf is 200% or more, and the GWP is 150 or less.

[0021] Therefore, the above refrigerant can be used as an alternative refrigerant to R1234yf.

[0022] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on their total sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the total sum of HFO-1132(E), R32, and propane is (100 - a) mass%, when the coordinates (x, y, z) are 0 < a ≦ 5.0, the following points are present: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point M (0.136a 2 -1.74a+11.6, 0.0, -0.136a 2 +0.74a+88.4), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2-0.4006a+93.406) and point H (0.0, 21.9, -a+78.1) When 5.0<a≦10.0, point I (-a+66.7, 22.1, 11.2), point D (-a+75.0, 0.0, 25.0), point M (-0.008a 2 -0.9a+11.0, 0.0, 0.008a 2 -0.1a+89.0), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2 When the temperature is within the range of the figure enclosed by the lines ID, DM, ML, LH, and HI connecting the five points (points L and H) and (-0.4006a+93.406) and point H (0.0, 21.9, -a+78.1), or on the lines ID, DM, ML, and HI (excluding points L and H), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R404A is 100% or more, and the GWP is 150 or less.

[0023] Therefore, the above refrigerant can be used as an alternative refrigerant to R404A.

[0024] The refrigerant of the present disclosure may contain HFO-1132(E) in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, based on the total amount of the refrigerant.

[0025] The refrigerant of the present disclosure may contain 10% by mass or more of propane, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more of propane, based on the total refrigerant.

[0026] The refrigerants of the present disclosure may contain additional refrigerants in addition to HFO-1132(E), R32, propane, and HFO-1132a, as long as the above-described properties and effects are not impaired. In this regard, in one embodiment, the refrigerants of the present disclosure preferably contain 99.5 mass% or more of HFO-1132(E), R32, propane, and HFO-1132a, based on the total refrigerant, more preferably 99.75 mass% or more, even more preferably 99.9 mass% or more, even more preferably 99.999 mass% or more, and most preferably 99.9999 mass% or more. The refrigerants of the present disclosure may consist essentially of only HFO-1132(E), R32 and propane, and HFO-1132a, in which case the refrigerants of the present disclosure may consist only of HFO-1132(E), R32 and propane, and HFO-1132a, and unavoidable impurities.The refrigerants of the present disclosure may consist only of HFO-1132(E), R32 and propane, and HFO-1132a.

[0027] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one type of additional refrigerant alone or two or more types of additional refrigerants.

[0028] Additional refrigerants include acetylene, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, 3,3,3-trifluoropropyne, and the like.

[0029] 2. Refrigerant Composition The refrigerant composition of the present disclosure contains at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure. The refrigerant composition of the present disclosure can be further mixed with at least a refrigerating machine oil to obtain a working fluid for a refrigerant. The refrigerant composition of the present disclosure contains at least one other component in addition to the refrigerant of the present disclosure. The refrigerant composition of the present disclosure may optionally contain at least one of the following other components. As described above, when used as a working fluid in a refrigerant, the refrigerant composition of the present disclosure is typically mixed with at least a refrigerating machine oil. Therefore, the refrigerant composition of the present disclosure is preferably substantially free of a refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure preferably has a refrigerating machine oil content of 1% by mass or less, more preferably 0.1% by mass or less, relative to the total refrigerant composition.

[0030] 2.1 Water The refrigerant composition of the present disclosure may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1 mass% or less based on the total refrigerant. By containing a trace amount of water in the refrigerant composition, the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant are stabilized, and oxidation of the unsaturated fluorocarbon compounds is also made less likely, thereby improving the stability of the refrigerant composition.

[0031] Compositions of the present disclosure also include compositions comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), R32, and R1234yf, and 0.1% or less water.

[0032] 2.2 Tracers Tracers are added to the refrigerant compositions of the present disclosure at detectable concentrations to allow for tracing any dilution, contamination, or other alteration of the refrigerant compositions of the present disclosure.

[0033] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0034] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0035] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (NO), etc. Particularly preferred tracers are hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers.

