Refrigerant-containing composition, use thereof, refrigerator containing the same, and operation method of the refrigerator

Abstract

To solve the above problem, the present application provides a composition containing a refrigerant, wherein the refrigerant contains 1,1-difluoroethene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

Description

Technical Field

[0001] This invention relates to compositions containing refrigerants, their applications, 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: HFC-32 or R32) and pentafluoroethane (C2HF5: HFC-125 or R125), and is an azeotropic-like composition.

[0003] However, R410A has a global warming potential (GWP) of 2088, indicating a high level of concern about global warming. Therefore, R32, with a GWP of 675, is used more often.

[0004] Therefore, various low-GWP mixed refrigerants that can replace R410A have been proposed (Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2015 / 141678 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The purpose of this invention is to provide a novel low-GWP mixed refrigerant.

[0010] Technical solutions for solving the problem

[0011] Item 1. A composition containing a refrigerant, wherein the refrigerant contains 1,1-difluoroethylene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropylene (R1234ze).

[0012] Item 2. The composition as described in Item 1, wherein the refrigerant contains 1.5 to 10% by mass of HFO-1132a relative to the total refrigerant.

[0013] Item 3. The composition as described in Item 1, wherein, in the refrigerant described above, when HFO-1132a, R32 and R1234ze are represented by mass % based on their sum as x, y and z respectively, in the three-component composition diagram where the sum of HFO-1132a, R32 and R1234ze is 100% by mass,

[0014] The coordinates (x, y, z) lie within the area bounded by the lines IB, BC, CD, and DI connecting the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8), or on the aforementioned lines.

[0015] Item 4. The composition as described in Item 1, wherein, in the above-described refrigerant, when HFO-1132a, R32, and R1234ze are represented by mass % based on their sum as x, y, and z respectively, in the three-component composition diagram where the sum of HFO-1132a, R32, and R1234ze is 100% by mass,

[0016] The coordinates (x, y, z) lie within the area bounded by the lines IB, BE, EF, and FI that connect the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), E (1.5, 56.2, 42.3), and F (10.0, 37.7, 52.3), or on the aforementioned lines.

[0017] Item 5. The composition as described in Item 1, wherein, in the refrigerant described above, when HFO-1132a, R32 and R1234ze are represented by mass % based on their sum as x, y and z respectively, in the three-component composition diagram where the sum of HFO-1132a, R32 and R1234ze is 100% by mass,

[0018] The coordinates (x, y, z) lie within the area bounded by the lines G'B, BG, and GG' that connect the three points G'(8.6, 73.9, 17.5), B(1.5, 73.9, 24.6), and G(1.5, 65.9, 32.6), or on the aforementioned lines.

[0019] Item 6. The composition as described in Item 1, wherein, in the refrigerant described above, when HFO-1132a, R32 and R1234ze are respectively set as x, y and z based on their total mass%, in the three-component composition diagram where the total mass of HFO-1132a, R32 and R1234ze is 100% by mass,

[0020] The coordinates (x, y, z) lie within the area bounded by the lines JB', B'C, CD, and DJ connecting the four points J (10.0, 59.0, 31.0), B' (1.5, 58.9, 39.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8), or on the aforementioned lines.

[0021] Item 7. The composition as described in Item 1, wherein, in the refrigerant described above, when HFO-1132a, R32 and R1234ze are represented by mass % based on their sum as x, y and z respectively, in the three-component composition diagram where the sum of HFO-1132a, R32 and R1234ze is 100% by mass,

[0022] The coordinates (x, y, z) lie within the area bounded by the lines JB', B'E, EF, and FJ connecting the four points J(10.0, 59.0, 31.0), B'(1.5, 58.9, 39.6), E(1.5, 56.2, 42.3), and F(10.0, 37.7, 52.3), or on the aforementioned lines.

[0023] Item 8. The composition of any one of items 1 to 7, wherein the refrigerant further contains 2,3,3,3-tetrafluoro-1-propylene (R1234yf).

[0024] Item 9. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in the three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0025] The coordinates (x, y, z) lie between points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and D (0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2 The area bounded by the lines AB, BC, CD, and DA connecting the four points (+0.6252a+73.215,0.0) or on AB and CD (excluding points A, B, C, and D).

[0026] Item 10. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in a three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0027] The coordinates (x, y, z) lie between points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and F (0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2 -2.0723a + 47.748, -0.0208a 2 The area bounded by the lines AB, BF, FE, and EA connecting the four points (+1.0723a+52.252,0.0) or the lines AB and FE (excluding points A, B, F, and E).

[0028] Item 11. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in a three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0029] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.1143a). 2 +2.3143a+62.686,0.0,0.1143a 2 -3.3143a+37.314) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0030] Given 7.5 ≥ x > 5.0, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.072a). 2 +1.9a+63.7,0.0,0.072a 2 -2.9a+36.3) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0031] Given 10.0 ≥ x > 7.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), R (73.9, 1.12a-8.4, -2.12a+34.5), and G (-0.0505a). 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AR, RG, and GA connecting the three points (-3.6396a+65.951,0.0) or on the lines AR and RG (excluding points A and G).

[0032] Item 12. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % as y, R1234ze mass % as z, and HFO-1132a mass % as a, in the three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0033] The coordinates (x, y, z) lie between points A'(59.0, -a+41.0, 0), B'(58.9, 0.0, -a+41.1), and D(0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2The area bounded by the lines A'B', B'D, DC, and CA' connecting the four points (+0.6252a+73.215,0.0) or the lines A'B' and DC (excluding points A', B', D, and C).

[0034] Item 13. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in the three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0035] The coordinates (x, y, z) lie between points A'(59.0, -a+41.0, 0.0), B'(58.9, 0.0, -a+41.1), and F(0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2 -2.0723a + 47.748, -0.0208a 2 The area bounded by the lines A'B', B'F, ​​FE, and EA' connecting the four points (+1.0723a+52.252,0.0) or the lines A'B' and FE (excluding points A', B', F, and E).

[0036] Item 14. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in a three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0037] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between point A' (59.0, -a+41.0, 0.0) and point P (-0.019a). 2 +0.1524a +58.714, -0.2571a 2 +4.1571a+9.5429,0.2761a 2 -5.3095a+31.7431) and point G(-0.0505a) 2+2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points -3.6396a+65.951,0.0) or on the lines A'P and PG (excluding points A' and G);

[0038] Given 10.0 ≥ x > 5, the coordinates (x, y, z) lie between points A' (59.0, -a+41.0, 0.0) and P (59.0, -0.136a). 2 +2.94a+12.6,0.136a 2 -3.94a+28.4) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points (-3.6396a+65.951,0.0) or the lines A'P and PG (excluding points A' and G).

[0039] Item 15. The composition of any one of items 1 to 14, which is used as an alternative refrigerant to R410A.

