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

Abstract

The invention provides a mixed refrigerant which can be used as an alternative refrigerant of R410A, has excellent performance coefficient and freezing capacity, is sufficiently low in GWP (global warming potential), and is non-combustible. Specifically, the present invention provides a refrigerant-containing composition characterized in that the refrigerant contains trifluoroiodomethane (CF3I) and difluoromethane (R32), and when the total amount of CF3I and R32 is taken as 100 mass%, the respective contents of CF3I and R32 in the refrigerant are 48 mass% > = CF3I > = 46 mass% and 54 mass% > = R32 > = 52 mass%.

Description

Technical Field

[0001] This invention relates to compositions containing refrigerant, their uses, and refrigerators having the compositions and methods of operating the refrigerators. Background Technology

[0002] R410A is currently used as a refrigerant for household air conditioners and other applications. R410A is a two-component mixture of difluoromethane (CH2F2; R32) and pentafluoroethane (C2HF5; R125), a near-azeotropic composition.

[0003] However, R410A has a global warming coefficient (GWP) of 2088, and due to increased concerns about global warming, R32, with a GWP of 675, is being used more extensively. Therefore, various low-GWP refrigerant blends have been proposed as alternatives to R410A (Patent Document 1).

[0004] In addition, as existing literature related to this invention, Patent Documents 2 and 3 disclose refrigerant compositions containing trifluoroiodomethane (CF3I).

[0005] Existing technical documents Patent documents Patent Document 1: International Publication No. 2015 / 141678 Patent Document 2: Japanese Patent Application Publication No. 2009-24152 Patent Document 3: Japanese Patent Application Publication No. 8-277389 Summary of the Invention

[0006] The problem that the invention aims to solve Through independent research, the inventors of this invention conceived of developing a refrigerant composition that combines four properties: the ability to replace the existing refrigerant R410A, excellent coefficient of performance (COP) and refrigeration capacity (cooling capacity, sometimes also referred to as capacity), sufficiently low gas per watt (GWP), and non-flammability. The object of this invention is to solve this unique problem.

[0007] Methods for solving problems 1. A composition containing a refrigerant, characterized in that: The above-mentioned refrigerant contains trifluoroiodine methane (CF3I) and difluoromethane (R32). When the total amount of CF3I and R32 in the above-mentioned refrigerant is set to 100% by mass, the contents of CF3I and R32 are respectively 48% by mass ≥ CF3I ≥ 46% by mass and 54% by mass ≥ R32 ≥ 52% by mass.

[0008] 2. A composition containing a refrigerant, characterized in that: The aforementioned refrigerant contains trifluoroiodomethane (CF3I), difluoromethane (R32), and pentafluoroethane (R125). When the mass percentages of R32, R125, and CF3I are set as x, y, and z respectively, in a three-component composition diagram where the sum of R32, R125, and CF3I is 100% by mass, the coordinates (x, y, z) of the composition lie within the area bounded by the line segments EF, FD, DX, and XE connecting the points E, F, D, and X respectively, but excluding the line segment FD. Point E (53.7, 11.0, 35.3). Point F (51.6, 0.0, 48.4). Point D (65.0, 0.0, 35.0). Point X (64.6.8.9, 26.5). The line segment EF is defined by coordinates (x, -1.1255x). 2 +123.76x - 3389.3, 1.1255x 2 -124.76x+3489.3) represents, and the above line segments FD, DX and XE are straight lines.

[0009] 3. A composition containing a refrigerant, characterized in that: The above-mentioned refrigerant contains trifluoroiodomethane (CF3I) and trans-1,2-difluoroethylene (HFO-1132(E)). The total amount of CF3I and HFO-1132(E) in the above-mentioned refrigerant is set to 100% by mass. The content of CF3I and HFO-1132(E) is 68% by mass ≥ CF3I ≥ 62% by mass and 38% by mass ≥ HFO-1132(E) ≥ 32% by mass.

[0010] 4. A composition containing a refrigerant, characterized in that: The aforementioned refrigerant contains trifluoroiodomethane (CF3I), difluoromethane (R32), and trans-1,2-difluoroethylene (HFO-1132(E)). When the mass percentages of HFO-1132(E), CF3I, and R32, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), CF3I, and R32 equals 100% by mass, the coordinates (x, y, z) of this composition lie within the area bounded by line segments JH, HY, and YJ connecting points Y, J, and H respectively, but excluding line segment JH. Point Y (32.5, 58.1, 9.4), Point J (0.0. 77.2, 22.8). Point H (0.0. 35.0, 65.0), The line segment YJ mentioned above is defined by coordinates (x, -0.0027x). 2 -0.5002x + 77.2, 0.0027x 2 -0.4998x+22.8) represents that the above line segments JH and HY are straight lines.

[0011] 5. A composition containing a refrigerant, characterized in that: The aforementioned refrigerant contains trifluoroiodimethane (CF3I), difluoromethane (R32), and trifluoroethylene (HFO-1123). When the mass percentages of HFO-1123, CF3I, and R32 (based on their sum) are set as x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1123, CF3I, and R32 is 100% by mass, the coordinates (x, y, z) of the composition lie within the area bounded by the line segments ZN, NL, and LZ connecting points Z, N, and L, respectively, but excluding the line segment NL. Point Z (41.6, 53.5, 4.9). Point N (0.0. 77.2, 22.8). Point L (0.0. 35.0, 65.0), The above line segment ZN is defined by coordinates (x, -0.0007x). 2 -0.5402x + 77.2, 0.0007x 2 -0.4598x+22.8) represents that the above line segments NL and LZ are straight lines.

[0012] 6. A composition containing a refrigerant, characterized in that: The aforementioned refrigerant contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I), and 2,3,3,3-tetrafluoroethylene (HFO-1234yf). The total concentration of R32, R125, CF3I, and HFO-1234yf was set to 100% by mass, and the concentration of HFO-1234yf was set to x% by mass. The aforementioned refrigerant composition includes one of refrigerant A or refrigerant B in the three-component composition diagram, where the total concentration of R32, R125, and CF3I is shown as (100-x) wt%. Refrigerant A: (1) -1 11.7% mass ≥ x ≥ 6.0% mass (1) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a quadrilateral or triangle with vertices C, D, F, and E, but excluding the line segment DF mentioned above. Point C (1.1753x + 41.14 / - 0.2282x + 13.464 / 100 - R1234yf - R32 - R125). Point D (0.0247x) 2 +0.563x+43.733 / 0.0 / 100-R1234yf-R32-R125), Point F (-0.8069x+64.948 / 0.0 / 100-R1234yf-R32-R125). Point E (-0.8247x+64.54 / 0.1581x+8.96 / 100-R1234yf-R32-R125); Refrigerant B: (2) -1 12.6% mass > x > 11.7% mass (2) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the triangle with vertices G, D, and F, but excluding the line segment DF mentioned above. Point G (-1.2222x) 2 +29.589x - 123.98 / 20.5x 2 -510.15x+3173.3 / 100-R1234yf-R32-R125), Point D (1.2213x+39.415 / 0.0 / 100-R1234yf-R32-R125). Point F (0.7787x+64.615 / 0.0 / 100-R1234yf-R32-R125).

[0013] 7. A composition containing a refrigerant, characterized in that: The aforementioned refrigerant contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I), and 1,3,3,3-tetrafluoropropylene (HFO-1234ze). The total concentration of R32, R125, CF3I, and HFO-1234ze was set to 100% by mass, and the concentration of HFO-1234ze was set to x% by mass. The aforementioned refrigerant composition includes one of refrigerant A or refrigerant B in the three-component composition diagram, where the total concentration of R32, R125, and CF3I is shown as (100-x) wt%. Refrigerant A: (1) -1 8.3% mass ≥ x ≥ 4.0% mass (1) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a quadrilateral or triangle with vertices C, D, F, and E, but excluding the line segment DF mentioned above. Point C (0.0435x) 2 +1.4652x+42.543 / -0.3726x+13.406 / 100-R1234ze-R32-R125), Point D (0.097x) 2 +0.6802x+44.628 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.8143x+64.967 / 0.0 / 100-R1234ze-R32-R125). Point E (-0.0061x) 2 -0.7393x+64.254 / 0.1631x+8.9386 / 100-R1234ze-R32-R125); Refrigerant B: (2) -1 8.9% mass > x > 8.3% mass (2) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the triangle with vertices G, D, and F, but excluding the line segment DF mentioned above. Point G (0.1667x + 56.3 / 2.7778x) 2 -64.944x+357.98 / 100-R1234ze-R32-R125), Point D (1.5625x) 2 -24.938x+155.98 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.6667x+63.733 / 0.0 / 100-R1234ze-R32-R125).

