A composition containing a refrigerant, its use, and a refrigerator having the same, and a method of operating the refrigerator.

Abstract

To provide a novel refrigerant that does not cause disproportionation reactions. [Solution] A composition containing a refrigerant, wherein the refrigerant comprises 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a, wherein the refrigerant comprises HFO-1132(E), R1234ze, R1234yf, and HFO-1132a, When the mass percent based on the sum of these is denoted as x, y, z, and a, respectively, the present invention provides a composition in which, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass percent, the coordinates (x,y,z) lie within the range of a figure enclosed by the lines CD, DH, HG, and GC connecting specific points C, D, H, and G, respectively, or on the aforementioned lines (except for points H and G).

Description

Technical Field

[0001] The present disclosure relates to a composition containing a refrigerant, its use, a refrigerator having the same, and an operating method of the refrigerator.

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a composition containing a refrigerant having a property that disproportionation reaction does not occur at 3 MPa and 150 °C. Another object of the present disclosure is to provide the use of the above composition, a refrigerator having the same, and an operating method of the refrigerator.

Means for Solving the Problems

[0005] The present disclosure provides an invention in the following aspects. Item 1. A composition containing a refrigerant, where the refrigerant contains 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a, In the aforementioned refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) and Point G(0.0, 100-a, 0.0) The area within the figure enclosed by the lines CD, DO, OG, and GC connecting the four points respectively, or located on the lines CD, DO, and GC (excluding points O and G), composition. Section 2. A composition containing a refrigerant, The refrigerant comprises 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a. In the aforementioned refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-1.75a+12.083, 0.0, 0.75a+87.917) and Point A(-1.75a+29.917, 0.75a+70.083, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (2) 0.4 <a<7.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-0.0051a 2 -1.5885a+12.036, 0.0, 0.0051a 2 (+0.5885a+87.964) and Point A(-0.0026a 2 -1.7943a + 29.918, 0.0026a 2 Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points +0.7943a+70.082, 0.0), or on the lines CD, DB, BA, and AC, (3) When 7.4 ≤ a ≤ 10 Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) Point B(0.0, -1.9091a 2 +46.718a-241.17, 1.9091a 2 -47.718a+341.17) and Point A(-0.0186a 2 -1.5217a + 28.782, 0.0186a 2 (+0.5217a+71.218, 0.0) Within the area of ​​the figure enclosed by the lines CD, DO, OB, BA, and AC connecting the five points, or on the lines CD, DO, BA, and AC (excluding points O and B), The composition described in item 1. Section 3. The refrigerant contains HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a. In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, R1234yf and HFO-1132a based on their total sum are x, y, z and a respectively, in a ternary composition diagram where the sum of HFO-1132(E), R1234ze and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are (1) When 0 < a ≤ 0.4 Point C(-a + 44.0, 56.0, 0.0) Point D(-a + 44.0, 0.0, 56.0) Point F(-1.5a + 8.4, 0.0, 0.5a + 91.6) and Point E(-1.5a + 27.2, 0.5a + 72.8, 0.0) within the range of the figure surrounded by the straight lines CD, DF, FE and EC connecting these four points respectively or on the straight lines CD, DF, FE and EC, (2) When 0.4 < a < 5.5 Point C(-a + 44.0, 56.0, 0.0) Point D(-a + 44.0, 0.0, 56.0) Point F(0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 +0.5508a + 91.58) and Point E(0.0024a 2 -1.7005a + 27.28, -0.0024a 2 +0.7005a + 72.72, 0.0) within the range of the figure surrounded by the straight lines CD, DF, FE and EC connecting these four points respectively or on the straight lines CD, DF, FE and EC, (3) When 5.5 ≤ a ≤ 10 Point C(-a + 44.0, 56.0, 0.0) Point D(-a + 44.0, 0.0, 56.0) Point O(0.0, 0.0, 100.0 - a) Point F(0.0, 0.8762a 2+23.914a-105.02, -0.8762a 2 -24.914a+205.02) and Point E(0.0031a 2 -1.7365a + 27.458, -0.0031a 2 +0.7365a+72.542, 0.0) Within the area of ​​the figure enclosed by the lines CD, DO, OF, FE, and EC connecting the five points, or on the lines CD, DO, FE, and EC (excluding points O and F), The composition described in item 1. Section 4. The refrigerant comprises HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a. In the refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-1.75a+24.317, 0.0, 0.75a+75.683) and Point J(-2.0a+39.0, a+61.0, 0.0) The area within the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or located on the lines CD, DK, KJ, and JC, (2) 0.4 <a≦10のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-0.0043a 2 -1.809a + 24.324, 0.0, 0.0043a 2 (+0.809a+75.676) and Point J(-0.0087a 2-2.0347a + 39.015, 0.0087a 2 +1.0347a+60.985, 0.0) Within the area of ​​the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or on the lines CD, DK, KJ, and JC, The composition described in item 1. Section 5. Furthermore, the composition according to any one of claims 1 to 4, which contains refrigeration oil and is used as a working fluid for a refrigeration unit. Section 6. The composition described in item 2, which is used as a substitute refrigerant for R1234yf. Section 7. The composition described in item 3, which is used as a substitute refrigerant for R404A. Section 8. The composition described in item 4, which is used as a substitute refrigerant for R410A. Section 9. Use of any composition described in item 1 to 8 as a refrigerant. Section 10. A refrigerator comprising a composition described in any one of items 1 to 8 as a working fluid. Section 11. A refrigeration method comprising the step of operating a refrigeration cycle using a composition described in any one of items 1 to 8. Section 12. A method for operating a refrigerator, comprising the step of circulating a composition described in any one of items 1 to 8 as a working fluid in the refrigerator. [Effects of the Invention]

