Refrigerant-containing composition, use thereof, refrigerator comprising same, and method for operating refrigerator

Abstract

The present disclosure provides a novel refrigerant mixture having a low GWP. Specifically, the present disclosure provides a refrigerant-containing composition, wherein the refrigerant includes trans-1,2-difluoroethylene (HFO-1132 (E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a). In a ternary phase diagram in which the sum of HFO-1132 (E), R32, and R1234yf is (100-a) mass%, and x, y, z, and a (0<a≤10.0) are mass% of HFO-1132 (E), R32, R1234yf, and HFO-1132a, respectively, on the basis of the total mass in the refrigerant, the coordinates (x, y, z) when 0<a≤0.4 are within the range of a shape surrounded by line segments CD, DE, EF, FB'', B''A'', and A''C, which connect the six points: point C (-a+60.0, 40.0, 0.0); point D (-a+44.0, 0.0, 56.0); point E (1.25a2-2.25a+24.3, 0.0, -1.25a2+1.25a+75.7); point F (0.0, -1.5a+15.5, 0.5a+84.5); point B'' (0.0, 73.9, -a+26.1); and point A'' (-a+26.0, 74.0, 0.0), respectively, or on the line segments CD, DE, EF, and B''A'' (excluding the points C, F, B'', and A''), and the coordinates (x, y, z) when 0.4<a≤10.0 are within the range of a shape surrounded by line segments CD, DE, EF, FB'', B''A'', and A''C, which connect the six points: point C (-a+60.0, 40.0, 0.0); point D (-a+44.0, 0.0, 56.0); point E (-0.0013a2-1.841a+24.337, 0.0, 0.0013a2+0.841a+75.663); point F (0.0, 0.0128a2-1.3516a+15.439, -0.0128a2+0.3516a+84.561); point B'' (0.0, 73.9, -a+26.1); and point A'' (-a+26.0, 74.0, 0.0) or on the line segments CD, DE, EF, and B''A'' (excluding the points C, F, B'', and A'').

Description

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

[0001] This disclosure relates to compositions containing refrigerants, their use, and refrigerators having them and methods for operating such refrigerators.

[0002] A thermal cycle working fluid containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed as a thermal cycle working fluid that can replace R410A (Patent Document 1).

[0003] International Publication No. 2015 / 141678

[0004] This disclosure aims to provide a novel low-GWP mixed refrigerant.