[0036] The following compounds are preferred as tracers: FC-14 (tetrafluoromethane, CF4), HCC-40 (chloromethane, CH3Cl), HFC-23 (trifluoromethane, CHF3), HFC-41 (fluoromethane, CH3Cl), HFC-125 (pentafluoroethane, CF3CHF2), HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F), HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2), HFC-143a (1,1,1-trifluoroethane, CF3CH3), HFC-143 (1,1,2-trifluoroethane, CHF2CH2F), HFC-152 (1,2-difluoroethane, CH2FCH2F), HFC-161 (fluoroethane, CH3CH2F). HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2) HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3) HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3) HCFC-22 (chlorodifluoromethane, CHClF2) HCFC-31 (chlorofluoromethane, CH2ClF) CFC-1113 (chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl trifluoroethyl ether, CF3OCH2CF3)

[0037] The refrigerant compositions of the present disclosure may contain a total of about 10 parts per million (ppm) by weight or more of tracers based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 1000 ppm or less of tracers based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 30 ppm or more of tracers based on the total refrigerant composition, more preferably about 50 ppm or more of tracers based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 500 ppm or less of tracers based on the total refrigerant composition, and may contain a total of about 300 ppm or less of tracers based on the total refrigerant composition.

[0038] 2.3 UV Fluorescent Dye The refrigerant composition of the present disclosure may contain one type of UV fluorescent dye alone or two or more types.

[0039] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from among commonly used ultraviolet fluorescent dyes.

[0040] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, and derivatives thereof. As the ultraviolet fluorescent dye, either or both of naphthalimide and coumarin are particularly preferred.

[0041] 2.4 Stabilizer The refrigerant composition of the present disclosure may contain one stabilizer alone or two or more stabilizers.

[0042] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0043] Examples of stabilizers include nitro compounds, ethers, and amines.

[0044] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0045] An example of the ethers is 1,4-dioxane.

[0046] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0047] Other examples include butylhydroxyxylene and benzotriazole.

[0048] The stabilizer content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the refrigerant, and is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the refrigerant.

[0049] 2.5 Polymerization Inhibitor The refrigerant composition of the present disclosure may contain one type of polymerization inhibitor alone, or may contain two or more types of polymerization inhibitors.

[0050] The polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.

[0051] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0052] The content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the refrigerant, and is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the refrigerant.

[0053] 3. Refrigerant Oil-Containing Working Fluid The refrigerant oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and a refrigerant oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerant oil-containing working fluid of the present disclosure is obtained by mixing the refrigerant oil used in the compressor of the refrigerator with the refrigerant or refrigerant composition. The refrigerant oil-containing working fluid generally contains 10 mass% or more of the refrigerant oil. The refrigerant oil-containing working fluid generally contains 50 mass% or less of the refrigerant oil.

[0054] 3.1 Refrigerating Machine Oil The composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oils.

[0055] The refrigerating machine oil is not particularly limited and can be appropriately selected from commonly used refrigerating machine oils. In this case, if necessary, a refrigerating machine oil that is superior in terms of miscibility with the mixture and the effect of improving the stability of the mixture can be appropriately selected.

[0056] The base oil of the refrigerating machine oil is preferably at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0057] The refrigerating machine oil may further contain, in addition to the base oil, an additive such as at least one selected from the group consisting of an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, a rust inhibitor, an oiliness agent, and an antifoaming agent.

[0058] From the viewpoint of lubrication, a refrigerating machine oil having a kinematic viscosity of 5 cSt or more at 40° C. is preferred. Also, a refrigerating machine oil having a kinematic viscosity of 400 cSt or less at 40° C. is preferred.

[0059] The refrigerating machine oil-containing working fluid of the present disclosure may further contain at least one additive, if necessary. Examples of the additive include the following compatibilizers.

[0060] 3.2 Compatibilizer The refrigerating machine oil-containing working fluid of the present disclosure may contain one type of compatibilizer alone or two or more types.

[0061] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0062] Examples of the compatibilizer include polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether, and 1,1,1-trifluoroalkane, etc. Polyoxyalkylene glycol ether is particularly preferred as the compatibilizer.

[0063] 4. Method for Operating a Refrigerator The method for operating a refrigerator of the present disclosure is a method for operating a refrigerator using the refrigerant of the present disclosure.

[0064] Specifically, a method of operating a refrigerator according to the present disclosure includes circulating a refrigerant according to the present disclosure in the refrigerator.

[0065] 5. Method for Suppressing Disproportionation Reaction The method for suppressing a disproportionation reaction of HFO-1132(E) disclosed herein includes a step of operating a refrigeration cycle using the refrigerant disclosed herein.