[0006] The refrigerant disclosed herein does not undergo a disproportionation reaction at 3 MPa and 150°C. [Brief explanation of the drawing]

[0007] [Figure 1] This diagram shows a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100% by mass, with points and line segments defining the refrigerant of this disclosure. [Figure 2]This figure shows the points and line segments that define the refrigerant of this disclosure at a = 0.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 3] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 0.4, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 4] This diagram shows the points and line segments that define the refrigerant of this disclosure at a=4, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 5] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 7.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 6] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 8.5, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 7] This figure shows the points and line segments that define the refrigerant of this disclosure at a=10, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 8] This diagram shows a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100% by mass, with points and line segments defining the refrigerant of this disclosure. [Figure 9]This figure shows the points and line segments that define the refrigerant of this disclosure at a = 0.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 10] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 0.4, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 11] This diagram shows the points and line segments that define the refrigerant of this disclosure at a=4, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 12] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 7.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 13] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 8.5, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 14] This figure shows the points and line segments that define the refrigerant of this disclosure at a=10, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 15] This diagram shows a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100% by mass, with points and line segments defining the refrigerant of this disclosure. [Figure 16]This figure shows the points and line segments that define the refrigerant of this disclosure at a = 0.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 17] This diagram shows the points and line segments that define the refrigerant of this disclosure at a = 0.4, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 18] This figure shows the points and line segments that define the refrigerant of this disclosure at a = 4.2, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Figure 19] This figure shows the points and line segments that define the refrigerant of this disclosure at a=10, where a is the content of HFO-1132a, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a is 100% by mass. [Modes for carrying out the invention]

[0008] In order to solve the above problems, the inventors conducted diligent research and found that the various mixed refrigerants described below possess the above characteristics.

[0009] This disclosure is the result of further research based on the aforementioned findings. This disclosure includes the following embodiments. <Definition of Terms> In this specification, the term "refrigerant" includes at least compounds that have been assigned a refrigerant number (ASHRAE number) beginning with R, as defined by ISO 817 (International Organization for Standardization), and also includes compounds that have equivalent refrigerant properties even if they have not yet been assigned a refrigerant number. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of their compound structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Examples of "non-fluorocarbon compounds" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).

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

[0011] In this specification, when the term “substitute” is used in the context of “substituting” a first refrigerant with a second refrigerant, the first type means that equipment designed to operate using the first refrigerant can be operated under optimal conditions using the second refrigerant with only minor changes to components (at least one of the following: refrigerant oil, gaskets, packings, expansion valves, dryers, and other components) and equipment adjustments as needed. In other words, this type refers to operating the same equipment with a “substitute” refrigerant. The forms of “substitution” in this type may be, in order of increasing degree of change or adjustment required when replacing with the second refrigerant, “drop-in substitution,” “nealy drop-in substitution,” and “retrofit.”

[0012] A second type of "substitution" includes using equipment designed to operate with a second refrigerant, but for the same existing applications as the first refrigerant, by installing the second refrigerant. This type refers to providing the same application by "substituting" a refrigerant.

[0013] In this specification, the term "refrigeration unit" refers to any device that removes heat from an object or space to a temperature lower than the surrounding ambient air and maintains that low temperature. In other words, a refrigerator is a conversion device that obtains energy from an external source, performs work, and converts energy in order to transfer heat from a lower temperature to a higher temperature.

[0014] Unless otherwise specified, the pressures described herein are in absolute pressure.

[0015] 1. refrigerant 1.1 Refrigerant components The refrigerants of this disclosure include HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a.

[0016] The refrigerant disclosed herein does not undergo disproportionation at 3 MPa and 150°C. Furthermore, it is a low GWP mixed refrigerant.

[0017] Furthermore, in the refrigerant of this disclosure, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and no measures are required to prevent disproportionation of the equipment.

[0018] <Requirements> When the mass percentages of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a, based on their sum, are x, y, z, and a respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: Point C(-a+44.0.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) and Point G(0.0, 100-a, 0.0) The area within the figure enclosed by the lines CD, DO, OG, and GC connecting the four points, or the area on the lines CD, DO, and GC (excluding points O and G).

[0019] In the refrigerant of this disclosure, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the refrigeration capacity (sometimes called Cooling Capacity, Capacity, or Cap.) relative to R1234yf is 125% or more.