[0040] Item 16. The composition as described in Item 2, wherein, in the refrigerant described above, when HFO-1132a, R32 and R1234ze are set as x, y and z respectively based on their total mass%, in the three-component composition diagram where the total mass of HFO-1132a, R32 and R1234ze is 100% by mass,

[0041] The coordinates (x, y, z) lie within the area bounded by the lines ST, TM, and MS connecting the three points S(10.0, 21.5, 68.5), T(1.9, 21.5, 76.6), and M(10.0, 12.5, 77.5), or on the aforementioned lines.

[0042] Item 17. The composition as described in Item 8, wherein, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, with R32 mass % set as x, R1234yf mass % set as y, R1234ze mass % set as z, and HFO-1132a mass % set as a, in the three-component composition diagram with the sum of R32, R1234yf, and R1234ze as (100-a) mass %...

[0043] Given 1.9 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between points A (21.8, -a+78.2, 0.0), T (21.5, -15.0a+28.5, 14.0a+50.0), and M (0.0035a). 2 -0.9809a + 10.358, -0.0035a 2 The area bounded by the lines A”T, TM and MA” connecting the three points -0.0191a+89.642,0.0) or on the lines A”T and TM (excluding points A” and M);

[0044] Given 10.0 ≥ x > 1.9, the coordinates (x, y, z) lie at points A (21.8, -a+78.2, 0.0), B (0.0108a+21.473, 0.0, -1.0108a+78.527), and L (0.0098a). 2 -1.2237a+23.804,0.0,-0.0098a 2 +0.2237a+76.196) and point M(0.0035a) 2 -0.9809a + 10.358, -0.0035a 2 The area bounded by the lines A”B”, B”L, LM and MA” connecting the four points -0.0191a+89.642,0.0) or the lines A”B” and LM (excluding points A”, B”, L and M).

[0045] Item 18. The composition as described in Item 16 or 17, which is used as an alternative refrigerant to R404A.

[0046] Item 19. The composition of any one of items 1 to 18, wherein it further comprises refrigeration oil for use as a working fluid for refrigeration equipment.

[0047] Item 20. A refrigeration machine, wherein the composition described in any one of items 1 to 14, 16, 17 and 19 is used as the working fluid.

[0048] Item 21. A method of operating a refrigeration machine, comprising the step of circulating the composition described in any one of items 1 to 14, 16, 17 and 19 as a working fluid in the refrigeration machine.

[0049] Item 22. Use of the composition of any one of items 1 to 14 as an alternative refrigerant to R410A.

[0050] Item 23. Use of the composition described in Item 16 or 17 as an alternative refrigerant to R404A.

[0051] Invention Effects

[0052] The refrigerant of this invention is a low-GWP refrigerant. Attached Figure Description

[0053] Figure 1 This is a diagram showing points A to J, A', B', and G', and the line segments connecting them to each other, in a three-component composition diagram with the sum of R32, HFO-1132a, and R1234ze being 100% by mass.

[0054] Figure 2 This is a diagram showing points A to H, P, A', B', C', G' and E', and the line segments connecting them, in a 3-component composition diagram with a total of 98.5% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 1.5% by mass).

[0055] Figure 3 This is a diagram showing points A to H, P, A' and B' and the line segments connecting them to each other, in a three-component composition diagram with a total of 98.5% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 1.5% by mass).

[0056] Figure 4 This is a diagram showing points A to H, P, A' and B' and the line segments connecting them to each other, in a three-component composition diagram with a total of 97.0% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 3.0% by mass).

[0057] Figure 5 This is a diagram showing points A to H, P, A' and B' and the line segments connecting them to each other, in a three-component composition diagram with a total of 95.0% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 5.0% by mass).

[0058] Figure 6 This is a diagram showing points A to H, P, A' and B' and the line segments connecting them to each other, in a three-component composition diagram with a total of 92.5% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 7.5% by mass).

[0059] Figure 7 This is a diagram showing points A to H, P, A' and B' and the line segments connecting them to each other, in a three-component composition diagram with a total of 90.0% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 10.0% by mass).

[0060] Figure 8 This is a diagram showing points A”, B”, L, M, S and T, and the line segments connecting them to each other, in a three-component composition diagram with the sum of R32, HFO-1132a and R1234ze being 100% by mass.

[0061] Figure 9 This is a diagram showing points A”, B”, L, L’, M and T, and the line segments connecting them to each other, in a three-component composition diagram with a total of 98.5% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 1.5% by mass).

[0062] Figure 10 This is a diagram showing points A”, B”, L, L’, M and T, and the line segments connecting them to each other, in a three-component composition diagram with a total of 98.5% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 1.5% by mass).

[0063] Figure 11 The diagram shows points A”, B”, L, M and T, and the line segments connecting them to each other, in a three-component composition diagram with a total of 98.1% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 1.9% by mass).

[0064] Figure 12 This is a graph showing points A”, B”, L and M, and the line segments connecting them to each other, in a three-component composition diagram with a total of 94.0% by mass of R32, R1234yf and R1234ze (HFO-1132a contains 6.0% by mass).

[0065] Figure 13 This is a graph showing points A”, B”, L and M, and the line segments connecting them to each other, in a three-component composition diagram with a total of R32, R1234yf and R1234ze of 90.0% by mass (HFO-1132a contains 10.0% by mass). Detailed Implementation

[0066] In order to solve the above-mentioned technical problems, the inventors of the present invention conducted in-depth research and found that the mixed refrigerant containing HFO-1132a, R32 and R1234ze has the above-mentioned characteristics.

[0067] This invention was completed based on further and repeated research based on the above insights. The invention includes the following embodiments.

[0068] <Definition of Terms>

[0069] In this specification, the term "refrigerant" includes at least compounds designated with an ASHRAE number (prefixed with R) as specified by ISO 817 (International Organization for Standardization), and also substances that, although not designated with a refrigerant number, possess equivalent refrigerant properties. From a structural perspective, refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0070] In this specification, the term "composition containing refrigerant" includes at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) a composition that also contains other components and is capable of being used to obtain a working fluid for refrigeration by mixing with at least refrigeration oil; and (3) a working fluid for refrigeration containing refrigeration oil. In this specification, in these three ways, the composition of (2) is distinguished from the refrigerant itself (including mixtures of refrigerants) and is referred to as "refrigerant composition". Furthermore, the working fluid for refrigeration containing (3) is distinguished from "refrigerant composition" and is referred to as "working fluid containing refrigeration oil".

[0071] In this specification, the term "replacement," when used in a context where a second refrigerant "replaces" a first refrigerant, refers to a situation where, in equipment designed for operation with the first refrigerant, only minor changes to components (refrigeration oil, gaskets, packing, expansion valves, dryers, and at least one of other components) and equipment adjustments are required to enable operation with the second refrigerant under optimal conditions. That is, this type refers to replacing the refrigerant to operate the same equipment. As for this type of "replacement," depending on the degree of change or adjustment required when replacing with the second refrigerant, the methods can be categorized from smallest to largest: "drop-in replacement," "near-drop-in replacement," and "retrofit."