[0066] The method for suppressing the disproportionation reaction disclosed herein has the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring, particularly when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0067] According to the method for suppressing a disproportionation reaction disclosed herein, it is possible to operate a refrigeration cycle while suppressing a disproportionation reaction even in a refrigerator that is not particularly provided with a means for suppressing a disproportionation reaction.

[0068] 6. Use for Suppressing Disproportionation Reactions The use disclosed herein is the use of R32, propane, and HFO-1132a to suppress the disproportionation reaction of HFO-1132(E), and the suppression of the disproportionation reaction is achieved by mixing R32, propane, HFO-1132a, and HFO-1132(E) in a mixing ratio that satisfies the refrigerant disclosed herein.

[0069] When used to inhibit disproportionation reactions according to the present disclosure, the effect is particularly pronounced in that the disproportionation reaction of HFO-1132(E) does not occur even when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0070] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0071] The present disclosure will be described in more detail below with reference to examples, but is not limited to these examples.

[0072] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, propane, and HFO-1132a in the mass percentages shown in Table 1, based on the total mass of these components.

[0073] Each of these mixed refrigerants was examined for the presence or absence of a disproportionation reaction using the following test method and test conditions. Test method: The refrigerant composition to be tested was transferred and filled into a test container and heated to 150°C. After that, a voltage was applied to the Pt wire inside the container, causing it to melt and break, thereby giving the refrigerant composition 30 J of energy. The presence or absence of a disproportionation reaction was determined by a sudden rise in pressure and temperature inside the device. Test conditions: Test container: 38 cc SUS container Test temperature: 150°C Pressure: 3 MPa Evaluation criteria: "No explosion": The temperature or pressure after the Pt wire melted was less than doubled, and no sudden disproportionation reaction occurred. "Explosion": The temperature or pressure after the Pt wire melted reached more than double, and a sudden disproportionation reaction occurred.

[0074]

[0075]

[0076] The results in Tables 1 and 2 show that the refrigerant of the present disclosure does not undergo disproportionation within the region shown in the ternary diagram in FIG.

[0077] The GWP of HFO-1132(E) was set to 1, and the GWP of R32, propane, and HFO-1132a were evaluated based on the values ​​in the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. The COP, refrigeration capacity, discharge temperature, and boiling point of the refrigerant mixture were calculated using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions by theoretically calculating the refrigeration cycle of the refrigerant mixture. The physical property data for HFO-1132(E) was determined from actual measurements. <Compared to R410A> Evaporation temperature 5°C Condensation temperature 45°C Superheat temperature 5K Subcooling temperature 5K Compressor efficiency 70% <Compared to R1234yf> Evaporation temperature -30°C Condensation temperature 30°C Superheat temperature 5K Subcooling temperature 5K Compressor efficiency 70% <Compared to R404A> Evaporation temperature -40°C Condensation temperature 40°C Superheat temperature 20K Subcooling temperature 0K Compressor efficiency 70%.

[0078] In the table below, "COP ratio" and "refrigeration capacity ratio" indicate the percentage (%) of each specified refrigerant. In the table, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa).

[0079] These values ​​are shown in the table below along with the GWP for each refrigerant mixture. Note that the specific COP and specific refrigeration capacity are shown as a percentage of R410A.

[0080] The coefficient of performance (COP) was calculated using the following formula: COP = (refrigeration capacity or heating capacity) / power consumption

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] The coordinates of each point were determined based on the least squares method as follows.

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] From the above results, in the refrigerant of the present disclosure, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 75.0, 0.0, 25.0), Point R (0.0011a 2 -1.0794a+19.594, 0.0, -0.0011a 2 +0.0794a+80.406), point Q (0.0, -0.0011a 2 -0.5366a+10.186, 0.0011a 2 It can be seen that when the temperature is within the range of the figure enclosed by the lines CD, DR, RQ, QB, BA, and AC connecting the six points of point A (-0.4634a+89.814), point B (0.0, 44.2, -a+55.8), and point A (-a+55.7, 44.3, 0.0), or on the lines CD, DR, RQ, and BA (excluding points C, Q, B, and A), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R410A is 70% or more, and the GWP is 300 or less.

[0094] Similarly, tests were conducted with the comparison subject changed to R1234yf.

[0095]

[0096]

[0097]

[0098]

[0099] The coordinates of each point were determined based on the least squares method as follows.