[0020] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-1.75a+12.083, 0.0, 0.75a+87.917) and Point A(-1.75a+29.917, 0.75a+70.083, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (2) 0.4 <a<7.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-0.0051a 2 -1.5885a+12.036, 0.0, 0.0051a 2 (+0.5885a+87.964) and Point A(-0.0026a 2 -1.7943a + 29.918, 0.0026a 2 +0.7943a+70.082, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (3) When 7.4 ≤ a ≤ 10 Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) Point B(0.0, -1.9091a 2 +46.718a-241.17, 1.9091a 2 -47.718a+341.17) and Point A(-0.0186a 2 -1.5217a + 28.782, 0.0186a 2 (+0.5217a+71.218, 0.0) The five points are located within the area of ​​the figure enclosed by the lines CD, DO, OB, BA, and AC connecting them, or on the lines CD, DO, BA, and AC (excluding points O and B). In this case, the refrigerant of this disclosure does not undergo a disproportionation reaction at 3 MPa and 150°C, and the refrigeration capacity ratio based on R1234yf is 125% or more.

[0021] In the refrigerant of this disclosure, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the cap. relative to R404A is 60% or more.

[0022] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point F(-1.5a+8.4, 0.0, 0.5a+91.6) and Point E(-1.5a+27.2, 0.5a+72.8, 0.0) The area within the figure enclosed by the lines CD, DF, FE, and EC connecting the four points, or located on the lines CD, DF, FE, and EC, (2) 0.4 <a<5.5のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point F(0.0036a 2 -1.5508a+8.42, 0.0, -0.0036a 2 (+0.5508a+91.58) and Point E(0.0024a 2 -1.7005a+27.28, -0.0024a 2 +0.7005a+72.72, 0.0) The area within the figure enclosed by the lines CD, DF, FE, and EC connecting the four points, or located on the lines CD, DF, FE, and EC, (3) When 5.5 ≤ a ≤ 10 Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100.0-a) Point F(0.0, 0.8762a 2 +23.914a-105.02, -0.8762a 2 -24.914a+205.02) and Point E(0.0031a 2 -1.7365a + 27.458, -0.0031a 2 +0.7365a+72.542, 0.0) The five points are located within the area of ​​the figure enclosed by the straight lines CD, DO, OF, FE, and EC connecting them, or on the aforementioned straight lines CD, DO, FE, and EC (excluding points O and F). In this case, the refrigerant of this disclosure does not undergo a disproportionation reaction at 3 MPa and 150°C, and its refrigeration capacity ratio to R404A is 60% or more.

[0023] In the refrigerant of this disclosure, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the Cap. relative to R410A is 60% or more.

[0024] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-1.75a+24.317, 0.0, 0.75a+75.683) and Point J(-2.0a+39.0, a+61.0, 0.0) The area within the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or located on the lines CD, DK, KJ, and JC, (2) 0.4 <a≦10のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-0.0043a 2 -1.809a + 24.324, 0.0, 0.0043a 2 (+0.809a+75.676) and Point J(-0.0087a 2 -2.0347a + 39.015, 0.0087a 2 +1.0347a+60.985, 0.0) The refrigerant may be located within the area of ​​the figure enclosed by the straight lines CD, DK, KJ, and JC connecting the four points, or on the aforementioned straight lines CD, DK, KJ, and JC. In this case, the refrigerant of this disclosure does not undergo a disproportionation reaction at 3 MPa and 150°C, and has a refrigeration capacity ratio of 60% or more compared to R410A.

[0025] The refrigerant of this disclosure may be a refrigerant containing HFO-1132(E) and R1234yf in amounts of 23±1% and 77±1% by mass or 31.5±1% and 68.5±1% by mass, respectively, based on their sum.

[0026] The refrigerant of this disclosure can suppress disproportionation reactions even when the refrigeration cycle locally reaches a refrigerant pressure of 3 MPa and a refrigerant temperature of 150°C.

[0027] The refrigerant of this disclosure may contain additional refrigerants in addition to HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a, to the extent that the above-described properties and effects are not impaired. In this regard, in some embodiments, the refrigerant of this disclosure preferably contains 99.5% by mass or more of the total of HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a, more preferably 99.75% by mass or more, even more preferably 99.9% by mass or more, even more preferably 99.999% by mass or more, and most preferably 99.9999% by mass or more of the total refrigerant. The refrigerant of this disclosure may consist substantially of only HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a, in which case the refrigerant of this disclosure may consist only of HFO-1132(E), R1234ze and / or R1234yf, HFO-1132a and unavoidable impurities. The refrigerant of this disclosure may consist only of HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a.

[0028] The additional refrigerant is not particularly limited and can be broadly selected. The mixed refrigerant may contain one type of additional refrigerant alone, or it may contain two or more types.

