Refrigerant-containing composition

Abstract

The present disclosure aims to provide a composition that suppresses disproportionation reactions of a refrigerant and has excellent refrigerant stability. The present disclosure aims to provide a composition containing a refrigerant that is useful in air conditioning systems. A composition containing a refrigerant, the refrigerant including a disproportionating refrigerant and a non-disproportionating refrigerant.

Description

[Technical Field]

[0001] The present disclosure relates to compositions containing refrigerants. [Background technology]

[0002] Patent Document 1 describes trifluoroethylene (HFO-1123) and difluoromethane (HFC-32). A working fluid for a heat cycle is disclosed, which comprises an azeotrope-like composition comprising:

[0003] Patent Document 2 describes a gas turbine engine that uses a refrigerant containing trifluoroethylene (HFO-1123) as a working fluid. The paper discloses a compressor that uses polyvinyl ether oil as a compressor lubricant, has compression chambers formed in both directions by meshing a fixed scroll and an orbiting scroll, each having a spiral wrap rising from an end plate, and has an injection hole in the compression chamber.

[0004] Patent Document 3 describes a compressor, a first heat exchanger, an expansion mechanism, and a second heat exchanger that are connected together. The higher the pressure and the more trifluoroethylene (HFO-1123) is contained, the more likely the chain reaction of disproportionation reactions will occur. The refrigeration cycle device disclosed includes a refrigerant circuit through which a reactive refrigerant circulates, and a control mechanism that includes an automatic reset pressure fuse in a compressor container that cuts off the neutral point of a three-phase stator winding connected by a Y connection of the compressor's electric element to prevent an explosion due to a chain reaction of disproportionation of the refrigerant when the pressure of the refrigerant in the flow path from the compressor to the expansion mechanism of the refrigerant circuit reaches a threshold value, thereby cutting off the flow of electricity between the compressor's electric element and an external power source. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-145452 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-214927 [Patent Document 3] Japanese Patent Application Publication No. 2018-112396 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide a composition that suppresses disproportionation reactions of a refrigerant and provides excellent refrigerant stability.

[0007] The present disclosure aims to provide refrigerant-containing compositions useful in air conditioning systems. [Means for solving the problem]

[0008] The present disclosure provides the following aspects of the invention.

[0009] Section 1. A composition containing a refrigerant, The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant has a temperature satisfying the formula: y < -1.5761x + 3.9516 A composition characterized in that the range is as shown below.

[0010] Section 2. A composition containing a refrigerant, The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant has a temperature satisfying the formula: y < -1.4941x + 3.6044 A composition characterized in that the range is as shown below.

[0011] Section 3. The refrigerants that do not undergo disproportionation include 3,3,3-trifluoropropene (HFO-1243zf), trifluoroiodomethane (CF3I), difluoromethane (HFC-32), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), hexafluoropropene (FO-1216), perfluoromethane (PFC-14), and pentafluoroethane. (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), CF3SCF3, propane, cyclopropane, propane 3. The composition according to item 1 or 2, further comprising at least one component selected from the group consisting of propylene, isobutene, isobutane, carbon dioxide, and ammonia.

[0012] Section 4. 4. The composition according to any one of items 1 to 3, further comprising a refrigerating machine oil and used as a refrigerating machine oil-containing working fluid.

[0013] Section 5. The refrigerating machine oil is selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), polyvinyl ether (PVE), silicone oil, and fluorine-containing oil. 5. The composition according to item 4, comprising at least one polymer.

[0014] Section 6. 6. The composition according to any one of items 1 to 5, which is used in an air conditioning system.

[0015] Section 7. 7. An air conditioning system using the composition according to any one of items 1 to 6.

[0016] Section 8. 7. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of items 1 to 6.

[0017] Section 9. 7. A method for operating a refrigeration system, comprising operating a refrigeration cycle using the composition according to any one of items 1 to 6.

[0018] Section 10. 7. A refrigeration device using the composition according to any one of items 1 to 6.

[0019] Section 11. Item 11. The refrigeration device according to item 10, which is an air conditioner, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a freezer showcase, a freezer / refrigerator unit, a freezer for a freezer / refrigerator warehouse, an in-vehicle air conditioner, a turbo freezer, or a screw freezer.

[0020] Section 12. 1. A method for storing a composition containing a refrigerant, comprising: The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The method according to claim 1, further comprising the step of:

[0021] Section 13. 1. A method for storing a composition containing a refrigerant, comprising: The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The method according to claim 1, further comprising the step of:

[0022] Section 14. 1. A method for mixing refrigerants, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The method according to claim 1, wherein the range is set as shown in

[0023] Section 15. 1. A method for mixing refrigerants, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The method according to claim 1, wherein the range is set as shown in

[0024] Section 16. A method for suppressing a disproportionation reaction of a refrigerant, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The method according to claim 1, wherein the range is set as shown in

[0025] Section 17. A method for suppressing a disproportionation reaction of a refrigerant, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated is selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1132b), and 1,1-difluoroethylene (HFO-1132c). from the group consisting of fluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) At least one selected component is included, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The method according to claim 1, wherein the range is set as shown in [Effects of the Invention]

[0026] In a composition containing a refrigerant according to the present disclosure, the disproportionation reaction of the refrigerant is suppressed, and the refrigerant has excellent stability.

[0027] Compositions containing the refrigerants of the present disclosure are useful in air conditioning systems. [Brief explanation of the drawings]

[0028] [Figure 1] FIG. 1 is a diagram illustrating the conditions under which a composition including a refrigerant of the present disclosure is operated in an air conditioning system. [Figure 2] FIG. 1 is a diagram illustrating the conditions under which a composition including a refrigerant of the present disclosure is operated in an air conditioning system. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that when a composition containing a refrigerant is used in an air conditioning system, the disproportionation reaction of the refrigerant used in the air conditioning system is suppressed when the refrigerant contains a refrigerant that disproportionates and a refrigerant that does not disproportionate, and the entire refrigerant in the composition is operated under conditions based on a specific relationship formula.

[0030] The present disclosure was completed as a result of further research based on this finding.

[0031] Hereinafter, embodiments included in the present disclosure will be described in detail.

[0032] <Terminology> In this specification, the term "refrigerant" includes at least compounds designated by ISO817 (International Organization for Standardization) with a refrigerant number (ASHRAE number) beginning with R, which indicates the type of refrigerant. Furthermore, even if a refrigerant number has not yet been assigned, it also includes refrigerants that have equivalent refrigerant properties.

[0033] Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" based on the chemical structure. "Fluorocarbon compounds" include hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). "Non-fluorocarbon compounds" include Carbon compounds include propane (R290), propylene (R1270), and butane (R600). , isobutane (R600a), etc.

[0034] In this specification, the term "composition containing a refrigerant" includes (1) a refrigerant itself (a mixture of refrigerants) and (2) a refrigerant itself (a mixture of refrigerants). (2) a mixture of at least refrigerant mixtures containing other ingredients; The present invention includes at least (1) a composition that can be used to obtain a refrigeration working fluid by mixing with a refrigeration oil, and (2) a refrigeration working fluid containing a refrigeration oil.

[0035] In this specification, of these three aspects, the composition (2) is referred to as the refrigerant itself ( The term "refrigerant composition" is used to distinguish it from a mixture of refrigerants. do.

[0036] In this specification, the working fluid for a refrigerating machine (3) is also distinguished from the "refrigerant composition." It is written as "working fluid containing refrigeration oil."

[0037] In this specification, the term "substitution," when used in the context of "replacing" a first refrigerant with a second refrigerant, means that equipment of the first type designed to operate using the first refrigerant can be operated under optimal conditions using the second refrigerant by simply changing a small number of components (at least one of refrigeration oil, gaskets, packings, expansion valves, dryers, and other components) and adjusting the equipment, as necessary.