[0014] 8. The composition of any one of items 1 to 7 above, further comprising refrigeration oil, wherein the composition is used as a working fluid for a refrigeration unit.

[0015] 9. The composition as described in any one of items 1 to 8 above, which is used as an alternative refrigerant to R410A.

[0016] 10. Use of the composition of any one of items 1 to 8 above as an alternative refrigerant to R410A.

[0017] 11. A refrigeration machine comprising, as any one of claims 1 to 9 above, the composition as the working fluid.

[0018] 12. A method of operating a refrigeration machine, comprising the step of circulating the composition described in any one of items 1 to 9 above in the refrigeration machine as a working fluid.

[0019] The effects of the invention The refrigerant of this invention possesses four properties: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Therefore, the refrigerant of this invention and compositions containing it are useful, for example, as working fluids for refrigeration machines. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the apparatus used in the non-flammability test of refrigerant.

[0021] Figure 2 It is a diagram showing the composition of the refrigerant 2 of this application within the area enclosed by the line segments EF, FD, DX, and XE connecting the four points E, F, D, and X respectively (but excluding the line segment FD mentioned above) in a three-component composition diagram where the sum of R32, R125, and CF3I is 100% by mass.

[0022] Figure 3 This is a diagram showing the composition of the refrigerant 4 of this application within the area enclosed by the line segments JH, HY, and YJ connecting points Y, J, and H respectively (but excluding the line segment JH mentioned above) in a three-component composition diagram where the sum of HFO-1132(E), CF3I, and R32 is 100% by mass.

[0023] Figure 4 This is a diagram showing the composition of the refrigerant 5 of this application within the area enclosed by the line segments ZN, NL, and LZ connecting points Z, N, and L respectively (but excluding the line segment NL mentioned above) in a three-component composition diagram where the sum of HFO-1123, CF3I, and R32 is 100% by mass.

[0024] Figure 5This is a diagram showing the composition of the refrigerant 6 of this invention when X=6 mass% in the three-component composition diagram shown, where the total concentration of R32, R125, CF3I and HFO-1234yf is set to 100% by mass, the concentration of HFO-1234yf is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass. That is, the composition within the quadrilateral with points C, D, F and E as vertices (but excluding line segment DF).

[0025] Figure 6 This is a diagram showing the composition of the refrigerant 6 of this invention when X=9 mass% in the three-component composition diagram shown, where the total concentration of R32, R125, CF3I and HFO-1234yf is set to 100% by mass, the concentration of HFO-1234yf is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass. That is, the composition within the quadrilateral with points C, D, F and E as vertices (but excluding line segment DF).

[0026] Figure 7 This is a diagram showing the composition of the refrigerant 6 of this invention when X = 11.7 mass% in the three-component composition diagram shown, where the total concentration of R32, R125, CF3I and HFO-1234yf is set to 100% by mass, the concentration of HFO-1234yf is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass. That is, the composition within the triangle with points C (=E=G), D and F as vertices (but excluding line segment DF).

[0027] Figure 8 This is a diagram showing the composition of the refrigerant 6 of this invention when X = 12.1 mass% in the three-component composition diagram shown, where the total concentration of R32, R125, CF3I and HFO-1234yf is set to 100% by mass, the concentration of HFO-1234yf is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass. That is, the composition within the triangle with points G, D and F as vertices (but excluding line segment DF).

[0028] Figure 9 This refers to the graph in the three-component composition diagram where the total concentration of R32, R125, CF3I, and HFO-1234yf is set to 100% by mass, the concentration of HFO-1234yf is set to x% by mass, and the total concentration of R32, R125, and CF3I is set to (100-x)% by mass. When X = 12.6% by mass, the composition converges to point D (=F=G). Here, point D does not belong to the refrigerant 6 of this invention.

[0029] Figure 10 This is a diagram showing the composition of the refrigerant 7 of this invention when X=4 mass% in the three-component composition diagram shown, where the total concentration of R32, R125, CF3I and HFO-1234ze is set to 100% by mass, the concentration of HFO-1234ze is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass. That is, the composition within the quadrilateral with points C, D, F and E as vertices (but excluding line segment DF).

[0030] Figure 11 This is a diagram showing the composition of the refrigerant 7 of this invention when X=6% in the three-component composition diagram shown, with the total concentration of R32, R125, CF3I and HFO-1234ze set to 100% by mass, the concentration of HFO-1234ze set to x% by mass, and the total concentration of R32, R125 and CF3I set to (100-x)% by mass, i.e., the composition within the quadrilateral with points C, D, F and E as vertices (but excluding line segment DF).

[0031] Figure 12 This is a diagram showing the composition of the refrigerant 7 of this invention when X = 8.3% of the total concentration of R32, R125, CF3I and HFO-1234ze is set to 100% by mass, the concentration of HFO-1234ze is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass, i.e., the composition within the triangle with points C (=E=G), D and F as vertices (but excluding line segment DF).

[0032] Figure 13 This is a diagram showing the composition of the refrigerant 7 of this invention when X = 8.6% of the total concentration of R32, R125, CF3I and HFO-1234ze is set to 100% by mass, the concentration of HFO-1234ze is set to x% by mass, and the total concentration of R32, R125 and CF3I is set to (100-x)% by mass, i.e., the composition within the triangle with points G, D and F as vertices (but excluding line segment DF).

[0033] Figure 14 This refers to the graph in which the composition converges to point D (=F=G) when X=8.9% of the total concentration of R32, R125, CF3I, and HFO-1234ze is set to 100% by mass, the concentration of HFO-1234ze is set to x% by mass, and the total concentration of R32, R125, and CF3I is set to (100-x)% by mass, as shown in the three-component composition graph. Here, point D does not belong to the refrigerant 7 of this invention. Detailed Implementation

[0034] In order to solve the above-mentioned problems, the inventors of the present invention conducted in-depth research and found that a refrigerant containing a specific composition of trifluoroiodomethane (CF3I) has the above-mentioned characteristics.

[0035] This invention was completed based on such insights and further repeated research. The invention includes the following embodiments.

[0036] <Definition of Terms> In this invention, the term "refrigerant" includes at least compounds with refrigerant serial numbers (ASHRAE numbers) beginning with R, as defined by ISO 817 (International Organization for Standardization), and also compounds that, while not bearing a refrigerant serial number, possess equivalent refrigerant properties. Refrigerants are broadly classified into "fluorinated hydrocarbon compounds" and "non-fluorinated hydrocarbon compounds" based on their compound structure. "Fluorinated hydrocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Examples of "non-fluorinated hydrocarbon compounds" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717). In this invention, the term "composition containing refrigerant" includes at least: (1) refrigerant itself (including mixtures of refrigerants), (2) a composition further containing other components, which can be used to obtain a working fluid for a refrigeration unit by mixing with at least refrigeration oil, and (3) a working fluid for a refrigeration unit containing refrigeration oil. In this specification, of these three aspects, the composition of (2) is distinguished from the refrigerant itself (including mixtures of refrigerants) and is referred to as "refrigerant composition". In addition, the working fluid for a refrigeration unit of (3) is distinguished from "refrigerant composition" and is referred to as "working fluid containing refrigeration oil".

[0037] In this invention, the term "replacement" refers to the use of statements such as "replacing" the first refrigerant with the second refrigerant. As a first type, it means that in a machine designed to operate using the first refrigerant, it is possible to operate under optimal conditions using the second refrigerant by only slightly changing components (at least one of other components such as refrigeration oil, gaskets, liners, expansion valves, and dryers) and adjusting the machine as needed. That is, this type refers to "replacing" the refrigerant to operate the same machine. As for the methods of "replacement" of this type, depending on the degree of change or adjustment when replacing with the second refrigerant, they are ranked from smallest to largest as "simple drop-in replacement," "nearly simple drop-in replacement," and "retrofit."

[0038] As a second type, the use of a second refrigerant for the same purpose as the existing use of the first refrigerant is also included in the term "replacement." This type refers to providing the same purpose by "replacing" the refrigerant.

[0039] In this invention, the term "refrigerating machine" refers to any machine that removes heat from an object or space, making it colder than the surrounding air, and maintains such a low temperature. In other words, a refrigerating machine is an energy conversion device that works by obtaining energy from the outside in order to move heat from a colder area to a warmer area.