[0072] As a second type, the use of a second refrigerant for equipment designed to operate with a second refrigerant for the same purpose as the existing use of the first refrigerant also falls under the term "substitution." This type refers to replacing the refrigerant to provide the same purpose.

[0073] In this specification, the term "refrigeration machine" refers to any device that extracts heat from an object or space, bringing it to a temperature lower than that of the surrounding external air, and maintains that low temperature. In other words, a refrigeration machine is an energy conversion device that extracts energy from the outside and performs work to transfer heat from a low temperature to a high temperature.

[0074] In this specification, the term "condensation temperature glide" refers to the temperature gradient in a non-azeotropic refrigerant mixture where the liquid and gas phases have different compositions, resulting in different condensation start and end temperatures in the heat exchanger.

[0075] 1. refrigerant

[0076] 1.1 Essential refrigerant components

[0077] The refrigerant of the present invention contains HFO-1132a, R32 and R1234ze.

[0078] The refrigerant of this invention is a low-GWP mixed refrigerant.

[0079] In the refrigerant of the present invention, HFO-1132a preferably contains 1.5 to 10% by mass relative to the total refrigerant. R32 preferably contains 74% by mass or less, more preferably 59% by mass or less, and more preferably 21.8% by mass or less when the refrigerant is an alternative to R404A.

[0080] In the refrigerant of the present invention, when the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf, and R410A is used as a substitute for the refrigerant, R32 preferably contains 11.9% by mass or more, more preferably 29.1% by mass or more, and even more preferably 37.9% by mass or more, relative to the total amount of the refrigerant. The combined amount of R1234ze and R1234yf preferably contains 14.5% by mass or more, more preferably 16.0% by mass or more, and even more preferably 31.0% by mass or more, relative to the total amount of the refrigerant. Furthermore, R1234ze preferably contains 71.8% by mass or less, more preferably 52.3% by mass or less, and even more preferably 32.6% by mass or less, relative to the total amount of the refrigerant. R1234yf preferably contains 78.1% by mass or less, more preferably 60.9% by mass or less, and even more preferably 60.6% by mass or less, relative to the total amount of the refrigerant.

[0081] In the refrigerant of the present invention, when the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf, and R404A is used as a substitute for the refrigerant, R32 preferably contains 0.9% by mass or more relative to the total refrigerant. Furthermore, the combined content of R1234ze and R1234yf preferably contains 68.2% by mass or more relative to the total refrigerant. R1234ze preferably contains 77.5% by mass or less relative to the total refrigerant. R1234yf preferably contains 89.6% by mass or less relative to the total refrigerant.

[0082] The refrigerant of the present invention preferably satisfies the following conditions. At this point, the GWP of the refrigerant of the present invention is 500 or less, and the cooling capacity ratio based on R410A is 70% or more.

[0083] <Conditions>

[0084] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines IB, BC, CD, and DI connecting the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8) respectively, or on the aforementioned straight lines.

[0085] The refrigerant of the present invention preferably satisfies the following conditions. At this point, the GWP of the refrigerant of the present invention is 500 or less, and the cooling capacity ratio based on R410A is 85% or more.

[0086] <Conditions>

[0087] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines IB, BE, EF, and FI connecting the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), E (1.5, 56.2, 42.3), and F (10.0, 37.7, 52.3) respectively, or on the aforementioned straight lines.

[0088] The refrigerant of the present invention preferably satisfies the following conditions: The GWP of the refrigerant of the present invention is 500 or less, and the condensation temperature glide is 5°C or less.

[0089] <Conditions>

[0090] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area enclosed by the straight lines G'B, BG, and GG' connecting the three points G'(8.6, 73.9, 17.5), B(1.5, 73.9, 24.6), and G(1.5, 65.9, 32.6) respectively, or on the aforementioned straight lines.

[0091] The refrigerant of the present invention preferably satisfies the following conditions. At this point, the GWP of the refrigerant of the present invention is 400 or less, and the cooling capacity ratio based on R410A is 70% or more.

[0092] <Conditions>

[0093] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines JB', B'C, CD, and DJ connecting the four points J (10.0, 59.0, 31.0), B' (1.5, 58.9, 39.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8) respectively, or on the aforementioned straight lines.

[0094] The refrigerant of the present invention preferably satisfies the following conditions. At this point, the GWP of the refrigerant of the present invention is 400 or less, and the cooling capacity ratio based on R410A is 85% or more.

[0095] <Conditions>

[0096] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines JB', B'E, EF, and FJ connecting the four points J (10.0, 59.0, 31.0), B' (1.5, 58.9, 39.6), E (1.5, 56.2, 42.3), and F (10.0, 37.7, 52.3) respectively, or on the aforementioned straight lines.

[0097] The refrigerant of the present invention may further contain 2,3,3,3-tetrafluoro-1-propylene (R1234yf).

[0098] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 500 or less, and the cooling capacity ratio based on R410A reaches 70% or more.

[0099] <Conditions>

[0100] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and D (0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2 The area bounded by the lines AB, BC, CD, and DA connecting the four points (+0.6252a+73.215,0.0) or on AB and CD (excluding points A, B, C, and D).

[0101] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 500 or less, and the cooling capacity ratio based on R410A reaches 85% or more.

[0102] <Conditions>

[0103] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and F (0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2 -2.0723a + 47.748, -0.0208a 2 The area bounded by the lines AB, BF, FE, and EA connecting the four points (+1.0723a+52.252,0.0) or the lines AB and FE (excluding points A, B, F, and E).

[0104] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 500 or less, and the condensing temperature glide reaches 5°C or less.

[0105] <Conditions>

[0106] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0107] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.1143a). 2 +2.3143a+62.686,0.0,0.1143a 2 -3.3143a+37.314) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a2 The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0108] Given 7.5 ≥ x > 5.0, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.072a). 2 +1.9a+63.7,0.0,0.072a 2 -2.9a+36.3) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0109] Given 10.0 ≥ x > 7.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), R (73.9, 1.12a-8.4, -2.12a+34.5), and G (-0.0505a). 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AR, RG, and GA connecting the three points (-3.6396a+65.951,0.0) or on the lines AR and RG (excluding points A and G).

[0110] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 400 or less, and the cooling capacity ratio based on R410A reaches 70% or more.

[0111] <Conditions>

[0112] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A'(59.0, -a+41.0, 0), B'(58.9, 0.0, -a+41.1), and D(0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2 The area bounded by the lines A'B', B'D, DC, and CA' connecting the four points (+0.6252a+73.215,0.0) or the lines A'B' and DC (excluding points A', B', D, and C).

[0113] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 400 or less, and the cooling capacity ratio based on R410A reaches 85% or more.