[0038] In other words, this type refers to operating the same equipment by "substituting" a refrigerant. The forms of "substitution" in this type can be "drop-in substitution," "nearly drop-in substitution," or "retrofit," in order of decreasing degree of change or adjustment required when switching to a second refrigerant.

[0039] 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.

[0040] In this specification, the term "refrigerator" refers to a device that removes heat from an object or space, thereby lowering the temperature below that of the surrounding air, and maintaining that low temperature. In other words, a refrigerator is a conversion device that receives energy from an external source, performs work, and converts it into energy in order to transfer heat from a low-temperature source to a high-temperature source.

[0041] In this specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0042] In this specification, when a numerical range is described in stages, the upper limit or lower limit of a numerical range in one stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage.

[0043] In this specification, the upper or lower limit of a numerical range described may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.

[0044] In this specification, the following is used:

[0045] Examples of disproportionating refrigerants trans-1,2-difluoroethylene: HFO-1132(E) ((E)-1,2-difluoroethylene) cis-1,2-difluoroethylene: HFO-1132(Z) ((Z)-1,2-difluoroethylene) (E) and / or (Z)-1,2-difluoroethylene: HFO-1132(E / Z) "(E / Z)" refers to the E-form (trans-form) and This means that it includes Z isomers (cis isomers) and / or Z isomers (cis isomers).

[0046] 1,1-Difluoroethylene: HFO-1132a Trifluoroethylene: HFO-1123 Tetrafluoroethylene: FO-1114

[0047] Examples of refrigerants that do not disproportionate 3,3,3-trifluoropropene: HFO-1243zf Trifluoroiodomethane: CF3I Difluoromethane: HFC-32 2,3,3,3-Tetrafluoropropene: HFO-1234yf Trans-1,3,3,3-tetrafluoropropene: HFO-1234ze(E) Hexafluoropropene: FO-1216 Perfluoromethane: PFC-14 Pentafluoroethane: HFC-125 1,1,2,2-Tetrafluoroethane: HFC-134 1,1,1,2-Tetrafluoroethane: HFC-134a 1,1,1-trifluoroethane: HFC-143a 1,1-Difluoroethane: HFC-152a Fluoroethane: HFC-161 1,1,1,2,3,3,3-Heptafluoropropane: HFC-227ea trans-1,2,3,3,3-pentafluoropropene: HFO-1225ye(E) cis-1,2,3,3,3-pentafluoropropene Pentafluoropropene: HFO-1225ye(Z) (E) and / or (Z)-1,2,3,3,3-pentafluoropropene Ropene: HFO-1225ye(E / Z) "(E / Z)" means that the E form (trans form) and / or the Z form (cis form) are included.

[0048] CF3SCF3 Propane: R290 Cyclopropane Propylene: R1270 Isobutene Isobutane: R600a Carbon dioxide: R744 Ammonia: R717

[0049] [1] Composition (1) Refrigerant The compositions of the present disclosure contain refrigerants, including disproportionating and non-disproportionating refrigerants.

[0050] Among the above refrigerants, the refrigerants that are disproportionated are trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a ), trifluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114) It contains at least one component selected from the group consisting of:

[0051] Of the refrigerants, the refrigerants that do not undergo disproportionation are preferably 3,3,3-trifluoropropene (HFO-1243zf), trifluoroiodomethane (CF3I), difluoromethane (HFC-32), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), hexafluoropropene (FO-1216), and perfluoromethane (PFC-14). , pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoroethane The mixture contains at least one component selected from the group consisting of 1,2,3,3,3-pentafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia.

[0052] The concentration (mol / m) of the disproportionating refrigerant in the vapor phase of the composition of the present disclosure 3) is defined as x, and the thermal diffusivity (mm 2 / s) is the common logarithm (log) of y When you say, The refrigerant has the formula: y < -1.5761x + 3.9516 The range is indicated by:

[0053] The concentration (mol / m) of the disproportionating refrigerant in the vapor phase of the composition of the present disclosure 3 ) is defined as x, and the thermal diffusivity (mm 2 / s) is the common logarithm (log) of y When you say, The refrigerant has the formula: y < -1.4941x + 3.6044 The range is indicated by:

[0054] The "total refrigerant" refers to the sum of the "disproportionating refrigerant" and the "non-disproportionating refrigerant." In the composition of the present disclosure, the refrigerant used is composed of the disproportionating refrigerant and the non-disproportionating refrigerant.

[0055] In the composition of the present disclosure, the method for producing the refrigerant to be contained is not particularly limited, and various refrigerants can be produced by, for example, known production methods. In some cases, HFO-1132(E / Z) is used to dehydrofluorinate 1,1,2-trifluoroethane (HFC-143) and to produce (E)- and / or (Z)-1,2-dichloro-1,2-difluoroethylene (CFO-1112(E / Z)). It can be produced by hydrogenation or dehydrochlorination of 1-chloro-1,2-difluoroethane (HCFC-142a).

[0056] In the composition, the total amount of the refrigerant can be determined by gas chromatography.

[0057] The refrigerant contained in the composition may preferably be a combination consisting essentially of at least one disproportionating refrigerant selected from the group consisting of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114, and a non-disproportionating refrigerant.

[0058] In the composition of the present disclosure, the content of the refrigerant is not particularly limited, and is usually preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, particularly preferably 70% by mass or less, and most preferably 60% by mass or less, based on the total composition. The content of the refrigerant is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, based on the total composition. It is particularly preferably 30% by mass or more, and most preferably 40% by mass or more.

[0059] The other refrigerant may contain impurities (unavoidable impurities) that may be mixed in during the production of the refrigerant.

[0060] In the case of HFO-1132(E / Z), for example, the impurities include hydrogen fluoride, fluoroethylene, Fluorocarbons, HFO-1123, 1,1,1-trifluoroethane, propylene, acetylene, HFC-32, trifluoromethane, fluoromethane, HFO-1123, HFC-152a, HFC-161, HFC-143, 2-chloro-1,1,1-trifluoroethane (HCFC-133b), 1-chloro-1,1,2-trifluoroethane (HCFC-133) , 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,2-difluoroethane (HFC-152), chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), HFC-125, HFO-1234yf, HFO-1225ye(E / Z), HFO-1234ze(E / Z), fluoroethylene (HFO-1141), 3,3,3-trifluoropropene (HFO-1243zf), HFO-1132a, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), ethylene, etc.

[0061] When the refrigerant contained in the composition of the present disclosure contains impurities of the refrigerant, the content thereof is not particularly limited, and may be, for example, about 0.1 ppm or more and 10,000 ppm or less by weight. Within this range, there is little risk that the stabilizing effect of the refrigerant in the composition will be impaired.

[0062] The refrigerant contained in the composition has a Global Warming Potential (GWP) of less than 10 It is required that the material be non-flammable, have low toxicity, and be non-combustible.

[0063] Refrigerants include HFO refrigerants (HFO-1132(E), HFO-1132(Z), HFO-1132a, HFO-1123, FO-1114) When used alone, the GWP is less than 10, which is preferable in terms of low toxicity, but it is flammable. However, there are also undesirable aspects such as poor stability (e.g., disproportionation reactivity). To address these undesirable points, attempts have been made to solve the problems by mixing the refrigerant with other refrigerants in the refrigerant composition, or by controlling the operating conditions, mixing, storage, etc. of the air conditioning system equipment.