[0005] Item 1. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf) and 1,1-difluoroethylene (HFO-1132a), and in the refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point C (-a + 60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points C, F, B'', FB'', B''A'', and A'', respectively, or lie on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 A composition characterized by being within the range of a figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points B'' (0.0, 73.9, -a+26.1) and A'' (-a+26.0, 74.0, 0.0), or lying on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''). Item 2. In the aforementioned refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, if the coordinates (x,y,z) are 0 < a ≤ 0.4, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), and point E (1.25a). 2 -2.25a + 24.3, 0.0, -1.25a 2Points C(-a + 60.0, 40.0, 0.0), D(-a + 44.0, 0.0, 56.0), E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a + 75.663), F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 +0.3516a + 84.561), B'(0.0, 44.1, -a + 55.9) and A'(-a + 55.7, 44.3, 0.0). The composition is within the figure surrounded by the line segments CD, DE, EF, FB', B'A' and A'C connecting these six points respectively or on the line segments CD, DE, EF and B'A' (excluding points C, F, B' and A'). When 0.4 < a ≤ 10.0, item 1. The composition according to item 1 is within the figure surrounded by the line segments CD, DE, EF, FB', B'A' and A'C connecting these six points respectively or on the line segments CD, DE, EF and B'A' (excluding points C, F, B' and A'). Item 3. In the refrigerant, taking the mass % based on the sum of HFO-1132(E), R32, R1234yf and HFO-1132a as x, y, z, and a respectively (where 0 < a ≤ 10.0), in the three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is (100 - a) mass %, the coordinates (x, y, z) are as follows. When 0 < a ≤ 0.4, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point E(1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2If the five points are +1.25a+75.7), point F(0.0, -1.5a+15.5, 0.5a+84.5), and point B(0.0, 21.8, -a+78.2), then the figure is enclosed by line segments GD, DE, EF, FB, and BG, which connect these five points respectively, or the figure lies on line segments GD, DE, EF, and BG (except for points F and B), and if 0.4 < a ≤ 10.0, then point G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point E(-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2The composition according to item 1, within the area enclosed by the line segments GD, DE, EF, FB, and BG connecting the five points (+0.3516a+84.561) and point B (0.0, 21.8, -a+78.2), or on the line segments GD, DE, EF, and BG (excluding points F and B). Item 4. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a), and in the refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point G (-a + 52.8, 22.0, 25.2), If the five points D (-a+44.0, 0.0, 56.0), I (-1.5a+8.4, 0.0, 0.5a+91.6), J (0.0, -a+5.2, 94.8), and B (0.0, 21.8, -a+78.2) are enclosed by line segments GD, DI, IJ, JB, and BG, respectively, or lie on the line segments GD, DI, IJ, and BG (excluding points J and B), and 0.4 < a ≤ 5.5, then point G (-a+52.8, 22.0, 25.2), point D (-a+44.0, 0.0, 56.0), point I (0.0036a) 2 -1.5508a+8.42, 0.0, -0.0036a 2 +0.5508a+91.58), point J (0.0, 0.0081a 2 -0.9892a+5.194, -0.0081a 2If 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G(-0.0108a + 94.806) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DI, IJ, and BG (excluding points J and B), and if 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DO, OB, and BG connecting the four points G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the following. Item 5. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf) and 1,1-difluoroethylene (HFO-1132a), wherein the mass percent of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass percent, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point G (-a + 52.8, 22.0, 25.2), If the five points D (-a+44.0, 0.0, 56.0), K (-4a+14.6, 0.0, 3a+85.4), L (0.0, -a+5.2, 94.8), and B (0.0, 21.8, -a+78.2) are located within the area enclosed by line segments GD, DK, KL, LB, and BG, respectively, or on the line segments GD, DK, KL, and BG (excluding points L and B), and 0.4 < a ≤ 3.5, then the points G (-a+52.8, 22.0, 25.2), D (-a+44.0, 0.0, 56.0), and K (-0.0457a) are located within the area enclosed by line segments GD, DK, KL. 2 -4.0153a+14.613, 0.0, 0.0457a 2(+3.0153a + 85.387), point L(0.0, 0.2245a 2 -3.1012a + 8.105, -0.2245a 2 The range of the figure surrounded by the line segments GD, DK, KL, LB, and BG connecting the five points of (+2.1012a + 91.895) and point B(0.0, 21.8, -a + 78.2) respectively, or on the line segments GD, DK, KL, and BG (however, excluding points L and B), and when 3.5 < a ≤ 10.0, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0), and point B(0.0, 21.8, -a + 78.2) are within the range of the figure surrounded by the line segments GD, DO, OB, and BG connecting the four points respectively, or on the line segments GD, DO, and BG (however, excluding points O and B). The composition is characterized by this. Item 6. Furthermore, it contains a refrigeration oil and is used as a working fluid for a refrigerator. The composition according to any one of Items 1 to 5. Item 7. The composition according to any one of Items 1 to 3, used as an alternative refrigerant to R410A. Item 8. Use of the composition according to any one of Items 1 to 3 as an alternative refrigerant to R410A. Item 9. The composition according to Item 4, used as an alternative refrigerant to R404A. Item 10. Use of the composition according to Item 4 as an alternative refrigerant to R404A. Item 11. The composition according to Item 5, used as an alternative refrigerant to R1234yf. Item 12. Use of the composition according to Item 5 as an alternative refrigerant to R1234yf. Item 13. A refrigerator containing the composition according to any one of Items 1 to 5 as a working fluid. Item 14. A method for operating a refrigerator, including the step of circulating the composition according to any one of Items 1 to 5 as a working fluid in the refrigerator.

[0006] The refrigerant of the present disclosure has a low GWP.

[0007] A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure. A triangular diagram showing the composition of the refrigerant of the present disclosure.

[0008] In order to solve the above problems, the inventors of the present invention conducted intensive studies and found that various mixed refrigerants described below have the above characteristics. The present disclosure has been completed by further studies based on such findings and includes the following aspects.

[0009] <Definition of terms> In this specification, the term "refrigerant" includes at least a compound with a refrigerant number (ASHRAE number) starting with R, which represents the type of refrigerant defined by ISO817 (International Organization for Standardization). Even if a refrigerant number has not been assigned yet, those having characteristics equivalent to those of such refrigerants are included. Refrigerants are roughly classified into "fluorocarbon-based compounds" and "non-fluorocarbon-based compounds" in terms of the structure of the compound. "Fluorocarbon-based compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[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,” “nearly drop-in substitution,” and “retrofit.”