[0040] In this invention, "non-flammable" means that the WCF (Worst case of formulation for flammability), which is the most flammable component among the refrigerant's permissible concentrations in the American ANSI / ASHRAE 34-2013 standard, is judged as "Class 1 (i.e., WCF non-flammable)" or as ASHRAE non-flammable.

[0041] Furthermore, the non-flammability mentioned above is determined based on the testing apparatus and method according to the flammability test in ASTM E681-2009. Specifically, the test is performed as described below.

[0042] Use a 12-liter capacity Figure 1 The spherical glass flask shown allows for visual observation or video recording of the combustion process. When excessive pressure is generated due to combustion, the top lid opens to release gas. Ignition is achieved by discharging from an electrode positioned at a height of one-third of the distance from the bottom. The experimental conditions are described below.

[0043] <Experimental Conditions> Test container: 280 mm φ spherical (internal volume: 12 liters) Test temperature: 60℃±3℃ Pressure: 101.3 kPa ± 0.7 kPa Moisture content: 0.0088 g ± 0.0005 g in 1 g of dry air. Bi-component refrigerant composition / air mixing ratio: 1 vol.% ± 0.2 vol.% Mixing of binary refrigerant compositions: ±0.1% by mass Ignition method: AC discharge, voltage 15kV, current 30mA, neon transformer Electrode spacing: 6.4 mm (1 / 4 inch) Discharge duration: 0.4 seconds ± 0.05 seconds Judgment criteria: • When a flame exceeding 90 degrees Celsius spreads from its ignition point, it constitutes combustion (propagation). • A flame below 90 degrees Celsius will spread outward from its ignition point without flame propagation (non-combustible). 1. Refrigerant 1.1 Refrigerant components The refrigerants of the present invention can be broadly classified into Embodiments 1 to 7 (also referred to as refrigerants 1 to 7, respectively) according to their embodiments. Refrigerants 1 to 7 all possess four properties: they can be used as alternatives to R410A, they have excellent coefficient of performance and freezing capacity, they have sufficiently low gas per watt (GWP), and they are non-flammable. Therefore, refrigerants 1 to 7 and compositions containing refrigerants 1 to 7 are useful, for example, as working fluids for refrigeration machines. Hereinafter, refrigerants 1 to 7 will be described.

[0044] <Implementation Method 1: Refrigerant 1> The refrigerant 1 of the present invention is characterized in that it contains trifluoroiodimethane (CF3I) and difluoromethane (R32). When the total amount of CF3I and R32 is set to 100% by mass, the content of CF3I and R32 in the above refrigerant is 48% by mass ≥ CF3I ≥ 46% by mass and 54% by mass ≥ R32 ≥ 52% by mass. That is, refrigerant 1 is a mixed refrigerant.

[0045] Refrigerant 1 possesses four key properties: it can replace R410A, it has excellent coefficient of performance (COP) and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, its COP is over 98% of R32, its freezing capacity is over 95% of R32, its GWP is below 750 (especially below 400), and it also has the ASHRAE non-flammability property.

[0046] Refrigerant 1 contains CF3I and R32. When the total amount of CF3I and R32 is set to 100% by mass, the individual contents of CF3I and R32 in the refrigerant are 48% by mass ≥ CF3I ≥ 46% by mass and 54% by mass ≥ R32 ≥ 52% by mass. Furthermore, the total amount of CF3I and R32 in the refrigerant is preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and most preferably 99.9% by mass or more. In addition to CF3I and R32, other components in the refrigerant include byproducts unavoidably present during the manufacture of CF3I and R32.

[0047] In addition, the ASHRAE non-flammability limits of CF3I and R32 can be confirmed by the following steps.

[0048] Based on ANSI / ASHRAE 34-2013, leakage tests during storage, transportation, and use were simulated using REFPROP 9.0. The WCFF (Worst case of fractionation for flammability) was determined to be the initial mixture composition of CF3I and R32, calculated using the method described in Implementation Method 6, with a non-flammable limit composition (CF3I / R32) of (35 wt% / 65 wt%). The result was an initial mixture composition of (CF3I / R32) of (46 wt% / 54 wt%), which became the ASHRAE non-flammable limit.

[0049] <Implementation Method 2: Refrigerant 2> The refrigerant 2 of the present invention is characterized in that it contains trifluoroiodomethane (CF3I), difluoromethane (R32), and pentafluoroethane (R125). When the mass percentages of R32, R125, and CF3I based on their sum are set as x, y, and z, respectively, in a three-component composition diagram where the sum of R32, R125, and CF3I is 100% by mass, the coordinates (x, y, z) of the composition lie within the area enclosed by the line segments EF, FD, DX, and XE that connect the points E, F, D, and X, respectively (but excluding the line segment FD). Point E (53.7, 11.0, 35.3) Point F (51.6, 0.0, 48.4) Point D (65.0, 0.0, 35.0) and Point X (64.6.8.9, 26.5) The line segment EF is defined by coordinates (x, -1.1255x). 2 +123.76x - 3389.3, 1.1255x 2 -124.76x+3489.3) represents, and the above line segments FD, DX and XE are straight lines.

[0050] That is, refrigerant 2 is a mixed refrigerant.

[0051] When refrigerant 2 meets the above requirements, it possesses four properties: it can be used as a substitute for R410A, it has excellent coefficient of performance (COP) and refrigeration capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, its COP is 98% or higher relative to R32, its refrigeration capacity is 95% or higher relative to R32, its GWP is 750 or lower (especially 600 or lower), and it also possesses the non-flammable property of WCF. Refrigerant 2 contains R32, R125, and CF3I, wherein the combined amount of R32, R125, and CF3I in the refrigerant is preferably 99.5% by mass or higher, more preferably 99.7% by mass or higher, and most preferably 99.9% by mass or higher. In addition to R32, R125, and CF3I, other components in the refrigerant include byproducts that are unavoidably present during the manufacture of R32, R125, and CF3I.

[0052] <Implementation Method 3: Refrigerant 3> The refrigerant 3 of the present invention is characterized in that it contains trifluoroiodomethane (CF3I) and trans-1,2-difluoroethylene (HFO-1132(E)). When the total amount of CF3I and HFO-1132(E) is set to 100% by mass, the content of CF3I and HFO-1132(E) in the above-mentioned refrigerant is 68% by mass ≥ CF3I ≥ 62% by mass and 38% by mass ≥ HFO-1132(E) ≥ 32% by mass. That is, refrigerant 3 is a mixed refrigerant.

[0053] Refrigerant 3 possesses four key properties: it can replace R410A, it has excellent coefficient of performance (COP) and freezing capacity, it has a very low gas per watt (GWP), and it is non-flammable. Specifically, its COP is over 100% (especially over 105%) compared to R410A, its freezing capacity is over 65% compared to R410A, its GWP is below 1, and it also has the non-flammable properties of WCF.

[0054] Refrigerant 3 contains CF3I and HFO-1132(E). When the total amount of CF3I and HFO-1132(E) is set to 100% by mass, the content of CF3I and HFO-1132(E) in the refrigerant is 68% by mass ≥ CF3I ≥ 62% by mass, and 38% by mass ≥ HFO-1132(E) ≥ 32% by mass. Furthermore, the total amount of CF3I and HFO-1132(E) in the refrigerant is preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and most preferably 99.9% by mass or more. In addition to CF3I and HFO-1132(E), other components in the refrigerant include byproducts unavoidably present during the manufacture of CF3I and HFO-1132(E).

[0055] <Implementation Method 4: Refrigerant 4> The refrigerant 4 of the present invention is characterized in that it contains trifluoroiodomethane (CF3I), difluoromethane (R32), and trans-1,2-difluoroethylene (HFO-1132(E)). When the mass percentages of HFO-1132(E), CF3I, and R32, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), CF3I, and R32 is 100% by mass, the coordinates (x, y, z) of the composition lie within the area enclosed by the line segments JH, HY, and YJ connecting the points Y, J, and H respectively (excluding the aforementioned line segment JH). Point Y (32.5, 58.1, 9.4), Point J (0.0. 77.2, 22.8) and Point H (0.0, 35.0, 65.0) The line segment YJ mentioned above is defined by coordinates (x, -0.0027x). 2 -0.5002x + 77.2, 0.0027x 2 -0.4998x+22.8) represents that the above line segments JH and HY are straight lines.

[0056] That is, refrigerant 4 is a mixed refrigerant.