[0064] The disproportionation reaction of HFO refrigerants HFO-1132(E) and HFO-1132(Z) is represented by the following formula: CHF=CHF → 2C+2HF

[0065] The disproportionation reaction is 1.Temperature , 2. Pressure and refrigerant composition , 3. Ignition energy It occurs when the following three elements are met:

[0066] 1.Temperature For example, when the temperature of the air conditioning system exceeds a predetermined temperature, the disproportionation reaction can be suppressed by depressurizing and controlling the temperature.

[0067] FIG. 1 shows the range of disproportionation occurrence in the air conditioning system of the present disclosure, as an example, The figures are shown by the composition ratio of the refrigerant HFO-1132(E) and the refrigerant HFO-1234yf that does not disproportionate. Disproportionation occurs when an ignition source is present under these temperature and pressure conditions. The "temperature and pressure conditions under which disproportionation occurs" are on the positive side of the horizontal axis of each graph.

[0068] 2. Pressure and refrigerant composition For example, it is conceivable to suppress the disproportionation reaction by stopping the power supply and controlling the pressure when the pressure of the air conditioning system reaches a predetermined pressure. Regarding the refrigerant composition, it is conceivable to suppress the disproportionation reaction by, for example, increasing the proportion of refrigerant that does not disproportionate. For example, it is conceivable to suppress the disproportionation reaction by using a mixture that includes HFC-32 as a refrigerant that does not disproportionate.

[0069] 3. Ignition energy There is no particular limitation.

[0070] Ignition energy: 30J assumed conditions For example, possible causes include layer shorts in the wiring inside the compressor, melting due to Joule heat, sparks, frictional heat in sliding parts, heat generated by the motor, adiabatic compression of the refrigerant inside the piping, collision energy between the refrigerant and the structure, etc. The magnitude of ignition energy varies, and it is thought that the greater the amount of energy, the more likely disproportionation will occur.

[0071] Generally, the ignition energy used in the combustion evaluation of refrigerants is 20 J or more according to the High Pressure Gas Safety Act. It is designed to give a force of 30J, which is actually measured.

[0072] As explained above, disproportionation reactions occur when three factors are met: 1. temperature, 2. pressure and refrigerant composition, and 3. ignition energy. Therefore, under an ignition energy of 30 J, a specific disproportionation reaction occurs. In a composition containing a refrigerant that disproportionates and a refrigerant that does not disproportionate, the concentration (mol / m) of the refrigerant that disproportionates in the gas phase of the composition 3 ) is expressed as x, and the refrigerant contained in the composition is Overall thermal diffusivity (mm 2 When the common logarithm (log) of the temperature (°C / s) is y, the refrigerant is Formula: y <-1.5761x + 3.9516 The disproportionation reaction can be suppressed by adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature falls within the range shown by the formula (1).

[0073] Ignition energy: 500J assumed conditions Generally, the ignition energy of frictional heat in sliding parts reaches 500J.

[0074] When the ignition energy is set to 500 J, in a composition containing a specific disproportionating refrigerant and a non-disproportionating refrigerant, the concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition is 3 ) The common logarithm (log) of x is the thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant has the formula: y < -1.4941x + 3.6044 The disproportionation reaction can be suppressed by adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature falls within the range shown by the formula (1).

[0075] Even when the ignition energy is set to 500 J, the condition under which the disproportionation reaction of the refrigerant contained in the composition can be suppressed (equation: y < -1.4941x + 3.6044) can be said to be more preferable than the condition under which the ignition energy is set to 30 J (equation: y < -1.5761x + 3.9516).

[0076] (2) Explanation of the general formula FIG. 2 illustrates that the compositions of the present disclosure include a disproportionating refrigerant and a non-disproportionating refrigerant, e.g., 1 is a graph showing the operating conditions of a refrigerant when used in a cooling system, and generalizing the refrigerant composition, temperature, and pressure conditions under which disproportionation reactions do not occur.

[0077] By generalizing the refrigerant composition, temperature, and pressure conditions under which the disproportionation reaction is suppressed when the composition of the present disclosure is used, for example, in an air conditioning system, the disproportionation reaction can be suppressed for a specific refrigerant composition, as shown in FIG. This allows the operation of an air conditioning system in which disproportionation reactions are suppressed under specific conditions of temperature and pressure.

[0078] The composition of the present disclosure can be used in, for example, an air conditioning system, as shown in FIG. By plotting the "diffusivity" and "concentration of the refrigerant that disproportionates," the "○" for "when disproportionation is suppressed" and the "×" for "when disproportionation occurs" are separated across the graph, at the bottom left (○) and top right (×).

[0079] The "lower left of the graph" is the area occupied by the "○", and the refrigerant is on the negative side of the y-axis of the graph (linear equation): y = -1.5761x + 3.9516, that is, y < -1.5761x + 3.9516 It is controlled within the range indicated by

[0080] The "upper right of the graph" is the area occupied by the "x" and the refrigerant is on the positive side of the y-axis of the graph (straight line equation): y = -1.5761x + 3.9516, that is, y > -1.5761x + 3.9516 It is controlled within the range indicated by

[0081] The composition of the present disclosure can be used in, for example, an air conditioning system, as shown in the graph (direct By operating the air conditioning system under conditions of refrigerant composition, temperature, and pressure that fall in the circle below and to the left of the boundary line of the equation of the line), in other words, by controlling the refrigerant within the range indicated by y < -1.5761x + 3.9516, it becomes possible to operate the air conditioning system with the disproportionation reaction suppressed.

[0082] The above description is based on the concentration (mol / m3) of the disproportionating refrigerant in the gas phase of the composition of the present disclosure. When the common logarithm (log) is x and the common logarithm (log) of the thermal diffusivity (mm / s) of the entire refrigerant contained in the composition is y, The refrigerant has the formula: y < -1.4941x + 3.6044 This can also be applied when the range is as shown in

[0083] (2-1) Explanation of the x-axis x-axis: log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) The compositions of the present disclosure may be used, for example, in air conditioning systems, to reduce impurities in the gas phase of the composition. Concentration of the refrigerant to be homogenized (mol / m 3 ) is expressed as "x" (x-axis).

[0084] In the compositions of the present disclosure, the x-axis range, i.e., "log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 ))" range is used, for example, in air conditioning systems, In terms of effectively suppressing the reaction, it is preferably -0.59 or more and 4.23 or less, and more preferably Preferably, it is 2.2 or more and 3.4 or less.

[0085] "Total of disproportionated refrigerants" refers to the total of disproportionated refrigerants in the refrigerant composition. When a single disproportionated refrigerant is used, it refers to that single refrigerant. When two or more disproportionated refrigerants are used in combination, it refers to the total of disproportionated refrigerants. When used in this context, it refers to the total of two or more types used in combination.

[0086] The common logarithm (log) of the value of "x" (x-axis) is the "disproportionation cooling rate in the gas phase of the composition." Solvent concentration (mol / m 3 ) depends on temperature, pressure, and refrigerant composition.

[0087] (2-2) Explanation of the y-axis y-axis: log (thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) The compositions of the present disclosure may be used, for example, in air conditioning systems to improve the thermal diffusivity (mm 2 Let the common logarithm (log) of ( / s) be "y" (y-axis).

[0088] In the compositions of the present disclosure, the range of the y-axis, i.e., "log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 The range of " / s)" is based on the formula and follows the range of the x-axis above.

[0089] The common logarithm (log) of the value of "y" (y-axis) is the "thermal diffusivity of the entire refrigerant (mm 2 / s)" , which can be calculated using the following formula:

[0090] Thermal diffusivity of the entire refrigerant (mm 2 / s) = Thermal conductivity [mW / (m K)] ÷ (Density [kg / (m 3 )] × specific heat [kJ / kg K]) The "thermal conductivity [mW / (m K)]" depends on the refrigerant composition, temperature, and pressure.