[0114] <Conditions>

[0115] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A'(59.0, -a+41.0, 0.0), B'(58.9, 0.0, -a+41.1), and F(0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2 -2.0723a + 47.748, -0.0208a 2The area bounded by the lines A'B', B'F, ​​FE, and EA' connecting the four points (+1.0723a+52.252,0.0) or the lines A'B' and FE (excluding points A', B', F, and E).

[0116] When the refrigerant of the present invention also contains R1234yf, the following conditions are preferably met. In this case, the GWP of the refrigerant of the present invention reaches 400 or less, and the condensing temperature glide reaches 5°C or less.

[0117] <Conditions>

[0118] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0119] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between point A' (59.0, -a+41.0, 0.0) and point P (-0.019a). 2 +0.1524a +58.714, -0.2571a 2 +4.1571a+9.5429,0.2761a 2 -5.3095a+31.7431) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points -3.6396a+65.951,0.0) or on the lines A'P and PG (excluding points A' and G);

[0120] Given 10.0 ≥ x > 5, the coordinates (x, y, z) lie between points A' (59.0, -a+41.0, 0.0) and P (59.0, -0.136a). 2 +2.94a+12.6,0.136a 2 -3.94a+28.4) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points (-3.6396a+65.951,0.0) or the lines A'P and PG (excluding points A' and G).

[0121] The refrigerants described above are preferred for use as working fluids in refrigeration units, and are particularly suitable as alternative refrigerants to R410A.

[0122] On the other hand, the refrigerants described below are preferably used as working fluids in refrigeration units, and are particularly suitable as alternative refrigerants to R404A.

[0123] Furthermore, the refrigerant of the present invention preferably satisfies the following conditions: The GWP of the refrigerant of the present invention reaches 150 or less, and the condensing temperature glide reaches 5°C or less. Also, the refrigeration capacity ratio based on R404A reaches 70% or more.

[0124] <Conditions>

[0125] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area enclosed by the straight lines ST, TM, and MS connecting the three points S (10.0, 21.5, 68.5), T (1.9, 21.5, 76.6), and M (10.0, 12.5, 77.5) respectively, or on the aforementioned straight lines.

[0126] Furthermore, the refrigerant of the present invention preferably satisfies the following conditions. At this time, the GWP of the refrigerant of the present invention reaches 150 or less, and the cooling capacity ratio based on R404A reaches 70% or more.

[0127] <Conditions>

[0128] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0129] Given 1.9 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between points A (21.8, -a+78.2, 0.0), T (21.5, -15.0a+28.5, 14.0a+50.0), and M (0.0035a). 2 -0.9809a + 10.358, -0.0035a 2The area bounded by the lines A”T, TM and MA” connecting the three points -0.0191a+89.642,0.0) or on the lines A”T and TM (excluding points A” and M);

[0130] Given 10.0 ≥ x > 1.9, the coordinates (x, y, z) lie at points A (21.8, -a+78.2, 0.0), B (0.0108a+21.473, 0.0, -1.0108a+78.527), and L (0.0098a). 2 -1.2237a+23.804,0.0,-0.0098a 2 +0.2237a+76.196) and point M(0.0035a) 2 -0.9809a + 10.358, -0.0035a 2 The area bounded by the lines A”B”, B”L, LM and MA” connecting the four points -0.0191a+89.642,0.0) or the lines A”B” and LM (excluding points A”, B”, L and M).

[0131] 1.2 Additional refrigerant components

[0132] The following describes the additional refrigerants that may be contained in the refrigerant of the present invention. In the refrigerant of the present invention, other additional refrigerants may be contained in addition to HFO-1132a, R32, and R1234ze, without impairing the aforementioned characteristics and effects. In this regard, in one embodiment, the refrigerant of the present invention preferably contains, relative to the total refrigerant, HFO-1132a, R32, and R1234ze in a total of 99.5% by mass or more, more preferably 99.75% by mass or more, further preferably 99.9% by mass or more, even more preferably 99.99% by mass or more, and most preferably 99.9999% by mass or more. The refrigerant of the present invention may be substantially composed only of HFO-1132a, R32, and R1234ze, and the refrigerant of the present invention may also be composed only of HFO-1132a, R32, and R1234ze. In cases where the refrigerant of the present invention is substantially composed only of HFO-1132a, R32, and R1234ze, the refrigerant of the present invention may be composed only of HFO-1132a, R32, and R1234ze, and unavoidable impurities. Alternatively, in another embodiment, the refrigerant of the present invention may contain other additional refrigerants besides HFO-1132a, R32, R1234ze, and R1234yf, without impairing the aforementioned characteristics and effects. Preferably, the refrigerant of the present invention contains a total of 99.5% by mass or more of HFO-1132a, R32, R1234ze, and R1234yf relative to the total refrigerant content; more preferably, 99.75% by mass or more; further preferably, 99.9% by mass or more; even more preferably, 99.99% by mass or more; and most preferably, 99.9999% by mass or more. The refrigerant of the present invention may consist substantially only of HFO-1132a, R32, R1234ze, and R1234yf, or it may consist solely of HFO-1132a, R32, R1234ze, and R1234yf. In the case where the refrigerant of the present invention consists substantially only of HFO-1132a, R32, R1234ze, and R1234yf, the refrigerant of the present invention may also consist solely of HFO-1132a, R32, R1234ze, and R1234yf, and unavoidable impurities.

[0133] There are no particular limitations on the type of refrigerant that can be added; a wide range of options are acceptable. The mixed refrigerant can contain only one type or two or more types.

[0134] 2. Refrigerant Composition

[0135] 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 to obtain a working fluid for refrigeration machines by further mixing with at least refrigeration oil.

[0136] The refrigerant composition of the present invention contains, in addition to the refrigerant of the present invention, at least one other component. 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 the working fluid of a refrigeration machine, 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, in the refrigerant composition of the present invention, the content of refrigeration oil relative to the total refrigerant composition is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass.

[0137] 2.1 Water

[0138] The refrigerant composition of the present invention may contain trace amounts of water. The water content in the refrigerant composition is preferably 0.1% by mass or less relative to the total refrigerant. By containing trace amounts of water in the refrigerant composition, the intramolecular double bonds of the unsaturated fluorocarbon compounds that may be contained in the refrigerant can be stabilized, and the oxidation of the unsaturated fluorocarbon compounds is less likely to occur, thus improving the stability of the refrigerant composition.

[0139] 2.2 tracer

[0140] In order to track any dilution, contamination, or other changes in the refrigerant composition of the present invention, a tracer is added to the refrigerant composition of the present invention at a detectable concentration.

[0141] In the refrigerant composition of the present invention, the tracer may be contained as a single element or as two or more elements.

[0142] There are no particular limitations on the tracer used; it can be appropriately selected from commonly used tracers.

[0143] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorinated ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N₂O). Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluorinated ethers are particularly preferred as tracers.

[0144] The following compounds are preferred as tracers.

