Refrigerant-containing composition, use thereof, refrigeration method, and refrigerating device

Abstract

The present invention provides a novel mixed refrigerant.　The present invention provides a refrigerant-containing composition, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E) or E-HFO-1132) and at least one hydrofluoroolefin represented by the general formula CHXXCX=CHX (wherein Xs are the same as or different from each other and each independently represent a hydrogen atom or a fluorine atom, and at least one of the Xs is a fluorine atom), and contains HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5 mass% or higher with respect to the whole mass of the refrigerant.

Description

Refrigerant-containing composition, its use, refrigeration method, and refrigeration device

[0001] The present disclosure relates to compositions containing refrigerants, their uses, refrigeration methods, and refrigeration devices.

[0002] A mixed refrigerant containing at least one compound selected from the group consisting of three fluoroolefins having specific structures has been proposed (Patent Document 1).

[0003] Special Publication No. 2009-518460

[0004] An object of the present disclosure is to provide a novel refrigerant mixture.

[0005] Item 1. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E); or E-HFO-1132) and at least one hydrofluoroolefin represented by the general formula: CHXXCX=CHX (wherein X is the same or different and is a hydrogen atom or a fluorine atom, and at least one of X is a fluorine atom), and the refrigerant comprises 99.5 mass% or more of HFO-1132(E) and the hydrofluoroolefin relative to the total mass of the refrigerant. Item 2. The composition according to Item 1, which has a boiling point of -40°C or lower. Item 3. Item 4. The composition according to any one of Items 1 to 3, wherein the hydrofluoroolefin is at least one hydrofluoroolefin selected from the group consisting of CHF2CH=CH2, CH3CF=CH2, CH3CH=CHF, E-CHF2CF=CHF, CHF2CF=CH2, CH2FCH=CH2, CH2FCF=CH2, E-CHF2CH=CHF, and Z-CHF2CH=CHF. Item 5. The composition according to any one of Items 1 to 3, wherein the refrigerant contains 25 to 60 mass% of HFO-1132(E) based on the total amount of the refrigerant. Item 6. The composition according to any one of Items 1 to 3, wherein the hydrofluoroolefin is CHF2CH=CH2, and the refrigerant contains: HFO-1132(E) and CHF2CH=CH2 in a total amount of 99.5 mass% or more based on the total amount of the refrigerant; and contains HFO-1132(E) in an amount of 25 to 56 mass% based on the total amount of the refrigerant. Item 7. Item 6. The composition according to any one of Items 1 to 3, wherein the hydrofluoroolefin is CH3CF=CH2, and the refrigerant: contains HFO-1132(E) and the CH3CF=CH2 in a total amount of 99.5 mass% or more, based on the total amount of the refrigerant; and contains HFO-1132(E) in an amount of 35 to 59 mass% based on the total amount of the refrigerant. Item 7. The composition according to any one of Items 1 to 3, wherein the refrigerant: contains HFO-1132(E) and the CH3CH=CHF in a total amount of 99.5 mass% or more, based on the total amount of the refrigerant; and contains HFO-1132(E) in an amount of 36 to 59 mass% based on the total amount of the refrigerant.Item 8. The composition according to any one of Items 1 to 3, wherein the refrigerant: comprises HFO-1132(E) and the E-CHF2CF=CHF in total at 99.5 mass% or more, based on the total amount of the refrigerant; and comprises HFO-1132(E) in an amount of 35 to 53 mass% based on the total amount of the refrigerant. Item 9. The composition according to any one of Items 1 to 3, wherein the refrigerant: comprises HFO-1132(E) and the CHF2CF=CH2 in total at 99.5 mass% or more, based on the total amount of the refrigerant; and comprises HFO-1132(E) in an amount of 31 to 59 mass% based on the total amount of the refrigerant. Item 10. Item 10. The composition according to any one of items 1 to 9, which is used as a replacement refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. Item 11. The composition according to any one of Items 1 to 9, which is a refrigerant for a heat pump or an automotive air conditioner. Item 12. The composition according to any one of Items 1 to 9, which is a refrigerant for a gasoline-powered vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen-powered vehicle. Item 13. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of Items 1 to 9. Item 14. A refrigeration device comprising the composition according to any one of Items 1 to 9 as a working fluid. Item 15. Use of the composition according to any one of Items 1 to 9 as a working fluid.

[0006] The present disclosure provides a new refrigerant mixture.

[0007] 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.

[0008] The present disclosure has been completed as a result of further research based on this finding. The present disclosure includes the following embodiments.

[0009] <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 their 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," a "composition containing a refrigerant," or a "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" or a "working fluid" to distinguish it from the "refrigerant composition."

[0011] 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.

[0012] 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.