[0012] A second type of "substitution" includes using equipment designed to operate with a second refrigerant, but instead using the second refrigerant for the same existing applications as the first 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] In this specification, "in-vehicle air conditioning equipment" refers to a type of refrigeration system used in automobiles such as gasoline cars, hybrid cars, electric cars, and hydrogen cars. In-vehicle air conditioning equipment refers to a refrigeration system consisting of a refrigeration cycle in which a liquid refrigerant undergoes heat exchange in an evaporator, the evaporated refrigerant gas is drawn in by a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied in a condenser, and then passed through an expansion valve to undergo adiabatically expanded refrigerant before being supplied back to the evaporator as liquid refrigerant.

[0015] In this specification, temperature glide can be rephrased as the absolute difference between the start temperature and the end temperature of the phase change process of a composition containing the refrigerant of this disclosure within a component of a thermal cycle system.

[0016] 1. Refrigerants The refrigerants of this disclosure include trans-1,2-difluoroethylene (HFO-1132(E), E-HFO-1132), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a).

[0017] The refrigerant in this disclosure is a low GWP mixed refrigerant.

[0018] In the refrigerant of this disclosure, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a (where 0 < a ≤ 10.0), respectively, and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 1-5) where the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 500 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0019] <Requirements> If 0 < a ≤ 0.4, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2 -2.25a + 24.3, 0.0, -1.25a 2If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points C, F, B'', FB'', B''A'', and A'', respectively, or lie on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'', and A''C, which connect the six points B'' (0.0, 73.9, -a+26.1) and A'' (-a+26.0, 74.0, 0.0), or it lies on the line segments CD, DE, EF, and B''A'' (excluding points C, F, B'', and A'').

[0020] In the refrigerant of this disclosure, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 1-5) where the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0021] <Requirements> If 0 < a ≤ 0.4, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2-2.25a + 24.3, 0.0, -1.25a 2 If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB', B'A', and A'C that connect the six points C, F, B', EF, FB', B'A', and A'C respectively, or lie on the line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A'), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments CD, DE, EF, FB', B'A', and A'C, which connect the six points B' (0.0, 44.1, -a+55.9) and A' (-a+55.7, 44.3, 0.0), or it lies on line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A').

[0022] In the refrigerant of this disclosure, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 1-5) where the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0023] <Requirements> If 0 < a ≤ 0.4, then point G (-a + 52.8, 22.0, 25.2), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2-2.25a + 24.3, 0.0, -1.25a 2 If the five points are +1.25a+75.7), point F(0.0, -1.5a+15.5, 0.5a+84.5), and point B(0.0, 21.8, -a+78.2), then the figure is enclosed by line segments GD, DE, EF, FB, and BG, which connect these five points respectively, or the figure lies on line segments GD, DE, EF, and BG (except for points F and B), and if 0.4 < a ≤ 10.0, then point G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point E(-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments GD, DE, EF, FB, and BG, which connect the five points (+0.3516a+84.561) and point B (0.0, 21.8, -a+78.2), or it lies on the line segments GD, DE, EF, and BG (excluding points F and B).

[0024] In the refrigerant of this disclosure, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 6-12) where the coordinates (x,y,z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R404A is 60% or more.

[0025] <Requirements> If 0 < a ≤ 0.4, the figure is within the area enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), I (-1.5a + 8.4, 0.0, 0.5a + 91.6), J (0.0, -a + 5.2, 94.8), and B (0.0, 21.8, -a + 78.2) respectively, or on the line segments GD, DI, IJ, and BG (except for points J and B). If 0.4 < a ≤ 5.5, the figure is within the area enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2) and D (-a + 44.0, 0.0, 56.0). Point I (0.0036a 2 -1.5508a+8.42, 0.0, -0.0036a 2 +0.5508a+91.58), point J (0.0, 0.0081a 2 -0.9892a+5.194, -0.0081a 2 If 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G(-0.0108a + 94.806) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DI, IJ, and BG (excluding points J and B), and if 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DO, OB, and BG connecting the four points G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DO, and BG (excluding points O and B).

[0026] In the refrigerant of this disclosure, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 13-19), when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less. When the boiling point is -40.0°C or less, there is an advantage that it is easy to use in heating by heat pump. For example, the refrigerant of this disclosure can be used to operate the refrigeration cycle of an in-vehicle air conditioning system, which has the advantage of enabling heating by heat pump, which consumes less power than electric heaters. Examples of in-vehicle air conditioning equipment include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0027] <Requirements> If 0 < a ≤ 0.4, the figure is within the area enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), K (-4a + 14.6, 0.0, 3a + 85.4), L (0.0, -a + 5.2, 94.8), and B (0.0, 21.8, -a + 78.2), or on the line segments GD, DK, KL, and BG (excluding L and B). If 0.4 < a ≤ 3.5, the figure is within the area enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), Point K (-0.0457a 2 -4.0153a+14.613, 0.0, 0.0457a 2 +3.0153a+85.387), point L (0.0, 0.2245a 2 -3.1012a+8.105, -0.2245a 2If 3.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point O(0.0, 0.0, -a+100.0), and point B(0.0, 21.8, -a+78.2), or is on the line segments GD, DO, OB, and BG connecting the four points G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point O(0.0, 0.0, -a+100.0), and point B(0.0, 21.8, -a+78.2), or is on the line segments GD, DO, and BG (excluding points O and B).