[0145] FC-14 (Tetrafluoromethane, CF4)

[0146] HCC-40 (chloromethane, CH3Cl)

[0147] HFC-23 (trifluoromethane, CHF3)

[0148] HFC-41 (fluoromethane, CH3Cl)

[0149] HFC-125 (pentafluoroethane, CF3CHF2)

[0150] HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)

[0151] HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)

[0152] HFC-143a (1,1,1-trifluoroethane, CF3CH3)

[0153] HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)

[0154] HFC-152a (1,1-difluoroethane, CHF2CH3)

[0155] HFC-152 (1,2-difluoroethane, CH2FCH2F)

[0156] HFC-161 (fluoroethane, CH3CH2F)

[0157] HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)

[0158] HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)

[0159] HFC-236ea(1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)

[0160] HFC-227ea(1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)

[0161] HCFC-22 (dichlorofluoromethane, CHClF2)

[0162] HCFC-31 (chlorofluoromethane, CH2ClF)

[0163] CFC-1113 (chlorotrifluoroethylene, CF2=CClF)

[0164] HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2)

[0165] HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)

[0166] HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)

[0167] HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)

[0168] HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0169] The refrigerant composition of the present invention may contain a total tracer amount of about 10 parts per million (ppm) to about 1000 ppm relative to the total refrigerant composition. The refrigerant composition of the present invention preferably contains a total tracer amount of about 30 ppm to about 500 ppm, more preferably about 50 ppm to about 300 ppm, relative to the total refrigerant composition.

[0170] 2.3 Ultraviolet fluorescent dyes

[0171] The refrigerant composition of the present invention may contain a single type or two or more ultraviolet fluorescent dyes.

[0172] As an ultraviolet fluorescent dye, there are no particular limitations, and it can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0173] Examples of ultraviolet fluorescent dyes include naphthalenediimide, coumarin, anthracene, phenanthrene, xanthracene, thioxanthene, benzoxanthracene, and fluorescein, as well as their derivatives. Naphthalenediimide and either or both of coumarin are particularly preferred as ultraviolet fluorescent dyes.

[0174] 2.4 stabilizer

[0175] In the refrigerant composition of the present invention, one or more stabilizers may be contained alone.

[0176] As a stabilizer, there are no particular limitations; it can be appropriately selected from commonly used stabilizers.

[0177] Examples of stabilizers include nitro compounds, ethers, and amines.

[0178] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0179] Examples of ethers include 1,4-dioxane.

[0180] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0181] In addition, butylated hydroxyxylene, benzotriazole, etc. can also be listed.

[0182] The proportion of stabilizer is not particularly limited, but it is generally preferred to be 0.01 to 5% by mass relative to the total refrigerant, and more preferably 0.05 to 2% by mass.

[0183] 2.5 Polymerization inhibitor

[0184] In the refrigerant composition of the present invention, a polymerization inhibitor may be contained as a single agent or as two or more agents.

[0185] There are no particular limitations on the type of polymerization inhibitor used; it can be appropriately selected from commonly used polymerization inhibitors.

[0186] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0187] The proportion of the polymerization inhibitor is not particularly limited, but it is generally preferred to be 0.01 to 5% by mass relative to the total refrigerant, and more preferably 0.05 to 2% by mass.

[0188] 3. Working fluid containing refrigeration oil

[0189] 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 is obtained by mixing refrigeration oil used in the compressor of the refrigeration unit with the refrigerant or refrigerant composition. The working fluid containing refrigeration oil typically contains 10 to 50% by mass of refrigeration oil.

[0190] 3.1 Refrigeration oil

[0191] The composition of the present invention may contain only one type of refrigeration oil or may contain two or more types.

[0192] There are no particular limitations on the type of refrigeration oil used; any commonly used refrigeration oil can be selected. However, depending on the specific needs, a refrigeration oil that excels in improving the miscibility and stability of the aforementioned mixture can be chosen.

[0193] As a base oil for refrigeration oil, it is preferably selected from at least one of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0194] In addition to base oil, refrigeration oil may also contain additives. These additives can be at least one selected from antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoamers.

[0195] From a lubrication perspective, refrigeration oils with a kinematic viscosity of 5 to 400 cSt at 40°C are preferred.

[0196] The working fluid containing refrigeration oil of the present invention may also contain at least one additive as needed. Examples of additives include compatibilizers, etc.

[0197] 3.2 Compatibilizer

[0198] In the working fluid containing refrigeration oil of the present invention, a single compatibilizer or two or more compatibilizers may be included.

[0199] There are no particular limitations on the compatibilizer; it can be appropriately selected from commonly used compatibilizers.

[0200] Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluorinated ethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as compatibilizers.

[0201] 4. How to operate a refrigeration unit

[0202] 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.

[0203] Specifically, the method of operating the refrigeration machine of the present invention includes the step of circulating the refrigerant of the present invention within the refrigeration machine.

[0204] The implementation methods have been described above, but it should be understood that various changes in manner and details may be made without departing from the spirit and scope of the claimed protection.

[0205] Example

[0206] The following examples provide a more detailed description. However, the present invention is not limited to these examples.

[0207] HFO-1132a, R32 and R1234ze were mixed at the mass percentages shown in Table 1 based on their total amount to prepare a mixed refrigerant.

[0208] The GWP of R410A (R32 = 50% / R125 = 50%) and the above-mentioned mixed refrigerants is evaluated based on the values ​​from the Intergovernmental Panel on Climate Change (IPCC) Fourth Report. The GWP of HFO-1132a is assumed to be 1. The refrigeration capacity of R410A and the above-mentioned mixed refrigerants was determined using the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) of the National Institute of Standards and Technology (NIST) by performing theoretical calculations on the mixed refrigerant refrigeration cycle under the following conditions.

[0209] For each of these refrigerant mixtures, the COP ratio and cooling capacity ratio, based on R410A, were calculated. The calculation conditions were set as follows.

[0210] Evaporation temperature: 5℃

[0211] Condensation temperature: 45℃

[0212] Overheating: 5K

[0213] Supercooling: 5K

[0214] Compressor efficiency: 70%

[0215] These values, along with the GWP of each refrigerant mixture, are shown in Table 1. Here, specific COP and specific cooling capacity are expressed relative to R410A.

[0216] The coefficient of performance (COP) is calculated using the following formula.

[0217] COP = (Cooling or Heating Capacity) / Electricity Consumption

[0218] [Table 1]

[0219]

[0220] These results indicate that these mixed refrigerants achieve a GWP below 500 and a cooling capacity ratio of over 70% based on R410A when the following conditions are met.

[0221] <Conditions>

[0222] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines IB, BC, CD, and DI connecting the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8) respectively, or on the aforementioned straight lines.

[0223] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 500 and the cooling capacity ratio based on R410A reaches above 85%.

[0224] <Conditions>

[0225] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines IB, BE, EF, and FI connecting the four points I (10.0, 74.0, 16.0), B (1.5, 73.9, 24.6), E (1.5, 56.2, 42.3), and F (10.0, 37.7, 52.3) respectively, or on the aforementioned straight lines.