[0057] When refrigerant 4 meets the above requirements, it possesses four properties: it can be used as a replacement for R410A, it has excellent coefficient of performance (COP) and refrigeration capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, its COP is above 99% compared to R32, its refrigeration capacity is above 80% compared to R32, its GWP is below 750 (especially below 450), and it also has the non-flammable properties of WCF.

[0058] Refrigerant 4 contains HFO-1132(E), CF3I, and R32. The total mass percentage of HFO-1132(E), CF3I, and R32 in the refrigerant is preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and most preferably 99.9% by mass or more. Furthermore, components other than HFO-1132(E), CF3I, and R32 in the refrigerant include byproducts unavoidably present during the manufacture of HFO-1132(E), CF3I, and R32.

[0059] <Implementation Method 5: Refrigerant 5> The refrigerant 5 of the present invention contains trifluoroiodomethane (CF3I), difluoromethane (R32), and trifluoroethylene (HFO-1123). When the mass percentages of HFO-1123, CF3I, and R32, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1123, CF3I, and R32 is 100% by mass, the coordinates (x, y, z) of the composition lie within the area enclosed by the line segments ZN, NL, and LZ connecting the points Z, N, and L respectively (excluding the line segment NL mentioned above). Point Z (41.6, 53.5, 4.9) Point N (0.0. 77.2, 22.8) and Point L (0.0, 35.0, 65.0) The above line segment ZN is defined by coordinates (x, -0.0007x). 2 -0.5402x + 77.2, 0.0007x 2 -0.4598x+22.8) represents that the above line segments NL and LZ are straight lines.

[0060] That is, refrigerant 5 is a mixed refrigerant.

[0061] When refrigerant 5 meets the above requirements, it possesses four properties: it can be used as a replacement for R410A, it has excellent coefficient of performance (COP) and refrigeration capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, its COP is above 99% compared to R32, its refrigeration capacity is above 80% compared to R32, its GWP is below 750 (especially below 450), and it also has the non-flammable properties of WCF.

[0062] Refrigerant 5 contains HFO-1123, CF3I, and R32. The preferred total mass percentage of HFO-1123, CF3I, and R32 in the refrigerant is 99.5% or more by mass, more preferably 99.7% or more by mass, and most preferably 99.9% or more by mass. Furthermore, components other than HFO-1123, CF3I, and R32 in the refrigerant include byproducts unavoidably present during the manufacture of HFO-1123, CF3I, and R32.

[0063] <Implementation Method 6: Refrigerant 6> The refrigerant 6 of the present invention contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I) and 2,3,3,3-tetrafluoroethylene (HFO-1234yf). The total concentration of R32, R125, CF3I, and HFO-1234yf was set to 100% by mass, and the concentration of HFO-1234yf was set to x% by mass. Refrigerant 6 includes either refrigerant A or refrigerant B in the three-component composition diagram, where the total concentration of R32, R125, and CF3I is shown as (100-x) mass % . Refrigerant A: (1) -1 11.7% mass ≥ x ≥ 6.0% mass (1) -2 The concentrations of R32, R125 and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratio shown within the range of a quadrilateral or triangle with vertices C, D, F and E (excluding the above line segment DF). Point C (1.1753x + 41.14 / - 0.2282x + 13.464 / 100 - R1234yf - R32 - R125). Point D (0.0247x) 2 +0.563x+43.733 / 0.0 / 100-R1234yf-R32-R125), Point F (-0.8069x+64.948 / 0.0 / 100-R1234yf-R32-R125). Point E (-0.8247x+64.54 / 0.1581x+8.96 / 100-R1234yf-R32-R125); Refrigerant B: (2) -1 12.6% mass > x ≥ 11.7% mass (2) The concentrations of R32, R125 and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratio shown within the range of a triangle with points G, D and F as vertices (excluding the above line segment DF). Point G (-1.2222x) 2 +29.589x - 123.98 / 20.5x 2 -510.15x+3173.3 / 100-R1234yf-R32-R125), Point D (1.2213x+39.415 / 0.0 / 100-R1234yf-R32-R125). Point F (0.7787x+64.615 / 0.0 / 100-R1234yf-R32-R125).

[0064] That is, refrigerant 6 is a mixed refrigerant.

[0065] When refrigerant 6 meets the above requirements at a concentration x of HFO-1234yf of (1) 11.7 wt% ≥ x ≥ 6.0 wt% and (2) 12.6 wt% > x ≥ 11.7 wt%, it possesses four properties: it can be used as a substitute for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low GWP, and it is non-flammable. Specifically, its coefficient of performance is more than 100% of that of R410A, its freezing capacity is more than 100% of that of R410A, its GWP is less than 750, and it also has the non-flammable properties of WCF.

[0066] Refrigerant 6 contains R32, R125, CF3I, and HFO-1234yf. The total mass percentage of R32, R125, CF3I, and HFO-1234yf in the refrigerant is preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and most preferably 99.9% by mass or more. Furthermore, components other than R32, R125, CF3I, and HFO-1234yf in the refrigerant include byproducts unavoidably present during the manufacture of R32, R125, CF3I, and HFO-1234yf.

[0067] The following explains how to determine points A, B, C, D, E, F, and G, considering the range of x. Furthermore, the technical significance of points A, B, C, D, E, F, and G is explained below. Additionally, the concentrations at each point are recorded as values ​​obtained in the embodiment 6 (refrigerant 6) described later.

[0068] A: Composition ratio with GWP=750 and CF3I concentration (mass%) of 0.0% B: Composition ratio with GWP=750 and R32 concentration (mass%) of 0.0% by mass. C: Composition ratio that has 100% freezing capacity relative to R410A and GWP=750. D: A composition with 100% freezing capacity relative to R410A and a concentration (mass%) of R125 of 0.0% by mass. E: Composition ratio that makes WCF non-flammable with a GWP of 750 F: Composition ratio that is WCF non-flammable and has an R125 concentration (mass%) of 0.0% G: A composition that is 100% refrigeration capacity relative to R410A and is non-flammable in WCF. (1) Method for finding points C, D, E, F, and G (1-1) Regarding point C 11.7% mass ≥ x ≥ 6.0% mass When the concentration of HFO-1234yf is 6.0% by mass, the total concentrations of R32, R125, and CF3I are (100-x)% by mass. Point C on the three-component composition plot is: The concentration of R32 (mass%) / the concentration of R125 (mass%) / the concentration of CF3I (mass%) = (48.2 / 12.1 / 33.7). When the concentration of HFO-1234yf is 9.0% by mass, the point C on the three-component composition plot with the total concentrations of R32, R125, and CF3I being (100-x)% by mass is: The concentration of R32 (mass%) / the concentration of R125 (mass%) / the concentration of CF3I (mass%) = (51.7 / 11.4 / 27.9). When the concentration of HFO-1234yf is 11.7% by mass, the total concentrations of R32, R125, and CF3I are (100-x)% by mass. Point C on the three-component composition plot is: (Concentration of R32 (mass%) / Concentration of R125 (mass%) / Concentration of CF3I (mass%)) = (54.9 / 10.8 / 22.6). Therefore, when the total concentration of R32, R125, CF3I, and HFO-1234yf is set to 100% by mass, and the concentration of R32 is set to y% by mass, the regression line obtained from the above three points plotted on the xy coordinate is expressed as follows: y = 1.1753x + 41.14.

[0069] Furthermore, when the concentration of R125 is set as y (mass%), the regression line obtained is expressed as follows: y = -0.2282x + 13.464.

[0070] Therefore, the CF3I concentration at point C is (100 - R1234yf - R32 - R125), and Based on the above, the total concentration of R32, R125, and CF3I is set as point C on the three-component composition diagram (100-x). The concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%) is expressed as (1.1753x+41.14 / -0.2282x+13.464 / 100-R1234yf-R32-R125).

[0071] 12.6% mass ≥ x > 11.7% mass The same calculations were performed for the range of X as described above. The results for point C for each concentration range of x are shown in Table 1 below (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)).

[0072] [Table 1] (1-2) Regarding points D, E, F, and G Next, points D, E, F, and G are determined in the same manner as for point C. The results are shown in Tables 2-5 below.

[0073] [Table 2] [Table 3] [Table 4] [Table 5] On a ternary composition plot where the total concentrations of R32, R125, and CF3I are set to (100-x), the set of points where GWP = 7500 is represented by the straight line connecting points A and B as a function of x when HFO - 1234yf = x. For example, in Figures 5-9 On the three-component composition diagram, in the region closer to the vertex side of CF3I than the straight line, GWP becomes below 750.