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] From the above results, in the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and propane, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are as follows: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point F (-1.104a + 20.72, 0.0, 0.104a + 79.28), Point E (0.0, 0.0011a 2 -0.6234a+11.514, -0.0011a 2It can be seen that when the temperature is within the range of the figure enclosed by lines ID, DF, FE, EH, and HI connecting the five points (points E (-0.3766a+88.486) and point H (0.0, 21.9, -a+78.1)) or on the lines ID, DF, FE, and HI (excluding points E and H), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R1234yf is 200% or more, and the GWP is 150 or less.

[0106] Similarly, tests were conducted with the comparison object changed to R404A.

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] The coordinates of each point were determined based on the least squares method as follows.

[0113]

[0114]

[0115] From the above results, in the refrigerant of the present disclosure, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, when the coordinates (x, y, z) are 0 < a ≦ 5.0, the following points are present: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point M (0.136a 2 -1.74a+11.6, 0.0, -0.136a 2 +0.74a+88.4), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2-0.4006a+93.406) and point H (0.0, 21.9, -a+78.1) When 5.0<a≦10.0, point I (-a+66.7, 22.1, 11.2), point D (-a+75.0, 0.0, 25.0), point M (-0.008a 2 -0.9a+11.0, 0.0, 0.008a 2 -0.1a+89.0), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2 It can be seen that when the temperature is within the range of the figure enclosed by the lines ID, DM, ML, LH, and HI connecting the five points (points L and H) and (0.0, 21.9, -a+78.1), or on the lines ID, DM, ML, and HI (excluding points L and H), no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R404A is 100% or more, and the GWP is 150 or less.

[0116] Other examples and comparative examples are shown below.

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

Claims

1. A composition comprising a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), propane, and 1,1-difluoroethylene (HFO-1132a), and may further comprise difluoromethane (R32), wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 75.0, 0.0, 25.0), Point R (0.0011a 2 -1.0794a+19.594, 0.0, -0.0011a 2 +0.0794a+80.406), point Q (0.0, -0.0011a 2 -0.5366a+10.186, 0.0011a 2 A composition that lies within the area of ​​a figure bounded by straight lines CD, DR, RQ, QB, BA, and AC respectively connecting the six points: point A (-0.4634a+89.814), point B (0.0, 44.2, -a+55.8), and point A (-a+55.7, 44.3, 0.0), or on said straight lines CD, DR, RQ, and BA (but excluding points C, Q, B, and A).

2. The composition according to claim 1, which is a replacement composition for R410A.

3. A composition comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), propane, and HFO-1132a, and may further comprise R32; wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, the coordinates (x, y, z) are: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point F (-1.104a + 20.72, 0.0, 0.104a + 79.28), Point E (0.0, 0.0011a 2 -0.6234a+11.514, -0.0011a 2 A composition that is within the area surrounded by straight lines ID, DF, FE, EH, and HI connecting the five points ID (-0.3766a+88.486) and point H (0.0, 21.9, -a+78.1) or on said straight lines ID, DF, FE, and HI (excluding points E and H).

4. The composition according to claim 3, which is a replacement composition for R1234yf.

5. A composition comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), propane, and HFO-1132a, and may further comprise R32; wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, propane, and HFO-1132a based on the sum of these are x, y, z, and a (where 0 < a ≦ 10.0), respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and propane is (100 - a) mass%, when the coordinates (x, y, z) are 0 < a ≦ 5.0, the following points occur: Point I (-a + 66.7, 22.1, 11.2), Point D (-a + 75.0, 0.0, 25.0), Point M (0.136a 2 -1.74a+11.6, 0.0, -0.136a 2 +0.74a+88.4), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2 -0.4006a+93.406) and point H (0.0, 21.9, -a+78.1) When 5.0<a≦10.0, point I (-a+66.7, 22.1, 11.2), point D (-a+75.0, 0.0, 25.0), point M (-0.008a 2 -0.9a+11.0, 0.0, 0.008a 2 -0.1a+89.0), point L (0.0, 0.0011a 2 -0.5994a+6.5943, -0.0011a 2 A composition that is within the area surrounded by straight lines ID, DM, ML, LH, and HI connecting the five points ID (-0.4006a+93.406) and point H (0.0, 21.9, -a+78.1) or on said straight lines ID, DM, ML, and HI (excluding points L and H).

6. The composition according to claim 5, which is a replacement composition for R404A.

7. A method of refrigeration comprising the step of operating a refrigeration cycle using the composition of any one of claims 1, 3 and 5.

8. A refrigeration system comprising the composition of any one of claims 1, 3 and 5 as a working fluid.

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