[0013] Pressures described in this specification are in units of absolute pressure unless otherwise specified.

[0014] Boiling points given in this specification are at standard atmospheric pressure unless otherwise specified.

[0015] 1. Refrigerant The refrigerant disclosed herein contains trans-1,2-difluoroethylene (HFO-1132(E)) and at least one hydrofluoroolefin represented by the general formula: CHXXCX=CHX (wherein X is the same or different and represents a hydrogen atom or a fluorine atom, and at least one X is a fluorine atom).

[0016] The refrigerant of the present disclosure preferably has a boiling point of -40°C or less.

[0017] The refrigerants of the present disclosure are preferably refrigerants that do not disproportionate at 150°C and 3 MPa.

[0018] The hydrofluoroolefin is preferably at least one hydrofluoroolefin selected from the group consisting of CHF2CH=CH2, CH3CF=CH2, CH3CH=CHF, E-CHF2CF=CHF, CHF2CF=CH2, CH2FCH=CH2, CH2FCF=CH2, E-CHF2CH=CHF, and Z-CHF2CH=CHF.

[0019] It is preferable that the refrigerant contains: HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5% by mass or more based on the total amount of the refrigerant; and HFO-1132(E) in an amount of 25 to 60% by mass based on the total amount of the refrigerant.

[0020] It is preferable that the refrigerant contains: HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5% by mass or more based on the total amount of the refrigerant; and HFO-1132(E) in an amount of 25 to 56% by mass based on the total amount of the refrigerant.

[0021] It is preferable that the refrigerant contains: HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5% by mass or more based on the total amount of the refrigerant; and HFO-1132(E) in an amount of 35 to 59% by mass based on the total amount of the refrigerant.

[0022] It is preferable that the refrigerant contains: HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5% by mass or more based on the total amount of the refrigerant; and HFO-1132(E) in an amount of 35 to 53% by mass based on the total amount of the refrigerant.

[0023] It is preferable that the refrigerant contains: HFO-1132(E) and the hydrofluoroolefin in a total amount of 99.5% by mass or more based on the total amount of the refrigerant; and HFO-1132(E) in an amount of 31 to 50% by mass based on the total amount of the refrigerant.

[0024] The refrigerants of the present disclosure may contain additional refrigerants in addition to HFO-1132(E) and the hydrofluoroolefin, as long as the above-described properties and effects are not impaired. In this regard, the refrigerants of the present disclosure preferably contain 99.5 mass% or more of HFO-1132(E) and the hydrofluoroolefin, based on the total amount of the 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 HFO-1132(E) and the hydrofluoroolefin. In this case, the refrigerants of the present disclosure may consist only of HFO-1132(E), the hydrofluoroolefin, and unavoidable impurities. Alternatively, the refrigerants of the present disclosure may consist solely of HFO-1132(E) and the hydrofluoroolefin.

[0025] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one or more additional refrigerants. Examples of additional refrigerants include R32, acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0026] Furthermore, the refrigerant of the present disclosure, when having a boiling point of −40.0° C. or lower, has the advantage of being easily usable in heating using a heat pump. For example, when the refrigerant of the present disclosure is used to operate the refrigeration cycle of an automotive air conditioner, it has the advantage of enabling heating using a heat pump that consumes less power than an electric heater. Examples of automotive air conditioners include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0027] 2. Refrigerant Composition The refrigerant composition of the present disclosure (also referred to as a "refrigerant-containing composition" or "composition") contains at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure. Furthermore, 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 refrigerating machine.

[0028] 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 the refrigerant composition of the present disclosure is used as a working fluid in a refrigerator, it is usually 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 contains 1% by mass or less, more preferably 0.1% by mass or less, of the refrigerating machine oil relative to the total refrigerant composition.

[0029] 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.

[0030] 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.

[0031] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0032] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0033] 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.

[0034] The following compounds are preferred as tracers: FC-14 (tetrafluoromethane, CF4), HCC-40 (chloromethane, CH3Cl), HFC-23 (trifluoromethane, CHF3), HFC-41 (fluoromethane, CH3F), 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)

[0035] 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.

[0036] 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.

[0037] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from among commonly used ultraviolet fluorescent dyes.

[0038] 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.

[0039] 2.4 Stabilizer The refrigerant composition of the present disclosure may contain one stabilizer alone or two or more stabilizers.

[0040] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0041] Examples of stabilizers include nitro compounds, ethers, and amines.

[0042] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0043] An example of the ethers is 1,4-dioxane.

[0044] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0045] Other examples include butylhydroxyxylene and benzotriazole.

[0046] 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.

[0047] 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.

[0048] The polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.

[0049] 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.

[0050] 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.