[0074] Furthermore, on a three-component composition plot where the total concentration of R32, R125, and CF3I is set to (100-x), the set of points representing 100% freezing capacity relative to R410A is approximated by the straight line connecting points C and D, which are functions of x when HFO-1234yf=x. For example, in Figures 5-9 On the three-component composition diagram, in the region on the vertex side of region R32, the freezing capacity relative to R410A becomes more than 100%.

[0075] Furthermore, on a three-component composition diagram where the total concentration of R32, R125, and CF3I is set to (100-x), the set of points where WCF is non-flammable approximates the straight line connecting points E and F, which are functions of x when HFO-1234yf=x. For example, in Figures 5-9 On the three-component composition diagram, in the region closer to the vertex side of CF3I than the approximate straight line, WCF becomes non-flammable.

[0076] Non-combustible limit (determining line segment EF) First, determine the non-flammability limit of the binary refrigerant mixture of flammable refrigerant (R32, 1234yf) and non-flammable refrigerant (CF3I, R125).

[0077] The non-flammability limit of the binary refrigerant mixture is determined based on the testing apparatus and method of the flammability test according to ASTM E681-2009 (details as described above).

[0078] As a result, for the mixture of flammable refrigerant R32 and non-flammable refrigerant CF3I, no flame propagation was confirmed at R32 = 65.0 wt% and CF3I = 35.0 wt%, and this composition was taken as the non-flammable limit. Furthermore, for the mixture of flammable refrigerant R32 and non-flammable refrigerant R125, no flame propagation was confirmed at R32 = 63.0 wt% and R125 = 37.0 wt%. For the mixture of flammable refrigerant 1234yf and non-flammable refrigerant CF3I, no flame propagation was confirmed at 1234yf = 80.0 wt% and CF3I = 20.0 wt%. For the mixture of flammable refrigerant 1234yf and non-flammable refrigerant R125, no flame propagation was confirmed at 1234yf = 79.0 wt% and R125 = 21.0 wt%, and these compositions were taken as the non-flammable limits. The results are summarized in Table 6.

[0079] [Table 6] Points E and F represent the non-flammability limit. In the relationship between the equivalent flammable refrigerant concentration of R32 = R32 + (63 / 37) * (21 / 79) * R1234yf and the equivalent non-flammable refrigerant concentration of R32 = (63 / 37) * R125 + (65 / 35) * CF3I, when the flammable refrigerant concentration minus the non-flammable refrigerant concentration < 0, it is judged as non-flammable. It is determined to be flammable when the concentration of flammable refrigerant equivalent to R32 minus the concentration of non-flammable refrigerant is greater than 0.

[0080] Table 7 details points E and F. The line segment EF is the regression line connecting these two points E and F.

[0081] [Table 7] <Implementation Method 7: Refrigerant 7> The refrigerant 7 of the present invention contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I) and 1,3,3,3-tetrafluoropropylene (HFO-1234ze). The total concentration of R32, R125, CF3I, and HFO-1234ze was set at 100% by mass, and the concentration of HFO-1234ze was set at x% by mass. Refrigerant 7 includes either refrigerant A or refrigerant B in the three-component composition diagram, where the total concentration of R32, R125, and CF3I is shown as (100-x) mass % . Refrigerant A: (1) -1 8.3% mass ≥ x ≥ 4.0% mass (1) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratio shown within the range of a quadrilateral or triangle with vertices C, D, F, and E (excluding the line segment DF mentioned above), Point C (0.0435x) 2 +1.4652x+42.543 / -0.3726x+13.406 / 100-R1234ze-R32-R125), Point D (0.097x) 2 +0.6802x+44.628 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.8143x+64.967 / 0.0 / 100-R1234ze-R32-R125). Point E (-0.0061x) 2 -0.7393x+64.254 / 0.1631x+8.9386 / 100-R1234ze-R32-R125); Refrigerant B: (2) -1 8.9% mass > x ≥ 8.3% mass (2) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the triangle formed by points G, D, and F (excluding the line segment DF mentioned above). Point G (0.1667x + 56.3 / 2.7778x) 2 -64.944x+357.98 / 100-R1234ze-R32-R125), Point D (1.5625x) 2 -24.938x+155.98 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.6667x+63.733 / 0.0 / 100-R1234ze-R32-R125).

[0082] That is, refrigerant 7 is a mixed refrigerant.

[0083] When refrigerant 7 meets the above requirements at a concentration x of HFO-1234ze of (1) 8.3 wt% ≥ x ≥ 4.0 wt% and (2) 8.9 wt% > x ≥ 8.3 wt%, it possesses four properties: it can be used as a substitute for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low GWP, and it is non-flammable. Specifically, its coefficient of performance is more than 100% of that of R410A, its freezing capacity is more than 100% of that of R410A, its GWP is less than 750, and it also has the non-flammable properties of WCF.

[0084] Refrigerant 7 contains R32, R125, CF3I, and HFO-1234ze. The total mass percentage of R32, R125, CF3I, and HFO-1234ze in the refrigerant is preferably 99.5% by mass or more, more preferably 99.7% by mass or more, and most preferably 99.9% by mass or more. Furthermore, components other than R32, R125, CF3I, and HFO-1234ze in the refrigerant include byproducts unavoidably present during the manufacture of R32, R125, CF3I, and HFO-1234ze.

[0085] The following explains how to determine points A, B, C, D, E, F, and G, considering the range of x. Furthermore, the technical significance of points A, B, C, D, E, F, and G is explained below. Additionally, the concentrations at each point are recorded as values ​​obtained in the embodiment 7 (refrigerant 7) described later.

[0086] A: Composition ratio with GWP=750 and CF3I concentration (mass%) of 0.0% B: Composition ratio with GWP=750 and R32 concentration (mass%) of 0.0% by mass. C: Composition ratio that has 100% freezing capacity relative to R410A and GWP=750. D: A composition with 100% freezing capacity relative to R410A and a concentration (mass%) of R125 of 0.0% by mass. E: Composition ratio that makes WCF non-flammable with a GWP of 750 F: Composition ratio that is WCF non-flammable and has an R125 concentration (mass%) of 0.0% G: A composition that is 100% refrigeration capacity relative to R410A and is non-flammable in WCF. (1) Method for finding points C, D, E, F, and G (1-1) Regarding point C 8.3% mass ≥ x ≥ 4.0% mass When the concentration of HFO-1234ze is 4.0% by mass, the point C on the three-component composition plot with the total concentrations of R32, R125, and CF3I being (100-x)% by mass is: The concentration of R32 (mass%) / the concentration of R125 (mass%) / the concentration of CF3I (mass%) = (49.1 / 11.9 / 35.0). When the concentration of HFO-1234yf is 6.0% by mass, the total concentrations of R32, R125, and CF3I are (100-x)% by mass. Point C on the three-component composition plot is: The concentration of R32 (mass%) / the concentration of R125 (mass%) / the concentration of CF3I (mass%) = (52.9 / 11.2 / 29.9). When the concentration of HFO-1234yf is 8.3% by mass, the total concentrations of R32, R125, and CF3I are (100-x)% by mass. Point C on the three-component composition diagram is: (Concentration of R32 (mass%) / Concentration of R125 (mass%) / Concentration of CF3I (mass%)) = (57.7 / 10.3 / 23.7). Therefore, when the total concentration of R32, R125, CF3I, and HFO-1234ze is set to 100% by mass, and the concentration of R32 is set to y% by mass, the regression line obtained from the above three points plotted on the xy coordinate is expressed as follows: y=0.0435x 2 +1.4652x+42.543.

[0087] Furthermore, when the concentration of R125 is set as y (mass%), the regression line obtained is expressed as follows: y = -0.3726x + 13.462.

[0088] Therefore, the CF3I concentration at point C is (100 - R1234ze - R32 - R125), and Based on the above, the total concentrations of R32, R125, and CF3I are set as (100-x). Point C on the three-component composition plot (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) is represented as (0.0435x). 2 +1.4652x+42.543 / -0.3726x+13.462 / 100-R1234ze-R32-R125).

[0089] 8.9% mass ≥ x > 8.3% mass The same calculations were performed for the range of X as described above. Table 8 below shows the results for point C for each concentration range of x (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)).

[0090] [Table 8] (1-2) Regarding points D, E, F, and G Next, points D, E, F, and G are determined in the same manner as point C. The results are shown in Tables 9-12 below.