[0029] Additional refrigerants include acetylene, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFC-152a, HFC-161, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0030] The compositions of this disclosure include: A composition containing a refrigerant, The aforementioned refrigerant: The composition also includes HFO-1132(E), R1234ze and / or R1234yf, HFO-1132a; and at least one additional refrigerant selected from the group consisting of acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, HFC-152a, HFC-161, and 3,3,3-trifluoropropyne. The total amount of the additional refrigerant is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, even more preferably 0.1% by mass or less, and most preferably 0.01% by mass or less, relative to the total amount of refrigerant.

[0031] 1.2 Purpose The refrigerant of this disclosure can preferably be used as a working fluid in a refrigerator.

[0032] In one of the embodiments described above, the compositions of this disclosure are suitable for use as substitute refrigerants for at least one refrigerant selected from the group consisting of R410A, R404A, and R1234yf.

[0033] 2. Refrigerant composition The refrigerant compositions of this disclosure contain at least the refrigerant of this disclosure and can be used for the same purposes as the refrigerant of this disclosure. Furthermore, the refrigerant compositions of this disclosure can be used to obtain a working fluid for a refrigerator by further mixing them with at least refrigerant oil. When using the refrigerant compositions of this disclosure as a working fluid for a refrigerator, they are typically used in mixture with at least refrigerant oil. Therefore, the refrigerant compositions of this disclosure preferably contain substantially no refrigerant oil. Specifically, the refrigerant composition of this disclosure preferably contains 1% by mass or less of refrigerant oil relative to the total refrigerant composition, and more preferably 0.1% by mass or less. The refrigerant compositions of this disclosure contain, in addition to the refrigerant of this disclosure, other components as may be further included. Even if the refrigerant of this disclosure is a refrigerant composition further containing other components, or a working fluid for a refrigerator containing refrigerant oil as described later, the refrigerant composition and the working fluid for a refrigerator will produce the same effects as those achieved by the refrigerant of this disclosure. Examples of other components include at least one of the following other components. The refrigerant compositions of this disclosure may contain one of the other components alone, or two or more of them. The proportion of the refrigerant to the total refrigerant composition of this disclosure is preferably 88% by mass or more, more preferably 94% by mass or more, even more preferably 98% by mass or more, even more preferably 99% by mass or more, and most preferably 99.9% or more.

[0034] 2.1 water The refrigerant composition of this disclosure may contain trace amounts of water. Preferably, the water content in the refrigerant composition is 0.1% by mass or less relative to the total refrigerant composition. The inclusion of trace amounts of water in the refrigerant composition stabilizes the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant, and also makes oxidation of unsaturated fluorocarbon compounds less likely, thereby improving the stability of the refrigerant composition.

[0035] The compositions of this disclosure also include compositions comprising a refrigerant, wherein the refrigerant comprises HFO-1132(E), R1234ze and / or R1234yf, HFO-1132a, and 0.1% by mass or less of water.

[0036] 2.2 tracer The tracer is added to the refrigerant composition of the Disclosure at a detectable concentration so that any changes to the refrigerant composition of the Disclosure can be tracked if it is diluted, contaminated, or otherwise altered.

[0037] The refrigerant composition of this disclosure may contain one tracer alone or two or more tracers.

[0038] The tracer is not particularly limited and can be appropriately selected from among commonly used tracers.

[0039] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are particularly preferred as tracers.

[0040] The following compounds are preferred as tracers. FC-14 (Tetrafluoromethane, CF4) HCC-40 (chloromethane, CH3Cl) HFC-23 (trifluoromethane, CHF3) HFC-41 (Fluoromethane, CH3Cl) HFC-125 (Pentafluoroethane, CF3CHF2) HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2) HFC-143a (1,1,1-trifluoroethane, CF3CH3) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-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 (Chlorodifluoromethane, CHClF2) HCFC-31 (Chlorofluoromethane, CH2ClF) CFC-1113 (chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0041] The refrigerant composition of this disclosure may contain tracers in total at about 10 parts per million by weight (ppm) or more relative to the entire refrigerant composition. Alternatively, the refrigerant composition of this disclosure may contain tracers in total at about 1000 ppm or less relative to the entire refrigerant composition. The refrigerant composition of this disclosure may preferably contain tracers in total at about 30 ppm or more, more preferably at about 50 ppm or more, relative to the entire refrigerant composition. The refrigerant composition of this disclosure may preferably contain tracers in total at about 500 ppm or less, and may contain tracers in total at about 300 ppm or less, relative to the entire refrigerant composition. Note that the compounds exemplified as tracers are compounds that can be used as refrigerants in general, so when these compounds are included as tracers, the tracer content shall be treated as the content of additional refrigerants of this disclosure.

[0042] 2.3 UV fluorescent dyes The refrigerant composition of this disclosure may contain one ultraviolet fluorescent dye alone, or it may contain two or more ultraviolet fluorescent dyes.

[0043] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0044] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as their derivatives. Naphthalimide and coumarin, or either or both, are particularly preferred as ultraviolet fluorescent dyes.

[0045] 2.4 Stabilizer The refrigerant composition of this disclosure may contain one stabilizer alone or two or more stabilizers.