[0028] The refrigerants of this disclosure may contain additional refrigerants in addition to the essential refrigerants, to the extent that they do not impair the above-mentioned properties and effects. In this regard, in some embodiments, the refrigerants of this disclosure preferably contain the total of the essential refrigerants in an amount of 99.5% by mass or more, 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. The refrigerants of this disclosure may consist substantially of only the essential refrigerants, in which case the refrigerants of this disclosure may consist only of the essential refrigerants and unavoidable impurities. Furthermore, the refrigerants of this disclosure may consist only of the essential refrigerants.

[0029] The additional refrigerants are not particularly limited and can be broadly selected. The mixed refrigerants may contain one additional refrigerant alone or two or more additional refrigerants. Examples of additional refrigerants include acetylene, methylamine, fluoroethylene (HFO-1141), trifluoroethylene (HFO-1123), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), cis-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2,2-difluoro-1-chloroethylene (HCFC-1122), and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC- Examples include 124), chlorotrifluoroethylene (CFC-1113), 3,3,3-trifluoropropyne, 1-chloro-1,1,2-trifluoroethane (HCFC-133), 2-chloro-1,1,1-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, and 1-chloro-1,2-difluoroethane (HCFC-142a).

[0030] 1.2 Applications The refrigerants of this disclosure include, for example, R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437 It can be used as a substitute refrigerant for A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R474A, R479A, R502, R507, R513A, R1234yf, or R1234ze(E). Among these, it is preferable to use it as a substitute refrigerant for at least one of R410A, R404A, and R1234yf.

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

[0032] 2. Refrigerant Compositions The refrigerant compositions of the present disclosure may contain at least the refrigerant of the present disclosure and may be used for the same purposes as the refrigerant of the present disclosure. Furthermore, the refrigerant compositions of the present disclosure may be used to obtain a working fluid for a refrigerator by further mixing them with at least refrigerant oil.

[0033] The refrigerant compositions of this disclosure contain, in addition to the refrigerant of this disclosure, at least one other component. The refrigerant compositions of this disclosure may optionally contain at least one of the following other components. As described above, when the refrigerant compositions of this disclosure are used as working fluids in a refrigerator, they are usually 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, and more preferably 0.1% by mass or less, of refrigerant oil relative to the total refrigerant composition.

[0034] 2.1 Water The refrigerant composition disclosed herein 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. 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] 2.2 Tracer Tracers are added to the refrigerant composition of the Disclosure in a detectable concentration so that any changes to the refrigerant composition of the Disclosure can be tracked if the composition is diluted, contaminated, or otherwise altered.

[0036] The refrigerant composition of this disclosure may contain one tracer alone or two or more tracers.

[0037] The tracer is not particularly limited and can be appropriately selected from among commonly used tracers.

[0038] 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.

[0039] The following compounds are preferred as tracers. FC-14 (tetrafluoromethane, CF4), HCC-40 (chloromethane, CH3Cl), HFC-23 (trifluoromethane, CHF3), HFC-41 (fluoromethane, CH3F), HFC-125 (pentafluoroethane, CF3CHF2), HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F), HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2), HFC-143a (1,1,1-trifluoroethane, CF3CH3), HFC-143 (1,1,2-trifluoroethane, CHF2CH2F), HFC-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).

[0040] The refrigerant composition of this disclosure may contain tracers in total at about 10 parts by weight per million (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 contain tracers in total at preferably about 30 ppm or more, more preferably about 50 ppm or more, relative to the entire refrigerant composition. The refrigerant composition of this disclosure may contain tracers in total at preferably about 500 ppm or less, and may also contain about 300 ppm or less, relative to the entire refrigerant composition.

[0041] 2.3 Ultraviolet fluorescent dyes The refrigerant composition of this disclosure may contain one ultraviolet fluorescent dye alone or two or more ultraviolet fluorescent dyes.

[0042] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0043] 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.

[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 Stabilizers The refrigerant compositions 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. The stabilizer content is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant.

[0053] 2.5 Polymerization Inhibitors The refrigerant compositions 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 polymerization inhibitor content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant. The polymerization inhibitor content is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant.