[0091] [Table 9] [Table 10] [Table 11] [Table 12] On a ternary composition plot where the total concentrations of R32, R125, and CF3I are set to (100-x), the set of points where GWP = 7500 is represented by the straight line connecting points A and B as a function of x when HFO - 1234ze = x. For example, in Figures 10-14 On the three-component composition diagram, in the region closer to the vertex side of CF3I than the straight line, GWP becomes below 750.

[0092] Furthermore, on a three-component composition plot where the total concentration of R32, R125, and CF3I is set to (100-x), the set of points representing 100% freezing capacity relative to R410A is approximated by the straight line connecting points C and D, which are functions of x when HFO-1234ze=x. For example, in Figures 10-14 On the three-component composition diagram, in the region on the vertex side of region R32, the freezing capacity relative to R410A becomes more than 100%.

[0093] Furthermore, on a three-component composition diagram where the total concentration of R32, R125, and CF3I is set to (100-x), the set of points where WCF is non-flammable approximates the straight line connecting points E and F, which are functions of x when HFO-1234ze=x. For example, in Figures 10-14 On the three-component composition diagram, in the region closer to the vertex side of CF3I than the approximate straight line, WCF becomes non-flammable.

[0094] Non-combustible limit (determining line segment EF) First, determine the non-flammability limit of the binary refrigerant mixture of flammable refrigerant (R32, 1234ze) and non-flammable refrigerant (CF3I, R125).

[0095] The non-flammability limit of the binary refrigerant mixture is determined based on the testing apparatus and method of the flammability test according to ASTM E681-2009 (details as described above).

[0096] As a result, for the mixture of flammable refrigerant R32 and non-flammable refrigerant CF3I, no flame propagation was confirmed at R32 = 65.0 wt% and CF3I = 35.0 wt%, and this composition was taken as the non-flammable limit. Furthermore, for the mixture of flammable refrigerant R32 and non-flammable refrigerant R125, no flame propagation was confirmed at R32 = 63.0 wt% and R125 = 37.0 wt%. For the mixture of flammable refrigerant 1234ze and non-flammable refrigerant CF3I, no flame propagation was confirmed at 1234ze = 80.0 wt% and CF3I = 20.0 wt%. For the mixture of flammable refrigerant 1234ze and non-flammable refrigerant R125, no flame propagation was confirmed at 1234yf = 79.0 wt% and R125 = 21.0 wt%, and these compositions were taken as the non-flammable limits. The results are summarized in Table 13.

[0097] [Table 13] Points E and F represent the non-flammability limit. In the relationship between the equivalent flammable refrigerant concentration of R32 = R32 + (63 / 37) * (21 / 79) * R1234ze and the equivalent non-flammable refrigerant concentration of R32 = (63 / 37) * R125 + (65 / 35) * CF3I, when the flammable refrigerant concentration minus the non-flammable refrigerant concentration is less than 0, it is judged as non-flammable. It is determined to be flammable when the concentration of flammable refrigerant equivalent to R32 minus the concentration of non-flammable refrigerant is greater than 0.

[0098] Table 14 details points E and F. The line segment EF is the regression line connecting these two points E and F.

[0099] [Table 14] 1.2 use The refrigerant of the present invention can be preferably used as the working fluid in a refrigeration unit.

[0100] The compositions of the present invention are suitable for use as an alternative refrigerant to R410A.

[0101] 2. Refrigerant composition The refrigerant composition of the present invention contains at least the refrigerant of the present invention and can be used for the same purposes as the refrigerant of the present invention. Furthermore, the refrigerant composition of the present invention can also be used as a working fluid for refrigeration machines by mixing with at least refrigeration oil.

[0102] The refrigerant composition of the present invention contains at least one other component besides the refrigerant of the present invention. The refrigerant composition of the present invention may contain at least one of the following other components as needed. As described above, when the refrigerant composition of the present invention is used as a working fluid in a refrigeration unit, it is typically used in combination with at least refrigeration oil. Therefore, the refrigerant composition of the present invention preferably contains substantially no refrigeration oil. Specifically, the content of refrigeration oil in the refrigerant composition of the present invention relative to the total refrigerant composition is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass.

[0103] 2.1 Water The refrigerant composition of the present invention may contain trace amounts of water. The water content in the refrigerant composition is preferably 0 to 0.1% by mass relative to the total refrigerant, more preferably 0 to 0.075% by mass, further preferably 0 to 0.05% by mass, and particularly preferably 0 to 0.025% by mass.

[0104] By containing trace amounts of moisture, the intramolecular double bonds of unsaturated fluorinated hydrocarbon compounds that may be present in the refrigerant are stabilized, and oxidation of these compounds is less likely, thus improving the stability of the refrigerant composition. From the viewpoint of achieving the aforementioned effects from the presence of moisture, the lower limit of the water content is approximately 0.001% by mass. For example, the water content can be adjusted within the ranges of 0.001–0.1% by mass, 0.001–0.075% by mass, 0.001–0.05% by mass, and 0.001–0.025% by mass.

[0105] 2.2 Tracers The tracer is added to the refrigerant composition of the present invention at a detectable concentration so as to track changes in the refrigerant composition of the present invention as it is diluted, contaminated, or otherwise altered.

[0106] The refrigerant composition of the present invention may contain one of the above-mentioned tracers alone, or it may contain two or more of them.

[0107] The tracer described above is not particularly limited and can be appropriately selected from commonly used tracers. Preferably, a compound that will not become an unavoidable impurity in the refrigerant of the present invention is selected as the tracer.

[0108] Examples of tracers that can be used include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N₂O). Among these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, fluorocarbons, and fluoroethers are preferred.

[0109] Specifically, the following compounds are more preferred as the tracers described above.

[0110] FC-14 (Tetrafluoromethane, CF4) HCC-40 (chloromethane, CH3Cl) HFC-23 (trifluoromethane, CHF3) HFC-41 (fluoromethane, CH3Cl) HFC-125 (pentafluoroethane, CF3CHF2) HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2) HFC-143a (1,1,1-trifluoroethane, CF3CH3) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-152a (1,1-difluoroethane, CHF2CH3) HFC-152 (1,2-difluoroethane, CH2FCH2F) HFC-161 (fluoroethane, CH3CH2F) HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2) HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3) HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3) HCFC-22 (dichlorofluoromethane, CHClF2) HCFC-31 (chlorofluoromethane, CH2ClF) CFC-1113 (chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl-methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3) The tracer compound may be present in the refrigerant composition at a total concentration of about 10 parts per million (ppm) to about 1000 ppm. Preferably, the tracer compound is present in the refrigerant composition at a total concentration of about 30 ppm to about 500 ppm, and most preferably, the tracer compound is present in the refrigerant composition at a total concentration of about 50 ppm to about 300 ppm.

[0111] 2.3 Ultraviolet Fluorescent Dyes The refrigerant composition of the present invention may contain one or more ultraviolet fluorescent dyes.

[0112] The aforementioned ultraviolet fluorescent dyes are not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0113] Examples of ultraviolet fluorescent dyes mentioned above include naphthalimide, coumarin, anthracene, phenanthrene, dibenzopyran, thioxanthracene, benzoxanthracene, and fluorescein, as well as their derivatives. Among these, naphthalimide and coumarin, or both, are preferred.

[0114] 2.4 Stabilizers The refrigerant composition of the present invention may contain one or more stabilizers.

[0115] There are no particular limitations on the stabilizers mentioned above; they can be appropriately selected from commonly used stabilizers.

[0116] Examples of stabilizers mentioned above include nitro compounds, ethers, and amines.

[0117] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitrobenzene, and aromatic nitro compounds such as nitrobenzene and nitrobenzene.

[0118] Examples of ethers include, for example, 1,4-dioxane.

[0119] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0120] In addition, butylated hydroxyxylene, benzotriazole, etc. can also be listed.

[0121] The proportion of stabilizer is not particularly limited, but it is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, relative to the total refrigerant.

[0122] 2.5 Polymerization inhibitor The refrigerant composition of the present invention may contain one type of polymerization inhibitor alone, or two or more types.

[0123] There are no particular limitations on the above-mentioned polymerization inhibitors; they can be appropriately selected from commonly used polymerization inhibitors.

[0124] Examples of polymerization inhibitors mentioned above include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tert-butylphenol, 2,6-tert-butyl-p-cresol, and benzotriazole.