[0091] The above "Density [kg / (m 3 ) depends on the refrigerant composition, temperature, and pressure.

[0092] The "specific heat [kJ / kg K]" depends on the refrigerant composition, temperature, and pressure.

[0093] Specific heat refers to constant pressure molar specific heat.

[0094] The thermal conductivity [mW / (m K)] and density [kg / (m 3 )] and "Specific heat [kJ / kg K] can be measured or calculated theoretically using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop). You may ask for it.

[0095] (2-3) Explain the relationship between x and y y < -1.5761x + 3.9516 x = log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) y = log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) The compositions of the present disclosure, when used in, for example, air conditioning systems, The refrigerant is calculated using the formula: y <-1.5761x + 3.9516 When operating under conditions controlled within the range shown in, for example, This makes it possible to operate an air conditioning system with suppressed disproportionation reactions at temperatures below this range.

[0096] The above description refers to the concentration (mol / m) of the disproportionating refrigerant in the vapor phase of the composition of the present disclosure. 3 )of The common logarithm (log) is defined as x, and the thermal diffusivity (mm2 / s), for example, under an ignition energy of 500 J, The refrigerant has the formula: y < -1.4941x + 3.6044 This can also be applied when the range is as shown in

[0097] When the composition of the present disclosure is used in, for example, an air conditioning system, the range of x is preferably −0.59 or more and 4.23 or less, so that the disproportionation reaction is well suppressed, and the range of y is based on the formula and follows the range of x above.

[0098] At an ignition energy of 500 J, the disproportionation reaction occurs under the following conditions: The conditions under which a disproportionation reaction occurs at an ignition energy of 500 J are within the allowable range under which the disproportionation reaction is suppressed.

[0099] At an ignition energy of 500 J, the condition for suppressing the disproportionation reaction is In this case, compared to the conditions under which the disproportionation reaction is suppressed, the conditions under which the disproportionation reaction is suppressed are safer and more preferable in that disproportionation is suppressed even under more severe conditions such as equipment failure or emergency situations.

[0100] (3) Description of refrigerant The "total refrigerant" refers to the sum of the refrigerant that disproportionates and the refrigerant that does not disproportionate in the refrigerant composition.

[0101] The disproportionating refrigerant is selected from the group consisting of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. It contains at least one component selected from the following, and may be used alone or in combination of two or more. It may be used.

[0102] The non-disproportionating refrigerant is preferably HFO-1243zf, CF3I, HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161 , HFC-227ea, HFO-1225ye(Z), HFO-1225ye(E), CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia, and one or more of them may be used alone or in combination.

[0103] When the composition of the present disclosure is used in an air conditioning system, for example, by having the above-described configuration, it becomes possible to provide an air conditioning system containing a refrigerant in which disproportionation reactions of the refrigerant are suppressed.

[0104] [2] Specific examples of use of the composition (1) Specific example 1 The refrigerant composition contains 60 mass% of HFO-1132(E / Z) as a disproportionating refrigerant and 40 mass% of HFO-1234yf as a non-disproportionating refrigerant, based on the total amount of refrigerant contained in the composition.

[0105] The temperature condition is set to 150°C.

[0106] The pressure condition is set to 3.00 MPa.

[0107] It is verified whether a disproportionation reaction occurs under the above refrigerant composition, temperature conditions, and pressure conditions.

[0108] (1-1) Calculate the right hand side of "y = -1.5761x + 3.9516" (-1.5761x + 3.9516) The common logarithm (log) on ​​the x-axis indicates the concentration (mol) of the disproportionating refrigerant in the gas phase of the composition. / m 3 )" is calculated.

[0109] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 76.912 kg / m at 150°C and 3.00 MPa. 3 ].

[0110] The concentration of the disproportionating refrigerant (HFO-1132 (E / Z), Mw: 64.035) is: 76.912 [kg / m 3 ]×0.6÷64.035[g / mol]=720.66[mol / m 3 ] becomes.

[0111] The x-axis is log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) =log(720.66) =2.8577.

[0112] In the equation between x and y: y = -1.5761x + 3.9516, if you substitute "2.857" for "x", "y" becomes "-0.55242".

[0113] Next, separately, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculate When the calculated value is "lower" than the value of "y" above, "-0.55242", that is, when the relationship between x and y is When the temperature crosses the graph and is "bottom left" of the boundary line of the graph (Fig. 2), the air conditioning system The system enables operation of an air conditioning system using a composition that "suppresses disproportionation reactions" when operated under the above refrigerant composition, temperature, and pressure conditions. The "bottom left of the graph" is the "position on the negative side of the y-axis of the graph (linear equation)."

[0114] Or, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculated When the value is "high" compared to the "y" value "-0.55242" mentioned above, that is, when the graph of the relationship between x and y When the temperature crosses the boundary line of the graph and becomes "upper right" from the boundary line of the graph (Figure 2), the air conditioning system When operating under the above refrigerant composition, temperature, and pressure conditions, the air conditioning system is operated using a composition that "causes a disproportionation reaction." The "upper right of the graph" is the "position on the positive side of the y-axis of the graph (linear equation)."

[0115] In other words, the refrigerant is controlled within the range y < -1.5761x + 3.9516. This makes it possible to operate an air conditioning system in which disproportionation reactions are suppressed.

[0116] (1-2) Calculate the left side "y" of "y = -1.5761x + 3.9516" The common logarithm (log) on ​​the y-axis indicates the thermal diffusivity (mm 2 / s) is calculated.

[0117] The "thermal conductivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 28,000 [mW / (m K)] at 150°C and 3.00 MPa.

[0118] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 76.912 kg / m at 150°C and 3.00 MPa. 3 ].

[0119] The specific heat of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 1.2482 [kJ / kg K] at 150°C and 3.00 MPa.

[0120] The thermal diffusivity of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) at 150°C and 3.00 MPa is 28.000 [mW / (m K)] ÷ (76.912 [kg / m 3 ]×1.2482 [kJ / kg K])=0.29167[mm 2 / s].

[0121] The y-axis is log(thermal diffusivity of the total refrigerant contained in the composition (mm 2 / s)) =log(0.29167) =-0.53511.

[0122] This y (log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)” value of “-0.53511” is calculated by the above “-1.5761x + 3.9516” (x: log(concentration of the disproportionating refrigerant in the gas phase of the composition (mol / m 3 ))) is "higher" than the value of "-0.55242", that is, when it straddles the graph of the relationship between X and y and is "upper right" from the boundary line of the graph, in other words, when it is "on the positive side of the y-axis of the graph (straight line equation)" (Figure 2).

[0123] (1-3) Explanation of specific example 1 The refrigerant composition may be, for example, 60% by mass of HFO-1132(E / Z) as a disproportionating refrigerant and 40% by mass of HFO-1234yf as a non-disproportionating refrigerant, based on the total refrigerant contained in the air conditioning system; When the temperature condition is 150°C and the pressure condition is 3.00 MPa, the composition contains a refrigerant in which "disproportionation reaction occurs."

[0124] (2) Specific example 2 The refrigerant composition contains 60 mass% of HFO-1132(E / Z) as a disproportionating refrigerant and 40 mass% of HFO-1234yf as a non-disproportionating refrigerant, based on the total amount of refrigerant contained in the composition.

[0125] The temperature condition is set to 150°C.

[0126] The pressure condition is set to 2.00 MPa.

[0127] It is verified whether a disproportionation reaction occurs under the above refrigerant composition, temperature conditions, and pressure conditions.

[0128] (2-1) Calculate the right hand side of "y = -1.5761x + 3.9516" (-1.5761x + 3.9516) The common logarithm (log) on ​​the x-axis indicates the concentration (mol) of the disproportionating refrigerant in the gas phase of the composition. / m 3 )" is calculated.