[0057] 3. Refrigerant Oil-Containing Working Fluid The refrigerant oil-containing working fluid of this disclosure contains 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 Refrigerant Oil The composition of this disclosure may contain one type of refrigerant 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] For refrigeration oil, a kinematic viscosity of 5 cSt or higher at 40°C is preferable from a lubrication standpoint. Furthermore, for refrigeration oil, a kinematic viscosity of 400 cSt or lower at 40°C is preferable from a lubrication standpoint.

[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 Compatibilizers The refrigeration 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. Method of operating the refrigerator The method of operating the refrigerator of this disclosure is a method of operating the refrigerator using the refrigerant of this disclosure.

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

[0069] 5. Method for suppressing disproportionation reaction The method for suppressing disproportionation reaction of HFO-1132(E) according to the present disclosure is a method for suppressing disproportionation reaction of HFO-1132(E) that includes the step of operating a refrigeration cycle using the refrigerant according to the present disclosure.

[0070] 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 even when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0071] 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.

[0072] 6. Use for Suppression of Disproportionation Reaction The use of the present disclosure is for suppressing the disproportionation reaction of R32, R1234yf and HFO-1132a of HFO-1132(E), which is achieved by mixing R32, R1234yf and HFO-1132a and HFO-1132(E) in the refrigerant mixing ratio of the present disclosure.

[0073] 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.

[0074] 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.

[0075] The following provides further details with reference to examples. However, this disclosure is not limited to these examples.

[0076] A refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf was mixed with one of the following refrigerants: HFO-1132a, HFO-1123, Z-HFO-1132, HFC-161, or ethylene, in the mass percentages shown in Table 1.

[0077] For each of these refrigerant mixtures, the GWP, COP ratio and refrigeration capacity ratio compared to R410A, and temperature glide were investigated (Table 1).

[0078] The GWP of HFO-1132(E) was set to 1, and the GWPs of R32, R1234yf, HFO-1132a, HFO-1123, Z-HFO-1132, HFC-161, and ethylene were evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. The COP and refrigeration capacity of each refrigerant mixture were determined by performing theoretical refrigeration cycle calculations using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions. The physical property data for HFO-1132(E) used in the theoretical refrigeration cycle calculations were obtained through actual measurements and added to Refprop 10.0. <Compared to R410A> Evaporation temperature: 5°C Condensation temperature: 45°C Superheating temperature: 5K Supercooling temperature: 5K Compressor efficiency: 70%

[0079] In Table 1 below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage relative to R410A.

[0080] The coefficient of performance (COP) was calculated using the following formula: COP = (refrigeration capacity or heating capacity) / power consumption

[0081]

[0082] In mixed refrigerants (Examples 1 and 2, and Comparative Examples 3 and 4) prepared by adding HFO-1132a or HFO-1123 to a refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf, the temperature glide was similar to that of a refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf (Comparative Example 2), while the refrigeration capacity ratio to R410A was improved. Furthermore, HFO-1132a improved the refrigeration capacity ratio to R410A of the mixed refrigerant with a smaller addition amount compared to HFO-1123. The results in Table 1 show that HFO-1132a is a superior additive compared to HFO-1123, Z-HFO-1132, HFC-161, and ethylene, in that it can improve the refrigeration capacity ratio to R410A while maintaining a similar temperature glide to refrigerant compositions consisting only of HFO-1132(E), R32, and R1234yf.

[0083] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, R1234yf, and HFO-1132a in the mass percentages shown in Tables 2 to 5, based on their sum.

[0084] For each of these mixed refrigerants, the presence or absence of disproportionation reactions was investigated under the following test methods and conditions. Test Method The refrigerant composition to be tested was transferred and filled into a test container, heated to 150°C, and then 30 J of energy was applied to the refrigerant composition by applying voltage to a Pt wire inside the container to melt it. The presence or absence of disproportionation reactions was determined by the rapid increase in pressure and temperature inside the apparatus. Test Conditions Test container: 38 cc SUS container Test temperature: 150°C Pressure: 3.0 MPa Judgment Criteria "No explosion": The temperature or pressure after melting the Pt wire was less than twice the original temperature, and no rapid disproportionation reaction occurred. "Explosion": The temperature or pressure after melting the Pt wire reached twice the original temperature or more, and a rapid disproportionation reaction occurred.

[0085]

[0086] From the results shown in Tables 2 to 5, it can be seen that the refrigerant of this disclosure does not undergo a disproportionation reaction at 3.0 MPa and 150°C when the region shown in the triangular diagrams in Figures 1 to 19, specifically when the coordinates (x, y, z) are on the line CD or below the line CD.