[0125] The content of the above-mentioned polymerization inhibitor is not particularly limited, but it is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, relative to the total refrigerant.

[0126] 3. Working fluids containing refrigeration oil The working fluid containing refrigeration oil of the present invention contains at least the refrigerant or refrigerant composition of the present invention and refrigeration oil, and is used as a working fluid in a refrigeration unit. Specifically, the working fluid containing refrigeration oil of the present invention can be obtained by mixing refrigeration oil, which can be used in the compressor of a refrigeration unit, with the refrigerant or refrigerant composition. The refrigeration oil in the working fluid typically contains 10-50% by mass.

[0127] 3.1 Refrigeration oil The composition of the present invention may contain only one type of refrigeration oil or may contain two or more types.

[0128] There are no particular limitations on the type of refrigeration oil; any commonly used refrigeration oil can be selected. However, depending on the requirements, a refrigeration oil that excels in improving the miscibility and stability of the mixture can be appropriately chosen.

[0129] As a base oil for refrigeration oil, it is preferably selected from at least one of polyalkylene glycol (PAG), polyol ether (POE), and polyvinyl ether (PVE).

[0130] In addition to the base oil, the above-mentioned refrigeration oils may also contain additives. The additives may be at least one selected from antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoamers.

[0131] For refrigeration oil, from a lubrication perspective, a kinematic viscosity of 5 to 400 cSt at 40°C is preferred.

[0132] The working fluid containing refrigeration oil of the present invention may further contain at least one additive as needed. Examples of additives include, for instance, compatibilizers.

[0133] 3.2 Compatible Solubilizer In the working fluid containing refrigeration oil of the present invention, the solubilizer may be one type or two or more types.

[0134] There are no particular limitations on the solubilizers used above; they can be appropriately selected from commonly used solubilizers.

[0135] Examples of compatibilizers include, for example, polyoxyalkylene diol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Among these, polyoxyalkylene diol ethers are preferred.

[0136] 4. How to operate a refrigeration unit The method of operating the refrigeration unit of the present invention is a method of operating the refrigeration unit using the refrigerant of the present invention.

[0137] Specifically, the method of operating the refrigeration unit of the present invention includes the step of circulating the refrigerant of the present invention within the refrigeration unit.

[0138] The above describes the implementation method. However, it should be understood that various changes can be made to the method and details as long as they do not exceed the essential points and scope of the patent claims.

[0139] Example The following examples illustrate the invention in more detail. However, the invention is not limited to these examples.

[0140] In the examples and comparative examples, the GWP of the mixed refrigerant was evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Report. Although the GWP of HFO-1132(E) is not recorded, it is assumed to be 1 based on HFO-1132a (GWP=1 or less) and HFO-1123 (GWP=0.3, as described in Patent Document 1). Furthermore, the freezing capacity of the mixed refrigerant was determined using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions through theoretical calculations of the mixed refrigerant's freezing cycle.

[0141] Evaporation temperature 5℃ Condensation temperature 45℃ Superheating temperature 5K Supercooling temperature 5K Compressor efficiency 70% In addition, the coefficient of performance (COP) of the mixed refrigerant is calculated using the following formula.

[0142] COP = (Cooling or heating capacity) / Electricity consumed Examples and comparative examples of implementation method 1 (refrigerant 1) Prepare a mixed refrigerant by mixing R32 and CF3I according to the total of these in the mass % (mass %) shown in Table 15.

[0143] [Table 15] Refrigerant 1 possesses four properties through its prescribed composition: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, it is known that the mixed refrigerants of Examples 1 to 3, which are specific examples of refrigerant 1, have a coefficient of performance of 98% or more relative to R32, a freezing capacity of 95% or more relative to R32, a GWP of 750 or less (especially 400 or less), and also possess the ASHRAE non-flammable property.

[0144] Examples and comparative examples of implementation method 2 (refrigerant 2) Prepare a mixed refrigerant by mixing R32, R125 and CF3I in the mass % (mass %) shown in Table 16, based on the sum of these.

[0145] [Table 16] Refrigerant 2 possesses four properties through its prescribed composition: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low GWP, and it is non-flammable. Specifically, it is known that the mixed refrigerants of Examples 4 to 9, which are specific examples of refrigerant 2, have a coefficient of performance of 98% or more relative to R32, a freezing capacity of 95% or more relative to R32, a GWP of 750 or less (especially 600 or less), and also possess the non-flammable properties of WCF.

[0146] Examples and comparative examples of implementation method 3 (refrigerant 3) HFO-1132(E) and CF3I were mixed according to the total of these amounts in the mass % (mass %) shown in Table 17 to prepare a mixed refrigerant.

[0147] [Table 17] Refrigerant 3 possesses four properties through its prescribed composition: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, it is known that the mixed refrigerants of Examples 10 to 14, which are specific examples of refrigerant 3, have a coefficient of performance of 100% or more (especially 105% or more) relative to R410A, a freezing capacity of 65% or more relative to R410A, a GWP of less than 1, and also possess the non-flammable properties of WCF.

[0148] Examples and comparative examples of implementation method 4 (refrigerant 4) Prepare a mixed refrigerant by mixing R32, HFO-1132(E) and CF3I according to the total of these in the mass % (mass %) shown in Table 18.

[0149] [Table 18] Refrigerant 4 possesses four properties through its prescribed composition: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, it is known that the mixed refrigerants of Examples 15 to 19, which are specific examples of refrigerant 4, have a coefficient of performance of 99% or more relative to R32, a freezing capacity of 80% or more relative to R32, a GWP of 750 or less (especially 450 or less), and also possess the non-flammable properties of WCF.

[0150] Examples and comparative examples of implementation method 5 (refrigerant 5) Prepare a mixed refrigerant by mixing R32, HFO-1123 and CF3I according to the total of these in the mass % (mass %) shown in Table 19.

[0151] [Table 19] Refrigerant 5 possesses four properties through its prescribed composition: it can be used as a replacement for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low gas per watt (GWP), and it is non-flammable. Specifically, it is known that the mixed refrigerants of Examples 20 to 24, which are specific examples of refrigerant 5, have a coefficient of performance of 99% or more relative to R32, a freezing capacity of 80% or more relative to R32, a GWP of 750 or less (especially 450 or less), and also possess the non-flammable properties of WCF.

[0152] Examples and comparative examples of implementation method 6 (refrigerant 6) Mix R32, R125, HFO-1234yf, and CF3I according to the total of these components and the mass percentages (mass%) shown in Table 20 (R1234yf = 6 wt%), Table 21 (R1234yf = 9 wt%), Table 22 (R1234yf = 11.7 wt%), Table 23 (R1234yf = 12.1 wt%), and Table 24 (R1234yf = 12.6 wt%) to prepare a mixed refrigerant.

[0153] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24] When refrigerant 6 meets the above requirements at the concentration x of HFO-1234yf as (1) 11.7 wt% ≥ x ≥ 6.0 wt% and (2) 12.6 wt% > x ≥ 11.7 wt%, it possesses four properties: it can be used as a substitute for R410A, it has excellent coefficient of performance and freezing capacity, it has a sufficiently low GWP, and it is non-flammable. Specifically, it can be seen that the coefficient of performance of the mixed refrigerant in the above table, which is a specific example of refrigerant 6, is more than 100% of that of R410A, its freezing capacity is more than 100% of that of R410A, its GWP is less than 750, and it also has the non-flammable properties of WCF.

[0154] Examples and comparative examples of implementation method 7 (refrigerant 7) Mix R32, R125, HFO-1234ze, and CF3I according to the total of these components and the mass percentages (mass%) shown in Table 25 (R1234ze = 4 wt%), Table 26 (R1234ze = 6 wt%), Table 27 (R1234ze = 8.3 wt%), Table 28 (R1234ze = 8.6 wt%), and Table 29 (R1234ze = 8.9 wt%) to prepare a mixed refrigerant.

[0155] [Table 25] [Table 26] [Table 27] [Table 28] [Table 29] When the concentration x of refrigerant 7 in HFO-1234ze satisfies the above respective requirements in the cases of (1) 8.3 mass% ≥ x ≥ 4.0 mass% and (2) 8.9 mass% > x ≥ 8.3 mass%, it has four properties: it can be a substitute refrigerant for R410A, has excellent coefficient of performance and refrigerating capacity, has a sufficiently small GWP, and is non-flammable. Specifically, it can be seen that the coefficient of performance of the mixed refrigerant in the above table, which is a specific example of refrigerant 7, is 100% or more relative to R410A, the refrigerating capacity is 100% or more relative to R410A, the GWP is 750 or less, and it has the property of being non-flammable in WCF.