[0226] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 500 and the condensing temperature glide reaches below 5°C.

[0227] <Conditions>

[0228] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area enclosed by the straight lines G'B, BG, and GG' connecting the three points G'(8.6, 73.9, 17.5), B(1.5, 73.9, 24.6), and G(1.5, 65.9, 32.6) respectively, or on the aforementioned straight lines.

[0229] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 400 and the cooling capacity ratio based on R410A reaches above 70%.

[0230] <Conditions>

[0231] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines JB', B'C, CD, and DJ connecting the four points J (10.0, 59.0, 31.0), B' (1.5, 58.9, 39.6), C (1.5, 35.8, 62.7), and D (10.0, 18.2, 71.8) respectively, or on the aforementioned straight lines.

[0232] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 400 and the cooling capacity ratio based on R410A reaches above 85%.

[0233] <Conditions>

[0234] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area of ​​the figure enclosed by the straight lines JB', B'E, EF, and FJ connecting the four points J (10.0, 59.0, 31.0), B' (1.5, 58.9, 39.6), E (1.5, 56.2, 42.3), and F (10.0, 37.7, 52.3) respectively, or on the aforementioned straight lines.

[0235] The same evaluation was performed on mixed refrigerants containing R1234yf in addition to HFO-1132a, R32, and R1234ze. The results are shown in Tables 2-4.

[0236] [Table 2]

[0237]

[0238] [Table 3]

[0239]

[0240] [Table 4]

[0241]

[0242] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 500 and the cooling capacity ratio based on R410A reaches above 70%.

[0243] <Conditions>

[0244] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and D (0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2 The area bounded by the lines AB, BC, CD, and DA connecting the four points (+0.6252a+73.215,0.0) or on AB and CD (excluding points A, B, C, and D).

[0245] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 500 and the cooling capacity ratio based on R410A reaches above 85%.

[0246] <Conditions>

[0247] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and F (0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2-2.0723a + 47.748, -0.0208a 2 The area bounded by the lines AB, BF, FE, and EA connecting the four points (+1.0723a+52.252,0.0) or the lines AB and FE (excluding points A, B, F, and E).

[0248] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 500 and the condensing temperature glide reaches below 5°C.

[0249] <Conditions>

[0250] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0251] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.1143a). 2 +2.3143a+62.686,0.0,0.1143a 2 -3.3143a+37.314) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0252] Given 7.5 ≥ x > 5.0, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), and H (-0.072a). 2 +1.9a+63.7,0.0,0.072a 2 -2.9a+36.3) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2The area bounded by the lines AB, BH, HG, and GA connecting the four points -3.6396a+65.951,0.0) or on the lines AB and HG (excluding points A, B, H, and G);

[0253] Given 10.0 ≥ x > 7.5, the coordinates (x, y, z) lie at points A (74.0, -a+26.0, 0.0), R (73.9, 1.12a-8.4, -2.12a+34.5), and G (-0.0505a). 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines AR, RG, and GA connecting the three points (-3.6396a+65.951,0.0) or on the lines AR and RG (excluding points A and G).

[0254] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 400 and the cooling capacity ratio based on R410A reaches above 70%.

[0255] <Conditions>

[0256] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A'(59.0, -a+41.0, 0), B'(58.9, 0.0, -a+41.1), and D(0.0098a). 2 -2.1856a+39.064,0.0,-0.0098a 2 +1.1856a+60.936) and point C(0.0138a) 2 -1.6252a + 26.785, -0.0138a 2 The area bounded by the lines A'B', B'D, DC, and CA' connecting the four points (+0.6252a+73.215,0.0) or the lines A'B' and DC (excluding points A', B', D, and C).

[0257] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 400 and the cooling capacity ratio based on R410A reaches above 85%.

[0258] <Conditions>

[0259] In the above refrigerant, taking the sum of R32, R1234yf, R1234ze, and HFO-1132a as the baseline, and setting the mass percentage of R32 as x, the mass percentage of R1234yf as y, the mass percentage of R1234ze as z, and the mass percentage of HFO-1132a as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass%, the coordinates (x, y, z) are located at points A'(59.0, -a+41.0, 0.0), B'(58.9, 0.0, -a+41.1), and F(0.0102a). 2 -2.2922a+59.604,0.0,-0.0102a 2 +1.2922a+40.396) and point E(0.0208a) 2 -2.0723a + 47.748, -0.0208a 2 The area bounded by the lines A'B', B'F, ​​FE, and EA' connecting the four points (+1.0723a+52.252,0.0) or the lines A'B' and FE (excluding points A', B', F, and E).

[0260] These results show that when these mixed refrigerants meet the following conditions, the GWP reaches below 400 and the condensing temperature glide reaches below 5°C.

[0261] <Conditions>

[0262] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0263] Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between point A' (59.0, -a+41.0, 0.0) and point P (-0.019a). 2 +0.1524a +58.714, -0.2571a 2 +4.1571a+9.5429,0.2761a 2 -5.3095a+31.7431) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2The area bounded by the lines A'P, PG, and GA' connecting the three points -3.6396a+65.951,0.0) or on the lines A'P and PG (excluding points A' and G);

[0264] Given 10.0 ≥ x > 5, the coordinates (x, y, z) lie between points A' (59.0, -a+41.0, 0.0) and P (59.0, -0.136a). 2 +2.94a+12.6,0.136a 2 -3.94a+28.4) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points (-3.6396a+65.951,0.0) or the lines A'P and PG (excluding points A' and G).

[0265] As shown in Tables 5 and 6, the approximate formulas representing the coordinates of each point can be obtained by taking the approximate formula of the curve connecting the three points.

[0266] [Table 5]

[0267]

[0268] [Table 6]

[0269]

[0270] For each refrigerant mixture, the COP ratio and cooling capacity ratio based on R404A were calculated. The calculation conditions were set as follows.

[0271] Evaporation temperature: -40℃

[0272] Condensation temperature: 40℃

[0273] Overheating: 20K

[0274] Supercooling: 0K

[0275] Compressor efficiency: 70%

[0276] These values, along with the GWP of each refrigerant mixture, are shown in Tables 7 and 8. Specific COP and specific cooling capacity are expressed relative to R404A.

[0277] The coefficient of performance (COP) is calculated using the following formula.

[0278] COP = (Cooling or Heating Capacity) / Electricity Consumption

[0279] The various properties of the mixed refrigerant were evaluated by varying the concentration of HFO-1132a, as shown in Tables 7 and 8.

[0280] [Table 7]

[0281]

[0282] [Table 8]

[0283]

[0284] As shown in Tables 7 and 8, these mixed refrigerants achieve a GWP of less than 150 and a cooling capacity ratio of more than 70% based on R404A when the following conditions are met.