[0129] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 52.060 kg / m at 130°C and 2.00 MPa. 3 ].

[0130] The concentration of the disproportionating refrigerant (HFO-1132 (E / Z), Mw: 64.035) is: 48.657 [kg / m 3 ]×0.6÷64.035[g / mol]= 455.91[mol / m 3 ] becomes.

[0131] The x-axis is log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) =log(455.91) =2.6589.

[0132] In the relationship between x and y: y = -1.5761x + 3.9516, if you substitute "2.6589" for "x", "y" becomes "-0.23909".

[0133] Next, separately, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculate When the calculated value is "lower" than the value of "y" above, "-0.23909", that is, when the relationship between x and y is When the temperature crosses the graph and is "bottom left" of the boundary line of the graph (Fig. 2), the air conditioning system The system enables operation of an air conditioning system using a composition that "suppresses disproportionation reactions" when operated under the above refrigerant composition, temperature, and pressure conditions. The "bottom left of the graph" is the "position on the negative side of the y-axis of the graph (linear equation)."

[0134] Or, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculated When the value is "high" compared to the "y" value "-0.23909" mentioned above, that is, when the graph of the relationship between x and y When the temperature crosses the boundary line of the graph and becomes "upper right" from the boundary line of the graph (Figure 2), the air conditioning system When operating under the above refrigerant composition, temperature, and pressure conditions, the air conditioning system is operated using a composition that "causes a disproportionation reaction." The "upper right of the graph" is the "position on the positive side of the y-axis of the graph (linear equation)."

[0135] In other words, the refrigerant is controlled within the range y < -1.5761x + 3.9516. This makes it possible to operate an air conditioning system in which disproportionation reactions are suppressed.

[0136] (2-2) Calculating the left side of "y" in "y = -1.5761x + 3.9516" The common logarithm (log) on ​​the y-axis indicates the thermal diffusivity (mm 2 / s) is calculated.

[0137] The "thermal conductivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 27.265 [mW / (m K)] at 150°C and 2.00 MPa.

[0138] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 48.657 kg / m at 150°C and 2.00 MPa. 3 ].

[0139] The specific heat of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 1.1962 [kJ / kg K] at 150°C and 2.00 MPa.

[0140] The "thermal diffusivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) at 150°C and 2.00 MPa is 27.265 [mW / (m K)] ÷ (48.657 [kg / m 3 ]×1.1962 [kJ / kg K])=0.46844[mm 2 / s].

[0141] The y-axis is log(thermal diffusivity of the total refrigerant contained in the composition (mm 2 / s)) =log(0.46844) =-0.32935.

[0142] This y (log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)” value of “-0.32935” is calculated by the above “-1.5761x + 3.9516” (x: log(concentration of the disproportionating refrigerant in the gas phase of the composition (mol / m 3 ))) is "lower" than the value of "-0.23909", that is, when it straddles the graph of the relationship between X and y and is "bottom left" of the boundary line of the graph, in other words, when it is "positioned on the negative side of the y-axis of the graph (straight line equation)" (Figure 2).

[0143] (2-3) Explanation of specific example 2 The refrigerant composition may be, for example, 60% by mass of HFO-1132(E / Z) as a disproportionating refrigerant and 40% by mass of HFO-1234yf as a non-disproportionating refrigerant, based on the total refrigerant contained in the air conditioning system; When the temperature condition is 130°C and the pressure condition is 2.00 MPa, the composition contains a refrigerant in which "disproportionation reaction is suppressed (does not occur)."

[0144] (3) Specific example 3 The refrigerant composition contains 50 mass% of HFO-1132(E / Z) as a disproportionating refrigerant and 50 mass% of HFO-1234yf as a non-disproportionating refrigerant, based on the total amount of refrigerant contained in the composition.

[0145] The temperature condition is set to 150°C.

[0146] The pressure condition is set to 5.00 MPa.

[0147] It is verified whether a disproportionation reaction occurs under the above refrigerant composition, temperature conditions, and pressure conditions.

[0148] (3-1) Calculate the right hand side of "y = -1.5761x + 3.9516" (-1.5761x + 3.9516) The common logarithm (log) on ​​the x-axis indicates the concentration (mol) of the disproportionating refrigerant in the gas phase of the composition. / m 3 )" is calculated.

[0149] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 153.33 kg / m at 150°C and 5.00 MPa. 3 ].

[0150] The concentration of the disproportionating refrigerant (HFO-1132 (E / Z), Mw: 64.035) is: 153.33 [kg / m 3 ]×0.5÷64.035[g / mol]=1197.2[mol / m 3 ] becomes.

[0151] The x-axis is log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) =log(1197.2) =3.0782.

[0152] In the relationship between x and y: y = -1.5761x + 3.9516, if you substitute "3.0782" for "x", "y" becomes "-0.89995".

[0153] Next, separately, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculate When the calculated value is "lower" than the value of "y" above, "-0.89995", that is, when the relationship between x and y is When the temperature crosses the graph and is "bottom left" of the boundary line of the graph (Fig. 2), the air conditioning system The system enables operation of an air conditioning system using a composition that "suppresses disproportionation reactions" when operated under the above refrigerant composition, temperature, and pressure conditions. The "bottom left of the graph" is the "position on the negative side of the y-axis of the graph (linear equation)."

[0154] Or, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculated When the value is "high" compared to the "y" value "-0.89995" mentioned above, that is, when the graph of the relationship between x and y When the temperature crosses the boundary line of the graph and becomes "upper right" from the boundary line of the graph (Figure 2), the air conditioning system When operating under the above refrigerant composition, temperature, and pressure conditions, the air conditioning system is operated using a composition that "causes a disproportionation reaction." The "upper right of the graph" is the "position on the positive side of the y-axis of the graph (linear equation)."

[0155] In other words, the refrigerant is controlled within the range y < -1.5761x + 3.9516. This makes it possible to operate an air conditioning system in which disproportionation reactions are suppressed.

[0156] (3-2) Calculating the left side of the equation "y" in "y = -1.5761x + 3.9516" The common logarithm (log) on ​​the y-axis indicates the thermal diffusivity (mm 2 / s) is calculated.

[0157] The "thermal conductivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 30.660 [mW / (m K)] at 150°C and 5.00 MPa.

[0158] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 153.33 kg / m at 150°C and 5.00 MPa. 3 ].

[0159] The specific heat of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 60 + 40) is 1.4033 [kJ / kg K] at 150°C and 5.00 MPa.

[0160] The "thermal diffusivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 150℃, 5.00MPa. In this case, 30.660 [mW / (m K)] ÷ (153.33 [kg / m 3 ]×1.4033[kJ / kg K])=0.14249[mm 2 / s].

[0161] The y-axis is log(thermal diffusivity of the total refrigerant contained in the composition (mm 2 / s)) =log(0.14249) =-0.84622.

[0162] This y (log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)” value of “-0.84622” is calculated by the above “-1.5761x + 3.9516” (x: log(concentration of the disproportionating refrigerant in the gas phase of the composition (mol / m 3 ))) is "higher" than the value of "-0.89995", that is, when it straddles the graph of the relationship between X and y and is "upper right" above the boundary line of the graph, in other words, when it is "on the positive side of the y-axis of the graph (straight line equation)" (Figure 2).

[0163] (3-3) Explanation of specific example 3 The refrigerant composition may be, for example, 50% by mass of HFO-1132(E / Z) as a disproportionating refrigerant and 50% by mass of HFO-1234yf as a non-disproportionating refrigerant, based on the total refrigerant contained in the air conditioning system; When the temperature condition is 150°C and the pressure condition is 5.00 MPa, the composition contains a refrigerant in which "disproportionation reaction occurs."