[0087] The GWP of HFO-1132(E) was set to 1, and the GWPs of R32, R1234yf, and HFO-1132a were evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. Furthermore, the COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were determined by performing theoretical calculations of the refrigeration cycle under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0). The physical property data for HFO-1132(E) used in the theoretical calculations were obtained through actual measurements and added to Refprop 10.0. <Compared to R410A> Evaporation temperature 5°C Condensation temperature 45°C Superheating temperature 5K Supercooling temperature 5K Compressor efficiency 70% <Compared to R404A> Evaporation temperature -40°C Condensation temperature 40°C Superheating temperature 20K Supercooling temperature 0K Compressor efficiency 70% <Compared to R1234yf> Evaporation temperature -30°C Condensation temperature 30°C Superheating temperature 5K Supercooling temperature 5K Compressor efficiency 70%

[0088] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage (%) relative to R410A, R404A, or R1234yf. Also, in the table, "boiling point (°C)" refers to the temperature at which the liquid phase of the refrigerant mixture reaches atmospheric pressure (101.33 kPa).

[0089] The coefficient of performance (COP) was calculated using the following formula: COP = (refrigeration capacity or heating capacity) / power consumption

[0090] These values, along with the GWP for each refrigerant mixture, are shown in the table below.

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097] The coordinates of each point were determined using the least squares method as follows.

[0098]

[0099] In the above embodiment, the refrigerant of this disclosure is such that, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x, y, z) satisfy the following requirements, then no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 500 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0100] <Requirements> If 0 < a ≤ 0.4, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2 -2.25a + 24.3, 0.0, -1.25a 2If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points C, F, B'', FB'', B''A'', and A'', respectively, or lie on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'', and A''C, which connect the six points B'' (0.0, 73.9, -a+26.1) and A'' (-a+26.0, 74.0, 0.0), or it lies on the line segments CD, DE, EF, and B''A'' (excluding points C, F, B'', and A'').

[0101] In the above embodiment, the refrigerant of this disclosure is characterized by the following: when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x, y, z) satisfy the following requirements, it can be seen that at 3.0 MPa and 150°C, no disproportionation reaction occurs, the GWP is 300 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0102] <Requirements> If 0 < a ≤ 0.4, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2-2.25a + 24.3, 0.0, -1.25a 2 If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB', B'A', and A'C that connect the six points C, F, B', EF, FB', B'A', and A'C respectively, or lie on the line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A'), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments CD, DE, EF, FB', B'A', and A'C, which connect the six points B' (0.0, 44.1, -a+55.9) and A' (-a+55.7, 44.3, 0.0), or it lies on line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A').

[0103] In the above embodiment, the refrigerant of this disclosure is characterized by the following: when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x, y, z) satisfy the following requirements, it can be seen that at 3.0 MPa and 150°C, no disproportionation reaction occurs, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R410A is 60% or more.

[0104] <Requirements> If 0 < a ≤ 0.4, then point G (-a + 52.8, 22.0, 25.2), point D (-a + 44.0, 0.0, 56.0), point E (1.25a) 2 -2.25a + 24.3, 0.0, -1.25a 2 If the five points are +1.25a+75.7), point F(0.0, -1.5a+15.5, 0.5a+84.5), and point B(0.0, 21.8, -a+78.2), then the figure is enclosed by line segments GD, DE, EF, FB, and BG, which connect these five points respectively, or the figure lies on line segments GD, DE, EF, and BG (except for points F and B), and if 0.4 < a ≤ 10.0, then point G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point E(-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The area is within the range of the figure enclosed by line segments GD, DE, EF, FB, and BG, which connect the five points (+0.3516a+84.561) and point B (0.0, 21.8, -a+78.2), or it lies on the line segments GD, DE, EF, and BG (excluding points F and B).

[0105] As shown above, the test results for each mixed refrigerant are presented (compared to R404A).

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] The coordinates of each point were determined using the least squares method as follows.

[0117]

[0118]

[0119] In the above embodiment, the refrigerant of this disclosure is such that, when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x, y, z) satisfy the following requirements, then no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R404A is 60% or more.

[0120] <Requirements> If 0 < a ≤ 0.4, the figure is within the area enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), I (-1.5a + 8.4, 0.0, 0.5a + 91.6), J (0.0, -a + 5.2, 94.8), and B (0.0, 21.8, -a + 78.2), or on the line segments GD, DI, IJ, and BG (except for points J and B). If 0.4 < a ≤ 5.5, the figure is within the area enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2) and D (-a + 44.0, 0.0, 56.0). Point I (0.0036a 2 -1.5508a+8.42, 0.0, -0.0036a 2 +0.5508a+91.58), point J (0.0, 0.0081a 2 -0.9892a+5.194, -0.0081a 2If 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G(-0.0108a + 94.806) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DI, IJ, and BG (excluding points J and B), and if 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DO, OB, and BG connecting the four points G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DO, and BG (excluding points O and B).