[0046] The stabilizer is not particularly limited and can be appropriately selected from among commonly used stabilizers.

[0047] Examples of stabilizers include nitro compounds, ethers, and amines.

[0048] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0049] Examples of ethers include 1,4-dioxane.

[0050] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0051] Other examples include butylhydroxyxylene and benzotriazole.

[0052] The stabilizer content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant composition. The stabilizer content is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant composition.

[0053] 2.5 Polymerization inhibitors The refrigerant composition of this disclosure may contain one polymerization inhibitor alone or two or more polymerization inhibitors.

[0054] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0055] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0056] The content of the polymerization inhibitor is not particularly limited, but is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the entire refrigerant composition. The content of the polymerization inhibitor is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the entire refrigerant composition.

[0057] 3. Working fluid containing refrigeration oil The refrigerant oil-containing working fluid of this disclosure comprises at least the refrigerant or refrigerant composition of this disclosure and refrigerant oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerant oil-containing working fluid of this disclosure is obtained by mixing refrigerant oil used in the compressor of a refrigerator with the refrigerant or refrigerant composition. The refrigerant oil-containing working fluid generally contains 10% by mass or more of refrigerant oil. The refrigerant oil-containing working fluid generally contains 50% by mass or less of refrigerant oil.

[0058] 3.1 Refrigerating machine oil The composition of this disclosure may contain one type of refrigeration oil alone, or it may contain two or more types.

[0059] The refrigerating oil is not particularly limited and can be appropriately selected from commonly used refrigerating oils. In that case, a refrigerating oil that is superior in terms of compatibility with the mixture and its ability to improve the stability of the mixture can be appropriately selected as needed.

[0060] As the base oil for the refrigeration oil, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferred.

[0061] Refrigerant oil may contain additives in addition to the base oil. The additives may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and defoaming agents.

[0062] As a refrigeration oil, the kinematic viscosity at 40°C is 5 cSt (5 × 10⁻¹⁰). -6 m 2 A lubrication oil with a kinematic viscosity of 400 cSt (400 × 10) or higher is preferable. Furthermore, as a refrigeration oil, one with a kinematic viscosity of 400 cSt (400 × 10) at 40°C is preferable. -6 m 2 A value of less than or equal to ( / s) is preferable in terms of lubrication.

[0063] The refrigerant oil-containing working fluid of this disclosure may optionally further contain at least one additive. Examples of additives include the following compatibilizers.

[0064] 3.2 Compatibilizer The refrigerant oil-containing working fluid of this disclosure may contain one type of compatibilizer alone, or it may contain two or more types of compatibilizers.

[0065] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0066] Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as compatibilizers.

[0067] 4. Refrigeration unit, refrigeration unit operation method The refrigerator of this disclosure includes the composition of this disclosure as a working fluid. The method of operating the refrigerator of this disclosure is a method of operating the refrigerator using the refrigerant composition of this disclosure.

[0068] Specifically, the method for operating the refrigerator of this disclosure includes the step of circulating the refrigerant composition of this disclosure in the refrigerator.

[0069] 5. Freezing method The refrigeration method of the present disclosure includes the step of operating a refrigeration cycle using the composition of the present disclosure.

[0070] 6. Methods for suppressing disproportionation reactions The method for suppressing the disproportionation reaction of HFO-1132(E) according to the present disclosure is a method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using the refrigerant composition according to the present disclosure.

[0071] In the method for suppressing disproportionation reactions of the present disclosure, the effect is obtained that the disproportionation reaction of HFO-1132(E) does not occur, in particular, when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0072] The method for suppressing disproportionation reactions disclosed herein makes it possible to suppress disproportionation reactions and operate the refrigeration cycle even in refrigerators that do not have means for suppressing disproportionation reactions.

[0073] 7. Use for suppressing disproportionation reactions The use of the present disclosure is for the purpose of suppressing the disproportionation reaction of HFO-1132(E) by mixing HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a in the refrigerant mixing ratio of the present disclosure.

[0074] In its use for suppressing disproportionation reactions, the HFO-1132(E) disproportionation reaction is particularly effective when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0075] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0076] The following provides further details with reference to examples. However, this disclosure is not limited to these examples.

[0077] Mixed refrigerants were prepared by mixing HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a in the mass percentages shown in Tables 1 to 4, based on their sum.

[0078] For each of these mixed refrigerants, the presence or absence of disproportionation reactions was investigated using the following test methods and test conditions. Test method The refrigerant to be tested was transferred to a test container, heated to 150°C, and then 30 J of energy was imparted to the refrigerant by applying voltage to a Pt wire inside the container to cause it to melt. The presence or absence of a disproportionation reaction was determined by the rapid increase in pressure and temperature inside the apparatus. Test conditions Test container: 38cc stainless steel container Test temperature: 150℃ Pressure: 3 MPa Judgment criteria "Non-explosive": The temperature or pressure after Pt wire cutting is less than twice the normal level, and no rapid disproportionation reaction has occurred. "Explosion": The temperature or pressure after the Pt wire cutting reached more than twice its original level, causing a rapid disproportionation reaction.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Table 3]

[0082] [Table 4]

[0083] From the results in Tables 1-4, it can be seen that the refrigerant of this disclosure does not undergo disproportionation reaction within the region enclosed by points C, D, O, and G in the triangular diagrams shown in Figures 2-7, 9-14, and 16-19.