[0164] (4) Specific example 4 The refrigerant composition contains 50 mass% of HFO-1132(E / Z) as a disproportionating refrigerant and 50 mass% of HFO-1234yf as a non-disproportionating refrigerant, based on the total amount of refrigerant contained in the composition.

[0165] The temperature condition is set to 150°C.

[0166] The pressure condition is set to 4.00 MPa.

[0167] It is verified whether a disproportionation reaction occurs under the above refrigerant composition, temperature conditions, and pressure conditions.

[0168] (4-1) Calculate the right hand side of "y = -1.5761x + 3.9516" (-1.5761x + 3.9516) The common logarithm (log) on ​​the x-axis indicates the concentration (mol) of the disproportionating refrigerant in the gas phase of the composition. / m 3 )" is calculated.

[0169] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 115.46 kg / m at 150°C and 4.00 MPa. 3 ].

[0170] The concentration of the disproportionating refrigerant (HFO-1132 (E / Z), Mw: 64.035) is: 115.46 [kg / m 3 ]×0.5÷64.035[g / mol]= 901.54[mol / m 3 ] becomes.

[0171] The x-axis is log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) =log(901.54) =2.9550.

[0172] In the relationship between x and y: y = -1.5761x + 3.9516, if you substitute "2.9550" for "x", "y" becomes "-0.70578".

[0173] Next, separately, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculate When the calculated value is "lower" than the value of "y" above, "-0.70578", that is, when the relationship between x and y is When the temperature crosses the graph and is "bottom left" of the boundary line of the graph (Fig. 2), the air conditioning system When the system is operated under the above refrigerant composition, temperature, and pressure conditions, "disproportionation reaction is suppressed." The composition can be used to operate an air conditioning system. The "bottom left of the graph" is the "position on the negative side of the y-axis of the graph (linear equation)."

[0174] Or, log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) and calculated When the value is "high" compared to the "y" value "-0.70578" mentioned above, that is, when the graph of the relationship between x and y When the temperature crosses the boundary line of the graph and becomes "upper right" from the boundary line of the graph (Figure 2), the air conditioning system When operating under the above refrigerant composition, temperature, and pressure conditions, the air conditioning system is operated using a composition that "causes a disproportionation reaction." The "upper right of the graph" is the "position on the positive side of the y-axis of the graph (linear equation)."

[0175] In other words, the refrigerant is controlled within the range y < -1.5761x + 3.9516. This makes it possible to operate an air conditioning system in which disproportionation reactions are suppressed.

[0176] (4-2) Calculating the left side of the equation "y" in "y = -1.5761x + 3.9516" The common logarithm (log) on ​​the y-axis indicates the thermal diffusivity (mm 2 / s) is calculated.

[0177] The "thermal conductivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 28.922 [mW / (m K)] at 150°C and 4.00 MPa.

[0178] The density of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 115.46 kg / m at 150°C and 4.00 MPa. 3 ].

[0179] The specific heat of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) is 1.3162 [kJ / kg K] at 150°C and 4.00 MPa.

[0180] The "thermal diffusivity" of the entire refrigerant (HFO-1132(E / Z) + HFO-1234yf = 50 + 50) at 150°C and 4.00 MPa is 28.922 [mW / (m K)] ÷ (115.46 [kg / m 3 ]×1.3162 [kJ / kg K])=0.19031[mm 2 / s].

[0181] The y-axis is log(thermal diffusivity of the total refrigerant contained in the composition (mm 2 / s)) =log(0.19031) =-0.72054.

[0182] This y (log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)” value of “-0.72054” is calculated by the above “-1.5761x + 3.9516” (x: log(concentration of the disproportionating refrigerant in the gas phase of the composition (mol / m 3 ))) is "lower" than the value of "-0.70578", that is, when it straddles the graph of the relationship between X and y and is "bottom left" of the boundary line of the graph, in other words, when it is "positioned on the negative side of the y-axis of the graph (straight line equation)" (Figure 2).

[0183] (4-3) Explanation of specific example 4 The refrigerant composition may be, for example, 50% by mass of HFO-1132(E / Z) as a disproportionating refrigerant and 50% by mass of HFO-1234yf as a non-disproportionating refrigerant, based on the total refrigerant contained in the air conditioning system; When the temperature condition is 150°C and the pressure condition is 4.00 MPa, the operation is carried out with a composition containing a refrigerant in which "disproportionation reaction is suppressed (does not occur)."

[0184] (5) Application of specific examples of use of the composition When the composition of the present disclosure is used in an air conditioning system, for example, as described in the above specific examples 1 to 4, under an ignition energy of, for example, 30 J, The refrigerant is calculated using the formula: y <-1.5761x + 3.9516 x = log(concentration of disproportionating refrigerant in the vapor phase of the composition (mol / m 3 )) y = log(thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s)) When the air conditioning system is operated under conditions controlled within the range shown by (1), it becomes possible to operate the air conditioning system with the disproportionation reaction suppressed.

[0185] The above explanation assumes that, for example, under an ignition energy of 500 J, The refrigerant is calculated using the formula: y < -1.4941x + 3.6044 When the air conditioning system is operated under conditions controlled within this range, it becomes possible to operate the air conditioning system with the disproportionation reaction suppressed.

[0186] When the composition of the present disclosure is used in, for example, an air conditioning system, the range of x is preferably −0.59 or more and 4.23 or less, more preferably 2.2 or more and 3.4 or less, so that the disproportionation reaction is well suppressed. The range of y is based on the formula and follows the range of x above.

[0187] At an ignition energy of 500 J, the disproportionation reaction occurs under the following conditions: The conditions under which the disproportionation reaction occurs at an ignition energy of 500 J are within the allowable range of conditions under which the disproportionation reaction is suppressed. The conditions under which the disproportionation reaction is suppressed at an ignition energy of 500 J are within the allowable range of conditions under which the disproportionation reaction is suppressed at an ignition energy of 30 J. These conditions are more preferable than those under which the disproportionation reaction is suppressed.

[0188] [3] Refrigerating machine oil The composition of the present disclosure preferably further contains a refrigerating machine oil and is used as a working fluid in a refrigerator (a working fluid for a refrigerator) or a working fluid containing a refrigerating machine oil.

[0189] Specifically, the composition of the present disclosure is obtained as a refrigerating machine oil-containing working fluid by mixing a refrigerating machine oil used in a compressor of a refrigerator with a refrigerant.

[0190] The composition of the present disclosure contains a refrigerating machine oil, and its composition changes during the refrigeration cycle. Specifically, the refrigerating machine oil content of the composition of the present disclosure is relatively high inside the compressor, and is relatively low during the period from when the composition is discharged from the compressor in the form of a mist, circulates through the refrigeration cycle, and returns to the compressor. For example, the refrigerating machine oil content of the composition of the present disclosure is 30% by mass to 70% by mass inside the compressor, and is preferably 0% by mass to 20% by mass, more preferably 1 ppm by mass to 10% by mass, during the period from when the composition is discharged from the compressor and returns to the compressor.

[0191] Refrigeration oil is primarily a base oil and a lubricant.

[0192] The refrigerating machine oil is preferably a polyalkylene glycol (PAG), a polyol ester, or a mixture thereof. Item 4. The composition according to item 3, comprising at least one polymer selected from the group consisting of polyvinyl ether (POE), polyvinyl ether (PVE), silicone oil, and fluorinated oil.

[0193] An example of the polyalkylene glycol (PAG) is "SUNICE P56" manufactured by Nippon Sun Oil Co., Ltd. An example of the polyol ester (POE) is "Ze-GLES RB32" manufactured by JX Nippon Oil & Energy Corporation.