[0156] Symbol Explanation 1: Ignition source 2: Sample inlet 3: Springs 4: 12-liter glass flask 5: Electrodes 6: Stirrer 7: Insulated chamber A: Composition ratio with GWP = 750 and CF3I concentration (mass%) of 0.0 mass% B: Composition ratio with GWP = 750 and R32 concentration (mass%) of 0.0 mass% C: Composition ratio with refrigerating capacity of 100% relative to R410A (refrigerating capacity is 100% relative to R410A) and GWP = 750 D: Composition ratio with refrigerating capacity of 100% relative to R410A (refrigerating capacity is 100% relative to R410A) and R125 concentration (mass%) of 0.0 mass% E: Composition ratio with non-flammable in WCF and GWP = 750 F: Composition ratio with non-flammable in WCF and R125 concentration (mass%) of 0.0 mass% G: Composition ratio with refrigerating capacity of 100% relative to R410A (refrigerating capacity is 100% relative to R410A) and non-flammable in WCF.

Claims

1. A composition containing a refrigerant, characterized in that: The refrigerant contains trifluoroiodine methane (CF3I) and difluoromethane (R32). When the total amount of CF3I and R32 in the refrigerant is set to 100% by mass, the contents of CF3I and R32 are respectively 48% by mass ≥ CF3I ≥ 46% by mass and 54% by mass ≥ R32 ≥ 52% by mass.

2. A composition containing a refrigerant, characterized in that: The refrigerant contains trifluoroiodomethane (CF3I), difluoromethane (R32), and pentafluoroethane (R125). When the mass percentages of R32, R125, and CF3I are set as x, y, and z respectively, in a three-component composition diagram where the sum of R32, R125, and CF3I is 100% by mass, the coordinates (x, y, z) of the composition lie within the area bounded by the line segments EF, FD, DX, and XE connecting the points E, F, D, and X respectively, but excluding the line segment FD. Point E (53.7, 11.0, 35.3) Point F (51.6, 0.0, 48.4) Point D (65.0, 0.0, 35.0) Point X (64.6.8.9, 26.5) The line segment EF is defined by coordinates (x, -1.1255x). 2 +123.76x - 3389.3, 1.1255x 2 -124.76x+3489.3) represents, and the line segments FD, DX and XE are straight lines.

3. A composition containing a refrigerant, characterized in that: The refrigerant contains trifluoroiodomethane (CF3I) and trans-1,2-difluoroethylene (HFO-1132(E)). The total amount of CF3I and HFO-1132(E) in the refrigerant is set to 100% by mass. The content of CF3I and HFO-1132(E) is 68% by mass ≥ CF3I ≥ 62% by mass and 38% by mass ≥ HFO-1132(E) ≥ 32% by mass.

4. A composition containing a refrigerant, characterized in that: The refrigerant contains trifluoroiodomethane (CF3I), difluoromethane (R32), and trans-1,2-difluoroethylene (HFO-1132(E)). When the mass percentages of HFO-1132(E), CF3I, and R32, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), CF3I, and R32 is 100% by mass, the coordinates (x, y, z) of the composition lie within the area bounded by line segments JH, HY, and YJ connecting points Y, J, and H respectively, but excluding line segment JH. Point Y (32.5, 58.1, 9.4), Point J (0.

0. 77.2, 22.8). Point H (0.

0. 35.0, 65.0), The line segment YJ is defined by coordinates (x, -0.0027x). 2 -0.5002x + 77.2, 0.0027x 2 -0.4998x+22.8) represents, and the line segments JH and HY are straight lines.

5. A composition containing a refrigerant, characterized in that: The refrigerant contains trifluoroiodimethane (CF3I), difluoromethane (R32), and trifluoroethylene (HFO-1123). When the mass percentages of HFO-1123, CF3I, and R32 (based on their sum) are set as x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1123, CF3I, and R32 is 100% by mass, the coordinates (x, y, z) of the composition lie within the area enclosed by the line segments ZN, NL, and LZ connecting points Z, N, and L, respectively, but excluding line segment NL. Point Z (41.6, 53.5, 4.9). Point N (0.

0. 77.2, 22.8). Point L (0.

0. 35.0, 65.0), The line segment ZN is defined by coordinates (x, -0.0007x). 2 -0.5402x + 77.2, 0.0007x 2 -0.4598x+22.8) represents, and the line segments NL and LZ are straight lines.

6. A composition containing a refrigerant, characterized in that: The refrigerant contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I), and 2,3,3,3-tetrafluoroethylene (HFO-1234yf). The total concentration of R32, R125, CF3I, and HFO-1234yf was set to 100% by mass, and the concentration of HFO-1234yf was set to x% by mass. The refrigerant composition includes one of refrigerant A or refrigerant B in a three-component composition diagram showing the total concentration of R32, R125, and CF3I as (100-x) mass % . Refrigerant A: (1) -1 11.7% mass ≥ x ≥ 6.0% mass (1) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a quadrilateral or triangle with vertices C, D, F, and E, but excluding the line segment DF. Point C (1.1753x + 41.14 / - 0.2282x + 13.464 / 100 - R1234yf - R32 - R125). Point D (0.0247x) 2 +0.563x+43.733 / 0.0 / 100-R1234yf-R32-R125), Point F (-0.8069x+64.948 / 0.0 / 100-R1234yf-R32-R125). Point E (-0.8247x+64.54 / 0.1581x+8.96 / 100-R1234yf-R32-R125); Refrigerant B: (2) -1 12.6% mass > x > 11.7% mass (2) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a triangle with vertices G, D, and F, but excluding the line segment DF. Point G (-1.2222x) 2 +29.589x - 123.98 / 20.5x 2 -510.15x+3173.3 / 100-R1234yf-R32-R125), Point D (1.2213x+39.415 / 0.0 / 100-R1234yf-R32-R125). Point F (0.7787x+64.615 / 0.0 / 100-R1234yf-R32-R125).

7. A composition containing a refrigerant, characterized in that: The refrigerant contains difluoromethane (R32), pentafluoroethane (R125), trifluoroiodomethane (CF3I), and 1,3,3,3-tetrafluoropropylene (HFO-1234ze). The total concentration of R32, R125, CF3I, and HFO-1234ze was set to 100% by mass, and the concentration of HFO-1234ze was set to x% by mass. The refrigerant composition includes one of refrigerant A or refrigerant B in a three-component composition diagram showing the total concentration of R32, R125, and CF3I as (100-x) mass % . Refrigerant A: (1) -1 8.3% mass ≥ x ≥ 4.0% mass (1) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a quadrilateral or triangle with vertices C, D, F, and E, but excluding the line segment DF. Point C (0.0435x) 2 +1.4652x+42.543 / -0.3726x+13.406 / 100-R1234ze-R32-R125), Point D (0.097x) 2 +0.6802x+44.628 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.8143x+64.967 / 0.0 / 100-R1234ze-R32-R125). Point E (-0.0061x) 2 -0.7393x+64.254 / 0.1631x+8.9386 / 100-R1234ze-R32-R125); Refrigerant B: (2) -1 8.9% mass > x > 8.3% mass (2) The concentrations of R32, R125, and CF3I (concentration of R32 (mass%) / concentration of R125 (mass%) / concentration of CF3I (mass%)) have the composition ratios shown within the range of a triangle with vertices G, D, and F, but excluding the line segment DF. Point G (0.1667x + 56.3 / 2.7778x) 2 -64.944x+357.98 / 100-R1234ze-R32-R125), Point D (1.5625x) 2 -24.938x+155.98 / 0.0 / 100-R1234ze-R32-R125), Point F (-0.6667x+63.733 / 0.0 / 100-R1234ze-R32-R125).

8. The composition according to any one of claims 1 to 7, characterized in that: It also contains refrigeration oil, and the composition is used as a working fluid for refrigeration machines.

9. The composition according to any one of claims 1 to 8, characterized in that: Used as an alternative refrigerant to R410A.

10. Use of the composition according to any one of claims 1 to 8 as an alternative refrigerant to R410A.

11. A refrigeration unit, characterized in that: The composition comprising any one of claims 1 to 9 is used as the working fluid.

12. A method for operating a refrigeration unit, characterized in that, include: The process of using the composition of any one of claims 1 to 9 as the working fluid to circulate it in a refrigeration unit.

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