[0084] Mixed refrigerants were prepared by mixing HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a in the mass percentages shown in Tables 5 to 8, based on their sum.

[0085] The GWP of HFO-1132(E) and HFO-1132a was set to 1, and the GWP of R1234ze and R1234yf was evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. Furthermore, the coefficient of performance (COP) ratio and refrigeration capacity (Cap.) ratio for the refrigerant mixtures shown in Tables 5-8 were calculated relative to R1234yf. The cycle performance of each refrigerant mixture was determined by performing theoretical refrigeration cycle calculations under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10). Note that the physical property data for HFO-1132(E) was obtained from measured values. Evaporation temperature: -30℃ Condensation temperature: 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency: 70%

[0086] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage relative to R1234yf.

[0087] The coefficient of performance (COP) was calculated using the following formula. COP = Refrigeration capacity / power consumption The evaluation results, along with the GWP for each refrigerant mixture, are shown in Tables 5-8.

[0088] [Table 5]

[0089] [Table 6]

[0090] [Table 7]

[0091] [Table 8]

[0092] Mixed refrigerants were prepared by mixing HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a in the mass percentages shown in Tables 9 to 14, based on their sum.

[0093] The COP and refrigeration capacity of the refrigerant mixtures in Tables 9 to 14 were determined by performing theoretical calculations of the refrigeration cycle of the refrigerant mixtures using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10) under the following conditions. Note that the physical property data for HFO-1132(E) was obtained from measured values. Evaporation temperature: -30°C Condensation temperature: 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency: 70%

[0094] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage (%) relative to R1234yf. The coefficient of performance (COP) was calculated using the following formula. COP = Refrigeration capacity / power consumption The evaluation results, along with the GWP for each refrigerant mixture, are shown in Tables 9-14.

[0095] [Table 9]

[0096] [Table 10]

[0097] [Table 11]

[0098] [Table 12]

[0099] [Table 13]

[0100] [Table 14]

[0101] These results show that in the refrigerant of this disclosure, which includes 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a, and where x, y, and z are the mass percent based on the sum of HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass percent, a disproportionation reaction does not occur at 3 MPa and 150°C when the coordinates (x,y,z) satisfy the following requirements.

[0102] <Requirements> The coordinates (x, y, z) are Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) and Point G(0.0, 100-a, 0.0) The area within the figure enclosed by the lines CD, DO, OG, and GC connecting the four points, or the area on the lines CD, DO, and GC (excluding points O and G).

[0103] Furthermore, in the refrigerant of this disclosure, which includes 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a, and where x, y, z, and a are the mass percent based on the sum of HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass percent, it can be seen that when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the Cap. relative to R1234yf is 125% or more.

[0104] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-1.75a+12.083, 0.0, 0.75a+87.917) and Point A(-1.75a+29.917, 0.75a+70.083, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (2) 0.4 <a<7.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point B(-0.0051a 2 -1.5885a+12.036, 0.0, 0.0051a 2 (+0.5885a+87.964) and Point A(-0.0026a 2 -1.7943a + 29.918, 0.0026a 2 +0.7943a+70.082, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (3) When 7.4 ≤ a ≤ 10 Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) Point B(0.0, -1.9091a 2 +46.718a-241.17, 1.9091a 2 -47.718a+341.17) and Point A(-0.0186a 2 -1.5217a + 28.782, 0.0186a 2 (+0.5217a+71.218, 0.0) The area within the figure enclosed by the lines CD, DO, OB, BA, and AC connecting the five points, or the area on the lines CD, DO, BA, and AC (excluding points O and B).

[0105] The coordinates of each point were determined by deriving an approximation formula based on the points listed in the table above. Specifically, the calculations were performed as shown in Tables 15-16.

[0106] [Table 15]

[0107] [Table 16]

[0108] Mixed refrigerants were prepared by mixing HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a in the mass percentages shown in Tables 17-20, based on their sum.

[0109] The COP and refrigeration capacity of the refrigerant mixtures in Tables 17 to 20 were determined by performing theoretical calculations of the refrigeration cycle of the refrigerant mixtures using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions. Note that the physical property data for HFO-1132(E) was obtained from measured values. Evaporation temperature: -40°C Condensation temperature 40℃ Superheat temperature 0K Supercooling temperature 20K Compressor efficiency: 70%

[0110] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage (%) relative to R404A. The coefficient of performance (COP) was calculated using the following formula. COP = Refrigeration capacity / power consumption The evaluation results, along with the GWP for each refrigerant mixture, are shown in Tables 17-20.