[0194] In addition to the base oil, the refrigerating machine oil preferably further contains at least one additive. is preferably at least one component selected from the group consisting of a compatibilizer, an ultraviolet fluorescent dye, a stabilizer, a polymerization inhibitor, 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.

[0195] From the viewpoint of lubrication, the refrigerating machine oil preferably has a kinematic viscosity at 40°C of 5 cSt to 400 cSt. do.

[0196] In addition to the base oil, the refrigerating machine oil preferably further contains an additive, which is preferably at least one selected from the group consisting of a compatibilizer, 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.

[0197] The compatibilizer is not particularly limited and can be appropriately selected from commonly used compatibilizers. The compatibilizer is preferably, for example, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether, 1,1,1-trifluoroalkane, etc. Among these, polyoxyalkylene glycol ether is more preferred. The refrigerating machine oil may preferably contain one type of compatibilizer alone or two or more types.

[0198] The refrigerating machine oil-containing working fluid preferably contains a trace amount of water, which stabilizes the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant. Furthermore, the refrigerating machine oil-containing working fluid also contains a trace amount of water, which makes oxidation of the unsaturated fluorocarbon compounds less likely to occur, thereby improving the stability of the refrigerant.

[0199] The tracer is added to the refrigerant in a detectable concentration so that any dilution, contamination, or other alteration of the refrigeration oil-containing working fluid can be traced. The tracer may be added singly or in combination.

[0200] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.Preferred examples of the ultraviolet fluorescent dye include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as derivatives thereof.Of these, naphthalimide and coumarin are preferred.The ultraviolet fluorescent dye may be contained alone or in combination of two or more.

[0201] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers, and preferred examples of the stabilizer include nitro compounds, ethers, amines, butylhydroxyxylene, and benzotriazole.

[0202] The nitro compounds are preferably, for example, aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene. The ethers are preferably, for example, 1,4-dioxane. The amines are preferably, for example, 2,2,3,3,3-pentafluoropropylamine and diphenylamine. The stabilizer may be contained alone or in combination of two or more.

[0203] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors. The polymerization inhibitor is preferably, for example, 4-methoxy-1-naphthol, hydroxybenzoate, or the like. Hydroquinone, Hydroquinone methyl ether, Dimethyl-t-butylphenol, 2,6-di-tert- Examples of the polymerization inhibitor include butyl-p-cresol and benzotriazole. One type of polymerization inhibitor may be contained alone, or two or more types may be contained.

[0204] [4] Air conditioning system operation method The compositions of the present disclosure are preferably used in operating air conditioning systems.

[0205] The compositions of the present disclosure are preferably used in a refrigeration method that includes operating a refrigeration cycle.

[0206] The composition of the present disclosure is preferably used in a method for operating a refrigeration cycle of a refrigeration device, the refrigeration device being preferably an air conditioner, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerated showcase, a freezer / refrigeration unit, a refrigerator for a refrigerated warehouse, an automotive air conditioner, a turbo refrigerator, or a screw refrigerator.

[0207] [5] Method for storing a composition containing a refrigerant In a method of storing a refrigerant-containing composition of the present disclosure, The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The process includes a step in which the range is as shown in FIG.

[0208] In a method of storing a refrigerant-containing composition of the present disclosure, The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The process includes a step in which the range is as shown in FIG.

[0209] In the method of storing a refrigerant-containing composition of the present disclosure, preferably the non-disproportionating refrigerant comprises at least one component selected from the group consisting of HFO-1243zf, CF3I, HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye(E / Z), CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia.

[0210] The method for storing a composition containing a refrigerant of the present disclosure preferably further includes a step of adding a refrigerating machine oil.

[0211] The components of the refrigerant, refrigerating machine oil, etc. used in the method for storing a refrigerant-containing composition of the present disclosure can be the components described in the section on the composition.

[0212] [6] Refrigerant mixing method In the method of mixing refrigerants of the present disclosure, The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of , The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The range is as shown below.

[0213] In the method of mixing refrigerants of the present disclosure, The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The range is as shown below.

[0214] In the method of blending a refrigerant-containing composition of the present disclosure, preferably the non-disproportionated refrigerant comprises at least one component selected from the group consisting of HFO-1243zf, CF3I, HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye(E / Z), CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia.

[0215] The method of mixing a composition containing a refrigerant of the present disclosure preferably further includes a step of adding a refrigerating machine oil.

[0216] The components of the refrigerant, refrigerating machine oil, etc. used in the method of mixing refrigerants of the present disclosure can be the components described in the composition section above.

[0217] [7] Methods for suppressing disproportionation reactions In the method for suppressing a disproportionation reaction of a refrigerant disclosed herein, The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.5761x + 3.9516 The range is as shown below.

[0218] In the method for suppressing a disproportionation reaction of a refrigerant disclosed herein, The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated consists of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. At least one component selected from the group The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, The refrigerant is calculated by the formula: y < -1.4941x + 3.6044 The range is as shown below.

[0219] Disproportionation is the process of disproportionating ethylene-based fluorine compounds with double bonds, such as HFO-1132(E), to the same chemical species. A chemical reaction in which two or more hydrocarbons (each component of a hydrocarbon) react with each other to give two or more different products.

[0220] The method for suppressing a disproportionation reaction of the present disclosure has the above-described configuration, and therefore, it is possible to suppress a disproportionation reaction by using at least one refrigerant selected from the group consisting of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114. It has the property of suppressing the disproportionation reaction of

[0221] The method for inhibiting a disproportionation reaction disclosed herein comprises using at least one refrigerant selected from the group consisting of HFO-1132(E / Z), HFO-1132a, HFO-1123, and HFO-1114 (or a composition containing such a refrigerant). and the refrigerant that does not disproportionate, as determined by the concentration (mol / m) of the refrigerant that disproportionates in the gas phase of the composition. 3 ) is defined as x, and the thermal diffusivity (mm 2 / s) When the common logarithm (log) is y, the refrigerant is Formula: y < -1.5761x + 3.9516 By mixing under the conditions in the range shown by Formula: y < -1.4941x + 3.6044 By mixing under the conditions in the range shown in It is possible to suppress the disproportionation reaction of the refrigerant.

[0222] In the method of suppressing a disproportionation reaction of a refrigerant disclosed herein, the refrigerant that does not disproportionate preferably contains at least one component selected from the group consisting of HFO-1243zf, CF3I, HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye(E / Z), CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia.

[0223] The method for suppressing a disproportionation reaction of a refrigerant according to the present disclosure preferably further includes a step of adding a refrigerating machine oil.

[0224] The components of the refrigerant, refrigerating machine oil, etc. used in the method for inhibiting a disproportionation reaction of a refrigerant according to the present disclosure can be the components described in the section on the composition. [Example]

[0225] The present disclosure will be described in more detail below with reference to examples, although the present disclosure is not limited to these examples.

[0226] How to operate an air conditioning system Refrigerant In the air conditioning system including the above, the refrigerant composition was a mixed refrigerant containing a refrigerant that disproportionates and a refrigerant that does not disproportionate, and the temperature and pressure conditions of the refrigerant were adjusted.

[0227] (1) Examples of disproportionating refrigerants HFO-1132(E): trans-1,2-difluoroethylene HFO-1123: Trifluoroethylene HFO-1132a: 1,1-difluoroethylene

[0228] (2) Examples of refrigerants that do not disproportionate HFO-1234yf: 2,3,3,3-tetrafluoropropene HFC-32: Difluoromethane HFO-1243zf: 3,3,3-trifluoropropene R13I1: Trifluoroiodomethane (CF3I) PFC-14: Perfluoromethane R290: Propane

[0229] (3) Temperature and pressure conditions Temperature: 25℃~180℃ Pressure: 0.60MPa to 5.34MPa Unless otherwise specified, pressure refers to absolute pressure.