[0121] As shown above, the test results for each mixed refrigerant are presented (compared to R1234yf).

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] The coordinates of each point were determined using the least squares method as follows.

[0133]

[0134] In the above embodiment, the refrigerant of this disclosure is characterized by the following: when the mass percentages of the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, in a three-component composition diagram (see Figures 13-19), the coordinates (x, y, z) satisfy the following requirements, it can be seen that at 3.0 MPa and 150°C, no disproportionation reaction occurs, the GWP is 150 or less, and the boiling point is -40°C or less.

[0135] <Requirements> If 0 < a ≤ 0.4, the figure is within the area enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), K (-4a + 14.6, 0.0, 3a + 85.4), L (0.0, -a + 5.2, 94.8), and B (0.0, 21.8, -a + 78.2), or on the line segments GD, DK, KL, and BG (excluding L and B). If 0.4 < a ≤ 3.5, the figure is within the area enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), Point K (-0.0457a 2 -4.0153a+14.613, 0.0, 0.0457a 2 +3.0153a+85.387), point L (0.0, 0.2245a 2 -3.1012a+8.105, -0.2245a 2If 3.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point O(0.0, 0.0, -a+100.0), and point B(0.0, 21.8, -a+78.2), or is on the line segments GD, DO, OB, and BG connecting the four points G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point O(0.0, 0.0, -a+100.0), and point B(0.0, 21.8, -a+78.2), or is on the line segments GD, DO, and BG (excluding points O and B).

[0136] HFO-1132(E), R32, R1234yf, and HFO-1132a were mixed in the mass percentages shown in Tables 41 and 42, based on their sum, and the acid content (acid component) and appearance of the resulting compositions were evaluated as follows.

[0137] In the stability test of the composition, the acid content in the gas was analyzed by the following method. After cooling, the tube was completely solidified using liquid nitrogen to remove the gas remaining inside. Then, the tube was opened and gradually thawed, and the gas was collected in a Tedlar bag. 5 g of pure water was poured into this Tedlar bag, and the acid was extracted into the pure water while keeping it in good contact with the collected gas. The extract was detected by ion chromatography to determine the presence of fluoride ions (F). - The content (mass ppm) of ) was measured.

[0138]

[0139]

[0140] As shown in Tables 41 and 42, the formation of oxidative decomposition products can be confirmed in the presence of 0.01 mol% or more of oxygen. Furthermore, it can be seen that the amount of oxidative decomposition products is suppressed when the amount of water added is at least 10 ppm by mass in the presence of 0.01 mol% or more of oxygen. In addition, it can be seen that the formation of solid matter is suppressed when the amount of water added is less than 2000 ppm by mass in the presence of 0.01 mol% or more of oxygen.

Claims

1. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a), and in the refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point C (-a + 60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 If 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) are within the range of the figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points C, F, B'', FB'', B''A'', and A'', respectively, or lie on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), and if 0.4 < a ≤ 10.0, then point C (-a + 60.0, 40.0, 0.0), point D (-a + 44.0, 0.0, 56.0), point E (-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 A composition characterized by being within the range of a figure enclosed by line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points B'' (0.0, 73.9, -a+26.1) and A'' (-a+26.0, 74.0, 0.0), or lying on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A'').

2. In the refrigerant, let the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a, based on their total sum, be x, y, z, and a respectively (where 0 < a ≤ 10.0). In the ternary composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) are: When 0 < a ≤ 0.4: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 + 1.25a + 75.7), Point F (0.0, -1.5a + 15.5, 0.5a + 84.5), Point B’ (0.0, 44.1, -a + 55.9), and Point A’ (-a + 55.7, 44.3, 0.0) are within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’, and A’C connecting these six points respectively or on the line segments CD, DE, EF, and B’A’ (excluding points C, F, B’, and A’). When 0.4 < a ≤ 10.0: Point C (-a + 60.0, 40.0, 0.0), Point D (-a + 44.0, 0.0, 56.0), Point E (-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), Point F (0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 + 0.3516a + 84.561), Point B’ (0.0, 44.1, -a + 55.9), and Point A’ (-a + 55.7, 44.3, 0.0) are within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’, and A’C connecting these six points respectively or on the line segments CD, DE, EF, and B’A’ (excluding points C, F, B’, and A’). The composition according to claim 1.