[0285] <Conditions>

[0286] In the above refrigerants, when the mass percentage of HFO-1132a, R32, and R1234ze is taken as the sum of their masses and set as x, y, and z respectively, in the three-component composition diagram with the sum of HFO-1132a, R32, and R1234ze as 100% by mass, the coordinates (x, y, z) are located within the area enclosed by the straight lines ST, TM, and MS connecting the three points S (10.0, 21.5, 68.5), T (1.9, 21.5, 76.6), and M (10.0, 12.5, 77.5) respectively, or on the aforementioned straight lines.

[0287] As shown in Tables 7 and 8, these mixed refrigerants achieve a GWP of less than 150 and a cooling capacity ratio of more than 70% based on R404A when the following conditions are met.

[0288] <Conditions>

[0289] In the above refrigerants, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a, and with R32's mass % set as x, R1234yf's mass % as y, R1234ze's mass % as z, and HFO-1132a's mass % as a, in the three-component composition diagram where the sum of R32, R1234yf, and R1234ze is (100-a) mass %,

[0290] Given 1.9 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between points A (21.8, -a+78.2, 0.0), T (21.5, -15.0a+28.5, 14.0a+50.0), and M (0.0035a). 2 -0.9809a + 10.358, -0.0035a 2The area bounded by the lines A”T, TM and MA” connecting the three points -0.0191a+89.642,0.0) or on the lines A”T and TM (excluding points A” and M);

[0291] Given 10.0 ≥ x > 1.9, the coordinates (x, y, z) lie at points A (21.8, -a+78.2, 0.0), B (0.0108a+21.473, 0.0, -1.0108a+78.527), and L (0.0098a). 2 -1.2237a+23.804,0.0,-0.0098a 2 +0.2237a+76.196) and point M(0.0035a) 2 -0.9809a + 10.358, -0.0035a 2 The area bounded by the lines A”B”, B”L, LM and MA” connecting the four points -0.0191a+89.642,0.0) or the lines A”B” and LM (excluding points A”, B”, L and M).

[0292] As shown in Table 9, the approximate formula for the coordinates of each point can be obtained by finding the approximate formula for the curve connecting the three points.

[0293] [Table 9]

[0294]

[0295] The following mixed refrigerants were also evaluated in the same way.

[0296] [Table 10]

[0297]

[0298] [Table 11]

[0299]

[0300] [Table 12]

[0301]

[0302] [Table 13]

[0303]

[0304] [Table 14]

[0305]

[0306] [Table 15]

[0307]

[0308] [Table 16]

[0309]

[0310] [Table 17]

[0311]

[0312] [Table 18]

[0313]

[0314] [Table 19]

[0315]

[0316] [Table 20]

[0317]

Claims

1. A composition comprising a refrigerant, characterized in that: the refrigerant contains 1,1-difluoroethene (HFO-1132a), difluoromethane (R32) and 1,3,3,3-tetrafluoropropene (R1234ze) in total of 99.5% by mass or more relative to the entire refrigerant, in the refrigerant, when mass% of HFO-1132a, R32 and R1234ze based on the total of them is respectively set to x, y and z, in a 3-component composition diagram in which the total of HFO-1132a, R32 and R1234ze is 100% by mass, a coordinate (x, y, z) is located within a range of or on a figure surrounded by straight lines IB, BE, EF and FI connecting 4 points of point I (10.0, 74.0, 16.0), point B (1.5, 73.9, 24.6), point E (1.5, 56.2, 42.3) and point F (10.0, 37.7, 52.3) respectively.

2. A composition comprising a refrigerant, characterized in that: the refrigerant contains HFO-1132a, R32 and R1234ze in total of 99.5% by mass or more relative to the entire refrigerant, in the refrigerant, when mass% of HFO-1132a, R32 and R1234ze based on the total of them is respectively set to x, y and z, in a 3-component composition diagram in which the total of HFO-1132a, R32 and R1234ze is 100% by mass, a coordinate (x, y, z) is located within a range of or on a figure surrounded by straight lines G'B, BG and GG' connecting 3 points of point G' (8.6, 73.9, 17.5), point B (1.5, 73.9, 24.6) and point G (1.5, 65.9, 32.6) respectively.

3. A composition comprising a refrigerant, characterized in that: the refrigerant contains HFO-1132a, R32 and R1234ze in total of 99.5% by mass or more relative to the entire refrigerant, in the refrigerant, when mass% of HFO-1132a, R32 and R1234ze based on the total of them is respectively set to x, y and z, in a 3-component composition diagram in which the total of HFO-1132a, R32 and R1234ze is 100% by mass, a coordinate (x, y, z) is located within a range of or on a figure surrounded by straight lines JB', B'E, EF and FJ connecting 4 points of point J (10.0, 59.0, 31.0), point B' (1.5, 58.9, 39.6), point E (1.5, 56.2, 42.3) and point F (10.0, 37.7, 52.3) respectively.

4. A composition comprising a refrigerant, characterized in that: the refrigerant contains HFO-1132a, R32, R1234ze and 2,3,3,3-tetrafluoro-1-propene (R1234yf) in total of 99.5% by mass or more relative to the entire refrigerant, ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100-a) mass%, The coordinates (x, y, z) are located in the area of the figure enclosed by the straight lines AB, BC, CD and DA, which are respectively connected to the four points A (74.0, -a + 26.0, 0.0), B (73.9, 0.0, -a + 26.1), D (0.0098a 2 - 2.1856a + 39.064, 0.0, -0.0098a 2 + 1.1856a + 60.936) and C (0.0138a 2 - 1.6252a + 26.785, -0.0138a 2 + 0.6252a + 73.215, 0.0), or on the AB and CD, excluding points A, B, C and D.

5. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100-a) mass%, The coordinates (x, y, z) are located in the area of the figure enclosed by the straight lines AB, BF, FE and EA connecting the four points A (74.0, -a + 26.0, 0.0), B (73.9, 0.0, -a + 26.1), F (0.0102a 2 - 2.2922a + 59.604, 0.0, -0.0102a 2 + 1.2922a + 40.396) and E (0.0208a 2 - 2.0723a + 47.748, -0.0208a 2 + 1.0723a + 52.252, 0.0) respectively, or on the straight lines AB and FE, with the exception of the points A, B, F and E.

6. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100-a) mass%, In the case of 5.0 > x > 1.5, the coordinates (x, y, z) are located in the range of a figure enclosed by straight lines AB, BH, HG and GA connecting four points A (74.0, -a + 26.0, 0.0), B (73.9, 0.0, -a + 26.1), H (-0.1143a + 62.686, 0.0, 0.1143a 2 + 2.3143a + 62.686, 0.0, 0.1143a 2 - 3.3143a + 37.314) and G (-0.0505a 2 + 2.6396a + 34.049, 0.0505a 2 - 3.6396a + 65.951, 0.0) respectively, or on the straight lines AB and HG, excluding points A, B, H and G; In the case of 7.5≥x>5.0, the coordinates (x, y, z) are located in the range of a figure enclosed by straight lines AB, BH, HG and GA connecting four points A (74.0, -a+26.0, 0.0), B (73.9, 0.0, -a+26.1), H (-0.072a 2 +1.9a+63.7, 0.0, 0.072a 2 -2.9a+36.3) and G (-0.0505a 2 +2.6396a+34.049, 0.0505a 2 -3.6396a+65.951, 0.0) respectively, or on the straight lines AB and HG, wherein points A, B, H and G are excluded; In the case of 10.0 > x > 7.5, the coordinates (x, y, z) are located in the range of the figure enclosed by the straight lines AR, RG and GA connecting the three points A (74.0, -a + 26.0, 0.0), R (73.9, 1.12a - 8.4, -2.12a + 34.5) and G (-0.0505a + 26.0, 0.0) respectively, or on the straight lines AR and RG, with the exception of the points A and G. 2 + 2.6396a + 34.049, 0.0505a 2 - 3.6396a + 65.951, 0.0) respectively.

7. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100-a) mass%, The coordinates (x, y, z) are located in the area of the figure enclosed by the straight lines A'B', B'D, DC and CA' connecting the four points A'(59.0, -a + 41.0, 0), B'(58.9, 0.0, -a + 41.1), D(0.0098a 2 -2.1856a + 39.064, 0.0, -0.0098a 2 +1.1856a + 60.936) and C(0.0138a 2 -1.6252a + 26.785, -0.0138a 2 +0.6252a + 73.215, 0.0), or on the straight lines A'B' and DC, not including the points A', B', D and C.

8. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100 - a) mass%, The coordinates (x, y, z) are located in the area of the figure enclosed by the straight lines A'B', B'F, FE and EA' connecting the four points A' (59.0, -a + 41.0, 0.0), B' (58.9, 0.0, -a + 41.1), F (0.0102a 2 - 2.2922a + 59.604, 0.0, -0.0102a 2 + 1.2922a + 40.396) and E (0.0208a 2 - 2.0723a + 47.748, -0.0208a 2 + 1.0723a + 52.252, 0.0) respectively, or on the straight lines A'B' and FE, excluding the points A', B', F and E.

9. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in a total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100 - a) mass%, Given 5.0 ≥ x ≥ 1.5, the coordinates (x, y, z) lie between point A' (59.0, -a+41.0, 0.0) and point P (-0.019a). 2 +0.1524a +58.714, -0.2571a 2 +4.1571a+9.5429,0.2761a 2 -5.3095a+31.7431) and point G(-0.0505a) 2 +2.6396a+34.049,0.0505a 2 The area bounded by the lines A'P, PG, and GA' connecting the three points (-3.6396a+65.951,0.0) or the lines A'P and PG, excluding points A' and G; In the case where 10.0 > x > 5, the coordinates (x, y, z) are located in the range of a figure enclosed by straight lines A'P, PG and GA' connecting three points A'(59.0, -a + 41.0, 0.0), P(59.0, -0.136a + 12.6, 0.136a) and G(-0.0505a + 2.94a + 12.6, 0.0505a 2 + 2.94a + 12.6, 0.136a 2 - 3.94a + 28.4) and G(-0.0505a + 2.6396a + 34.049, 0.0505a 2 + 2.6396a + 34.049, 0.0505a 2 - 3.6396a + 65.951, 0.0) respectively, or on the straight lines A'P and PG, wherein points A' and G are excluded.

10. The composition according to any one of claims 1 to 9, characterized by being used as a substitute refrigerant for R410A.

11. A composition containing a refrigerant, characterized by comprising: the refrigerant contains HFO-1132a, R32, R1234ze, and R1234yf in a total of 99.5 mass% or more relative to the entire refrigerant, In the refrigerant, when the mass% of R32 is x, the mass% of R1234yf is y, the mass% of R1234ze is z, and the mass% of HFO-1132a is a, based on the total of R32, R1234yf, and R1234ze and HFO-1132a, in a ternary composition diagram in which the total of R32, R1234yf, and R1234ze is (100 - a) mass%, 12. The composition according to claim 11, characterized by being used as a substitute refrigerant for R404A. In the case where 1.9 > x > 1.5, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines A" T, TM and MA" connecting the three points A" (21.8, -a + 78.2, 0.0), T (21.5, -15.0a + 28.5, 14.0a + 50.0) and M (0.0035a 2 -0.9809a + 10.358, -0.0035a 2 -0.0191a + 89.642, 0.0) or on the straight lines A" T and TM, not including the points A" and M. In the case where 1.9 > x > 1.5, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines A" T, TM and MA" connecting the three points A" (21.8, -a + 78.2, 0.0), T (21.5, -15.0a + 28.5, 14.0a + 50.0) and M (0.0035a -0.9809a + 10.358, -0.0035a -0.0191a + 89.642, 0.0) or on the straight lines A" T and TM, not including the points A" and In the case where 10.0 > x > 1.9, the coordinates (x, y, z) are located within the range of a figure enclosed by straight lines A" B", B" L, LM and MA" connecting four points A" (21.8, -a + 78.2, 0.0), B" (0.0108a + 21.473, 0.0, -1.0108a + 78.527), L (0.0098a + 21.991, 0.0, -1.0098a + 78.009) and M (0.0035a + 22.035, 0.0, -1.0035a + 77.965) respectively or on the straight lines A" B" and LM, wherein the points A", B", L and M are excluded. 2 -1.2237a + 23.804, 0.0, -0.0098a 2 +0.2237a + 76.196) and M (0.0035a 2 -0.9809a + 10.358, -0.0035a 2 In the case where 10.0 > x > 1.9, the coordinates (x, y, z) are located within the range of a figure enclosed by straight lines A" B", B" L, LM and MA" connecting four points A" (21.8, -a + 78.2, 0.0), B" (0.0108a + 21.473, 0.0, -1.0108a + 78.527), L (0.0098a + 21.991, 0.0, -1.0098a + 78.009) and M (0.0035a + 22.035, 0.0, -1.0035a + 77.965) respectively or on the straight lines A" B" and LM, wherein the points A", B", L and M are excluded.

13. The composition according to any one of claims 1 to 9, 11, characterized by further comprising a refrigeration machine oil, and being used as a working fluid for a refrigeration machine.

14. A refrigeration machine, characterized by comprising the composition according to any one of claims 1 to 9, 11, and 13 as a working fluid. including: a step of circulating the composition according to any one of claims 1 to 9, 11, and 13 as a working fluid in a refrigeration machine.

16. Use of the composition according to any one of claims 1 to 9 as a substitute refrigerant for R410A.

17. Use of the composition according to claim 11 as a substitute refrigerant for R404A.

15. A method of operating a refrigerator, characterized by, 18. The composition according to claim 10, characterized by further comprising a refrigeration machine oil, and being used as a working fluid for a refrigeration machine.

19. The composition according to claim 12, characterized by further comprising a refrigeration machine oil, and being used as a working fluid for a refrigeration machine. ​ ​ ​ ​ ​ ​

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