[0111] [Table 17]

[0112] [Table 18]

[0113] [Table 19]

[0114] [Table 20]

[0115] Mixed refrigerants were prepared by mixing HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a in the mass percentages shown in Tables 21 to 26, based on their sum.

[0116] The COP and refrigeration capacity of the refrigerant mixtures in Tables 21 to 26 were determined by performing theoretical calculations of the refrigeration cycle of the refrigerant mixtures using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10) under the following conditions. Note that the physical property data for HFO-1132(E) was obtained from measured values. Evaporation temperature: -40°C Condensation temperature 40℃ Superheat temperature 0K Supercooling temperature 20K Compressor efficiency: 70%

[0117] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage (%) relative to R404A. The coefficient of performance (COP) was calculated using the following formula. COP = Refrigeration capacity / power consumption The evaluation results, along with the GWP for each refrigerant mixture, are shown in Tables 21-26.

[0118] [Table 21]

[0119] [Table 22]

[0120] [Table 23]

[0121] [Table 24]

[0122] [Table 25]

[0123] [Table 26]

[0124] From these results, it can be seen that, in the refrigerant of this disclosure, when x, y, and z are the mass percent based on the sum of HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass percent, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the Cap. relative to R404A is 60% or more.

[0125] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point F(-1.5a+8.4, 0.0, 0.5a+91.6) and Point E(-1.5a+27.2, 0.5a+72.8, 0.0) The area within the figure enclosed by the lines CD, DF, FE, and EC connecting the four points, or located on the lines CD, DF, FE, and EC, (2) 0.4 <a<5.5のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a + 44.0, 0.0, 56.0) Point F(0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 +0.5508a + 91.58) and Point E(0.0024a 2 -1.7005a + 27.28, -0.0024a 2 +0.7005a + 72.72, 0.0) within the range of the figure surrounded by the straight lines CD, DF, FE, and EC connecting the four points respectively, or on the straight lines CD, DF, FE, and EC, (3) When 5.5 ≦ a ≦ 10 Point C(-a + 44.0, 56.0, 0.0) Point D(-a + 44.0, 0.0, 56.0) Point O(0.0, 0.0, 100.0 - a) Point F(0.0, 0.8762a 2 +23.914a - 105.02, -0.8762a 2 -24.914a + 205.02) and Point E(0.003​​​​​​​​​​​​​​​​​​​​​A mixed refrigerant was prepared by mixing HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a in the mass percentages shown in Tables 28 to 30, respectively, based on the sum of these.

[0129] The COP and refrigerating capacity of the mixed refrigerants from Table 28 to Table 30 were obtained by performing theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10). The physical property data of HFO-1132(E) was obtained from measured values. Evaporation temperature: 5°C Condensation temperature: 45°C Superheat temperature: 5 K Subcooling temperature: 5 K Compressor efficiency: 70%

[0130] In the following tables, the "COP ratio" and the "refrigerating capacity ratio" indicate the ratio (%) with respect to R410A. The coefficient of performance (COP) was obtained by the following formula. COP = Refrigerating capacity / Power consumption The evaluation results are shown in Tables 28 to 30 together with the GWP for each mixed refrigerant.

[0131]

Table 28

[0132]

Table 29

[0133]

Table 30

[0134] A mixed refrigerant was prepared by mixing HFO-1132(E), R1234ze and / or R1234yf and HFO-1132a at the mass percentages shown in Tables 31 to 34 respectively based on their total sum.

[0135] The COP and refrigerating capacity of the mixed refrigerants from Table 31 to Table 34 were obtained by performing theoretical calculations of the refrigeration cycle of the mixed refrigerants under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10). The physical property data of HFO-1132(E) was obtained from measured values. Evaporation temperature: 5°C Condensation temperature: 45°C Superheat temperature: 5 K Subcooling temperature: 5 K Compressor efficiency: 70%

[0136] In the following tables, "COP ratio" and "refrigerating capacity ratio" indicate the ratios (%) with respect to R410A. The coefficient of performance (COP) was obtained by the following formula. COP = Refrigerating capacity / Power consumption The evaluation results are shown in Tables 31 to 34 together with the GWP for each mixed refrigerant.

[0137]

Table 31

[0138]

Table 32

[0139]

Table 33

[0140]

Table 34

[0141] From these results, it can be seen that, in the refrigerant of this disclosure, when x, y, and z are the mass percent based on the sum of HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass percent, when the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, and the Cap. relative to R410A is 60% or more.

[0142] <Requirements> The coordinates (x, y, z) are (1)0 <a≦0.4のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-1.75a+24.317, 0.0, 0.75a+75.683) and Point J(-2.0a+39.0, a+61.0, 0.0) The area within the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or located on the lines CD, DK, KJ, and JC, (2) 0.4 <a≦10のとき Point C(-a+44.0, 56.0, 0.0) Point D(-a+44.0, 0.0, 56.0) Point K(-0.0043a 2 -1.809a + 24.324, 0.0, 0.0043a 2 (+0.809a+75.676) and Point J(-0.0087a 2 -2.0347a + 39.015, 0.0087a 2 +1.0347a+60.985, 0.0) The figure is located within the area enclosed by the lines CD, DK, KJ, and JC connecting the four points, or on the lines CD, DK, KJ, and JC.