3. In the refrigerant, the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a, based on their sum, are x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, if the coordinates (x,y,z) are 0 < a ≤ 0.4, then point G (-a + 52.8, 22.0, 25.2), point D (-a + 44.0, 0.0, 56.0), point E (1.25a). 2 -2.25a + 24.3, 0.0, -1.25a 2 If the five points are +1.25a+75.7), point F(0.0, -1.5a+15.5, 0.5a+84.5), and point B(0.0, 21.8, -a+78.2), then the figure is enclosed by line segments GD, DE, EF, FB, and BG, which connect these five points respectively, or the figure lies on line segments GD, DE, EF, and BG (except for points F and B), and if 0.4 < a ≤ 10.0, then point G(-a+52.8, 22.0, 25.2), point D(-a+44.0, 0.0, 56.0), point E(-0.0013a) 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a+75.663), point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 The composition according to claim 1, wherein the area is within the range of the figure enclosed by line segments GD, DE, EF, FB, and BG that connect the five points (+0.3516a+84.561) and point B (0.0, 21.8, -a+78.2), or lies on the line segments GD, DE, EF, and BG (excluding points F and B).

4. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf) and 1,1-difluoroethylene (HFO-1132a), and in the refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point G (-a + 52.8, 22.0, 25.2), If the five points D (-a+44.0, 0.0, 56.0), I (-1.5a+8.4, 0.0, 0.5a+91.6), J (0.0, -a+5.2, 94.8), and B (0.0, 21.8, -a+78.2) are enclosed by line segments GD, DI, IJ, JB, and BG, respectively, or lie on the line segments GD, DI, IJ, and BG (excluding points J and B), and 0.4 < a ≤ 5.5, then point G (-a+52.8, 22.0, 25.2), point D (-a+44.0, 0.0, 56.0), point I (0.0036a) 2 -1.5508a+8.42, 0.0, -0.0036a 2 +0.5508a+91.58), point J (0.0, 0.0081a 2 -0.9892a+5.194, -0.0081a 2 If 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DI, IJ, JB, and BG connecting the five points G(-0.0108a + 94.806) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DI, IJ, and BG (excluding points J and B), and if 5.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DO, OB, and BG connecting the four points G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) respectively, or is on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the following features.

5. A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf) and 1,1-difluoroethylene (HFO-1132a), and in the refrigerant, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a, respectively (where 0 < a ≤ 10.0), and in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, when the coordinates (x,y,z) are 0 < a ≤ 0.4, point G (-a + 52.8, 22.0, 25.2), If the five points D (-a+44.0, 0.0, 56.0), K (-4a+14.6, 0.0, 3a+85.4), L (0.0, -a+5.2, 94.8), and B (0.0, 21.8, -a+78.2) are located within the area enclosed by line segments GD, DK, KL, LB, and BG, respectively, or on the line segments GD, DK, KL, and BG (excluding points L and B), and 0.4 < a ≤ 3.5, then the points G (-a+52.8, 22.0, 25.2), D (-a+44.0, 0.0, 56.0), and K (-0.0457a) are located within the area enclosed by line segments GD, DK, KL. 2 -4.0153a+14.613, 0.0, 0.0457a 2 +3.0153a+85.387), point L(0.0, 0.2245a 2 -3.1012a+8.105, -0.2245a 2 If 3.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DK, KL, LB, and BG connecting the five points G (-a + 2.1012a + 91.895) and point B (0.0, 21.8, -a + 78.2), or is on the line segments GD, DK, KL, and BG (excluding points L and B), and if 3.5 < a ≤ 10.0, the area is within the range of the figure enclosed by line segments GD, DO, OB, and BG connecting the four points G (-a + 52.8, 22.0, 25.2), D (-a + 44.0, 0.0, 56.0), O (0.0, 0.0, -a + 100.0), and B (0.0, 21.8, -a + 78.2), or is on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the following features.

6. The composition according to any one of claims 1 to 5, further comprising refrigeration oil and used as a working fluid for a refrigeration unit.

7. A composition according to any one of claims 1 to 3, which is used as a substitute refrigerant for R410A.

8. Use of the composition according to any one of claims 1 to 3 as a substitute refrigerant for R410A.

9. The composition according to claim 4, which is used as a substitute refrigerant for R404A.

10. Use of the composition according to claim 4 as a substitute refrigerant for R404A.

11. The composition according to claim 5, which is used as a substitute refrigerant for R1234yf.

12. Use of the composition according to claim 5 as a substitute refrigerant for R1234yf.

13. A refrigerator comprising the composition according to any one of claims 1 to 5 as a working fluid.

14. A method for operating a refrigerator, comprising the step of circulating a composition described in any one of claims 1 to 5 as a working fluid in the refrigerator.

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