[0051] 3. Refrigerant Oil-Containing Working Fluid The refrigerant oil-containing working fluid (also referred to as "working fluid") of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and 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 refrigerant oil. The refrigerant oil-containing working fluid generally contains 50 mass% or less of refrigerant oil.

[0052] 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.

[0053] 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.

[0054] 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).

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0060] 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.

[0061] 4.1 Freezing Method The freezing method of the present disclosure is a freezing method that uses the composition of the present disclosure.

[0062] Specifically, the refrigeration method of the present disclosure includes operating a refrigeration cycle using the composition of the present disclosure described above.

[0063] 4.2 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 a 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 Reaction The use disclosed herein is a use of at least one hydrofluoroolefin represented by the general formula: CHXXCX=CHX (where X is the same or different and is a hydrogen atom or a fluorine atom) for suppressing the disproportionation reaction of HFO-1132(E), and the suppression of the disproportionation reaction is achieved by mixing HFO-1132(E) and the hydrofluoroolefin at 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] 7. Use as an alternative refrigerant The compositions of the present disclosure are preferably used as replacement refrigerants for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze.

[0071] 8. Use as a Working Fluid The compositions of the present disclosure can be used as working fluids.

[0072] That is, the use of the present disclosure is the use of the composition of the present disclosure described above as a working fluid.

[0073] 9. Refrigeration Device The refrigeration device of the present disclosure comprises the above-described composition.

[0074] That is, the refrigeration device of the present disclosure is a refrigeration device that contains the above-described composition of the present disclosure as a working fluid.

[0075] 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.

[0076] The present disclosure will be described in more detail below with reference to examples, but is not limited to these examples.

[0077] Mixed refrigerants were prepared by mixing HFO-1132(E) and the example CHXXCX=CHX in the mass percentages shown in each table, based on the sum of these.

[0078] 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.

[0079]

[0080] In addition, a mixed refrigerant was prepared using HFO-1132(E), which has a boiling point of -52.6°C, and the CHXXCX=CHX example, and the concentration of HFO-1132(E) that resulted in a boiling point of -40°C was investigated.

[0081] Table 2 shows the boiling points of substances with example molecular formulas, the concentration of HFO-1132(E) when the boiling point of a mixture of the substance shown by the molecular formula and HFO-1132(E) is -40°C, and the concentration of HFO-1132(E) when the mixture of the substance shown by the molecular formula and HFO-1132(E) reaches the disproportionation limit of HFO-1132(E).

[0082]

Claims

1. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E); or E-HFO-1132) and at least one hydrofluoroolefin represented by the general formula: CHXXCX=CHX (X is the same or different and is a hydrogen atom or a fluorine atom, and at least one is a fluorine atom), and the refrigerant contains 99.5% by mass or more of the total of HFO-1132(E) and the hydrofluoroolefin with respect to the whole refrigerant.

2. The composition according to claim 1, having a boiling point of -40°C or lower.

3. The composition according to claim 1, wherein the hydrofluoroolefin is at least one hydrofluoroolefin selected from the group consisting of CHF2CH=CH2, CH3CF=CH2, CH3CH=CHF, E-CHF2CF=CHF, CHF2CF=CH2, CH2FCH=CH2, CH2FCF=CH2, E-CHF2CH=CHF, and Z-CHF2CH=CHF.

4. The composition according to claim 1, wherein the refrigerant contains 25 to 60% by mass of HFO-1132(E) with respect to the whole refrigerant.

5. The hydrofluoroolefin is CHF2CH=CH2, and the refrigerant: contains 99.5% by mass or more of the total of HFO-1132(E) and CHF2CH=CH2 with respect to the whole refrigerant; and contains 25 to 56% by mass of HFO-1132(E) with respect to the whole refrigerant. The composition according to claim 1.

6. The hydrofluoroolefin is CH3CF=CH2, and the refrigerant: contains 99.5% by mass or more of the total of HFO-1132(E) and CH3CF=CH2 with respect to the whole refrigerant; and contains 35 to 59% by mass of HFO-1132(E) with respect to the whole refrigerant. The composition according to claim 1.

7. The composition according to any one of claims 1 to 6, which is used as an alternative refrigerant to R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze.

8. The composition according to any one of claims 1 to 6, which is a refrigerant for a heat pump or a refrigerant for an in-vehicle air conditioner.

9. The composition according to any one of claims 1 to 6, which is a refrigerant for a gasoline vehicle, a refrigerant for a hybrid vehicle, a refrigerant for an electric vehicle, or a refrigerant for a hydrogen vehicle.

10. A refrigeration method including a step of operating a refrigeration cycle using the composition according to any one of claims 1 to 6.

11. A refrigeration device including the composition according to any one of claims 1 to 6 as a working fluid.

12. Use of the composition according to any one of claims 1 to 6 as a working fluid.

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