[0230] (4) Ignition energy conditions Ignition energy: 30J (Tables 1-5) Ignition energy: 500J (Table 6) The ignition energy was optimized by adjusting the voltage, current, and time so that disproportionation would most easily occur under the same heat quantity.

[0231] (5) Results As shown in the table, in an air conditioning system, by adjusting the composition of the refrigerant that disproportionates and the refrigerant that does not disproportionate in the mixed refrigerant, and by adjusting the temperature and pressure conditions under which the mixed refrigerant is used, the conditions were divided into those under which the disproportionation reaction was suppressed (results marked with ○) and those under which the disproportionation reaction occurred (results marked with ×).

[0232] Table results ○: Conditions under which disproportionation reaction is suppressed Results in the table ×: Conditions under which disproportionation reaction occurs

[0233] (6) Ignition energy of Tables 1 to 5: 30 J

[0234] [Table 1]

[0235] [Table 2]

[0236] [Table 3]

[0237] [Table 4]

[0238] [Table 5]

[0239] In Tables 1 to 5, the conditions under which the disproportionation reaction is suppressed at an ignition energy of 30 J are evaluated as "○". The condition where the disproportionation reaction occurs is expressed as "x".

[0240] (7) Ignition energy in Table 6: 500J [Table 6]

[0241] In Table 6, the conditions under which the disproportionation reaction is suppressed at an ignition energy of 500 J are evaluated as "○". Table 6 shows the more favorable conditions for suppressing the disproportionation reaction. In the condition where the disproportionation reaction occurs, the "△" rating is given to the condition where the disproportionation reaction occurs at an ignition energy of 30 J. The condition in which the disproportionation reaction occurs at an ignition energy of 500 J is evaluated as "△", which is within the allowable range for suppressing the disproportionation reaction in this disclosure, and is therefore referred to as a "reference example".

[0242] Based on the results, the conditions under which the disproportionation reaction is suppressed (results marked with ○) and the conditions under which the disproportionation reaction occurs (results marked with ×) are plotted (Figure 2), with the y-axis representing the thermal diffusivity of the entire refrigerant and the x-axis representing the concentration of the disproportionating refrigerant in the gas phase of the composition. The boundary between the two is approximated as follows: It can be expressed as the formula:

[0243] (8) Discussion of the results Based on the results, when a composition containing a refrigerant is used, for example, in an air conditioning system, the refrigerant includes a disproportionating refrigerant such as HFO-1132(E), HFO-1132a, or HFO-1123, and a non-disproportionating refrigerant such as HFO-1234yf, HFC-32, HFO-1243zf, trifluoroiodomethane (CF3I), PFC-14, or propane, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of ( / s) is y, When operating the air conditioning system, assuming an ignition energy of 30J, Formula: y <-1.5761x + 3.9516 For the line obtained by, or When operating the air conditioning system, assuming an ignition energy of 500J, Formula: y < -1.4941x + 3.6044 The refrigerant that disproportionates and the refrigerant that does not disproportionate are plotted on the negative side ( ) (the area occupied by "○" and the area "bottom left of the graph"), it can be said that "disproportionation of the refrigerant is suppressed" in the air conditioning system.

Claims

1. 1. A method for storing a composition containing a refrigerant and a stabilizer, comprising: The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); Under 30J ignition energy, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The refrigerant is mixed with a refrigerant having a temperature of 1000° C. or less according to the formula: y < −1.5761x + 3.9516 and adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature, pressure and / or refrigerant composition are within the ranges indicated by the formula:

2. 1. A method for storing a composition containing a refrigerant and a stabilizer, comprising: The refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); Under 500J ignition energy, The concentration (mol / m) of the disproportionating refrigerant in the gas phase of the composition 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The refrigerant is mixed with a refrigerant having a temperature of 1000° C. or less according to the formula: y < −1.4941x + 3.6044 and adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature, pressure and / or refrigerant composition are within the ranges indicated by the formula:

3. 1. A method for mixing refrigerants, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); The composition obtained by the mixing step further contains a stabilizer, Under 30J ignition energy, The concentration (mol / m) of the refrigerant to be disproportionated in the gas phase of the composition obtained by the mixing step 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The refrigerant is mixed with a refrigerant having a temperature of 1000° C. or less according to the formula: y < −1.5761x + 3.9516 and adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature, pressure and / or refrigerant composition are within the ranges indicated by the formula:

4. 1. A method for mixing refrigerants, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); The composition obtained by the mixing step further contains a stabilizer, Under 500J ignition energy, The concentration (mol / m) of the refrigerant to be disproportionated in the gas phase of the composition obtained by the mixing step 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The refrigerant is mixed with a refrigerant having a temperature of 1000° C. or less according to the formula: y < −1.4941x + 3.6044 and adjusting or controlling the temperature, pressure and / or refrigerant composition so that the temperature, pressure and / or refrigerant composition are within the ranges indicated by the formula:

5. A method for suppressing a disproportionation reaction of a refrigerant, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); The composition obtained by the mixing step further contains a stabilizer, Under 30J ignition energy, The concentration (mol / m) of the refrigerant to be disproportionated in the gas phase of the composition obtained by the mixing step 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The refrigerant is mixed with a refrigerant having a temperature of 1000° C. or less according to the formula: y < −1.5761x + 3.9516 The method according to claim 1, wherein the range is set as shown in

6. A method for suppressing a disproportionation reaction of a refrigerant, comprising: The method includes a step of mixing a refrigerant to be disproportionated with a refrigerant that is not disproportionated, The refrigerant to be disproportionated contains at least one component selected from the group consisting of trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (HFO-1114); The composition obtained by the mixing step further contains a stabilizer, Under 500J ignition energy, The concentration (mol / m) of the refrigerant to be disproportionated in the gas phase of the composition obtained by the mixing step 3 ) is taken as x, The thermal diffusivity (mm 2 When the common logarithm (log) of (√s) is y, The method, characterized in that the refrigerant is in the range represented by the formula: y < -1.4941x + 3.6044.

7. The non-disproportionating refrigerant is 3,3,3-trifluoropropene (HFO-1243zf), trifluoroiodomethane (CF 3 I), difluoromethane (HFC-32), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), hexafluoropropene (FO-1216), perfluoromethane (PFC-14), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), CF 3 SCF 3 7. The method according to claim 1, wherein the mixture contains at least one component selected from the group consisting of propane, cyclopropane, propylene, isobutene, isobutane, carbon dioxide, and ammonia.

8. The method according to any one of claims 1 to 7, wherein the composition further contains a refrigerating machine oil and is used as a refrigerating machine oil-containing working fluid.

9. 9. The method according to claim 8, wherein the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), polyvinyl ether (PVE), silicone oil, and fluorinated oil.

10. The method according to any one of claims 1 to 9, used in an air conditioning system.

11. An air conditioning system using the method according to any one of claims 1 to 10.

12. A refrigeration method comprising the step of operating a refrigeration cycle using the method according to any one of claims 1 to 10.

13. A method for operating a refrigeration system, comprising operating a refrigeration cycle using the method according to any one of claims 1 to 10.

14. A refrigeration device using the method according to any one of claims 1 to 10.

15. 15. The refrigeration device according to claim 14, which is an air conditioner, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a freezer showcase, a freezer / refrigerator unit, a freezer for a freezer / refrigerator warehouse, an in-vehicle air conditioner, a turbo freezer, or a screw freezer.

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