[0143] The coordinates of each point were determined by deriving an approximation formula based on the points listed in the table above. Specifically, the calculations were performed as shown in Table 35.

[0144] [Table 35]

Claims

1. A composition containing a refrigerant, The refrigerant comprises 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a. In the aforementioned refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) and Point G (0.0, 100-a, 0.0) The figure is located within the area enclosed by the lines CD, DO, OG, and GC connecting the four points, or on the lines CD, DO, and GC (excluding points O and G), composition.

2. A composition containing a refrigerant, The refrigerant comprises 1,3,3,3-tetrafluoropropene (R1234ze) and / or 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,2-difluoroethylene (HFO-1132(E)), and HFO-1132a. In the aforementioned refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: (1) When 0 < a ≤ 0.4 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point B (-1.75a+12.083, 0.0, 0.75a+87.917) and Point A (-1.75a + 29.917, 0.75a + 70.083, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (2) When 0.4 < a < 7.4 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point B (-0.0051a 2 -1.5885a+12.036, 0.0, 0.0051a 2 (+0.5885a+87.964) and Point A (-0.0026a 2 -1.7943a + 29.918, 0.0026a 2 +0.7943a + 70.082, 0.0) Within the area of ​​the figure enclosed by the lines CD, DB, BA, and AC connecting the four points, or on the lines CD, DB, BA, and AC, (3) When 7.4 ≤ a ≤ 10 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100-a) Point B (0.0, -1.9091a 2 +46.718a-241.17, 1.9091a 2 -47.718a+341.17) and Point A (-0.0186a) 2 -1.5217a+28.782, 0.0186a 2 +0.5217a+71.218, 0.0) Within the area of ​​the figure enclosed by the lines CD, DO, OB, BA, and AC connecting the five points, or on the lines CD, DO, BA, and AC (excluding points O and B), The composition according to claim 1.

3. The refrigerant comprises HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a. In the refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: (1) When 0 < a ≤ 0.4 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point F (-1.5a+8.4, 0.0, 0.5a+91.6) and Point E (-1.5a+27.2, 0.5a+72.8, 0.0) The area within the figure enclosed by the lines CD, DF, FE, and EC connecting the four points, or located on the lines CD, DF, FE, and EC, (2) When 0.4 < a < 5.5 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point F(0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 + 0.5508a + 91.58) and Point E (0.0024a) 2 -1.7005a+27.28, -0.0024a 2 +0.7005a+72.72, 0.0) The area within the figure enclosed by the lines CD, DF, FE, and EC connecting the four points, or located on the lines CD, DF, FE, and EC, (3) When 5.5 ≤ a ≤ 10 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point O(0.0, 0.0, 100.0-a) Point F (0.0, 0.8762a 2 +23.914a-105.02, -0.8762a 2 -24.914a+205.02) and Point E (0.0031a) 2 -1.7365a+27.458, -0.0031a 2 +0.7365a+72.542, 0.0) Within the area of ​​the figure enclosed by the lines CD, DO, OF, FE, and EC connecting the five points, or on the lines CD, DO, FE, and EC (excluding points O and F), The composition according to claim 1.

4. The refrigerant comprises HFO-1132(E), R1234ze and / or R1234yf, and HFO-1132a. In the refrigerant, when the mass percentages based on the sum of HFO-1132(E), R1234ze, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: (1) When 0 < a ≤ 0.4 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point K (-1.75a+24.317, 0.0, 0.75a+75.683) and Point J (-2.0a+39.0, a+61.0, 0.0) The area within the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or located on the lines CD, DK, KJ, and JC, (2) When 0.4 < a ≤ 10 Point C (-a+44.0, 56.0, 0.0) Point D (-a+44.0, 0.0, 56.0) Point K (-0.0043a 2 -1.809a + 24.324, 0.0, 0.0043a 2 (+0.809a+75.676) and Point J (-0.0087a) 2 -2.0347a+39.015, 0.0087a 2 +1.0347a+60.985, 0.0) Within the area of ​​the figure enclosed by the lines CD, DK, KJ, and JC connecting the four points respectively, or on the lines CD, DK, KJ, and JC, The composition according to claim 1.

5. Furthermore, the composition according to any one of claims 1 to 4, which contains refrigeration oil and is used as a working fluid for a refrigeration unit.

6. The composition according to claim 2, which is used as a substitute refrigerant for R1234yf.

7. The composition according to claim 3, which is used as a substitute refrigerant for R404A.

8. The composition according to claim 4, which is used as a substitute refrigerant for R410A.

9. Use of the composition according to any one of claims 1 to 4 as a refrigerant.

10. A refrigerator comprising the composition described in any one of claims 1 to 4 as a working fluid.

11. A refrigeration method comprising the step of operating a refrigeration cycle using the composition described in any one of claims 1 to 4.

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