Composition including refrigerant, use thereof, and refrigeration machine comprising the same and operation method of refrigeration machine

Abstract

To provide a novel low GWP mixed refrigerant.SOLUTION: There is provided a composition including a refrigerant, the refrigerant includes: trans-1,2-difluoroethylene(HFO-1132(E)), difluoromethane(R32) and 2,3,3,3-tetrafluoropropene(HFO-1234yf). In a three-component composition diagram in which, when mass% of each of the HFO-1132(E), R32 and R1234yf based on a total sum of them, is expressed as x, y, z, respectively, the total sum of the HFO-1132(E), R32 and R1234yf is 100 mass%, the x, y, z are in a range of a graphic surrounded by straight lines C1D, DG, GH, HB' and B'C1 connecting five points (x,y,z) on specific coordinates, or on the straight lines C1D and B'C1 (except for the point D and point B').SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to compositions containing refrigerants, uses thereof, and chillers having same and methods of operating such chillers. [Background technology]

[0002] As a working fluid for heat cycle that can replace R410A, a working fluid for 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] International Publication No. 2015 / 141678 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure aims to provide a novel low GWP refrigerant mixture. [Means for solving the problem]

[0005] Section 1. A composition containing a refrigerant for use in operating an automotive air conditioner, the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf); When the mass percentages of HFO-1132(E), R32 and R1234yf based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C1 (52.0, 36.9, 11.1), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area of ​​the figure enclosed by the lines C1D, DG, GH, HB', and B'C1 which respectively connect the above five points, or on the lines C1D and B'C1 (however, points D and B' are excluded), composition. Section 2. In the refrigerant, the coordinates (x, y, z) are: Point C2 (49.1, 23.5, 27.4), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B (0.0, 23.3, 76.7) Within the area of ​​the figure enclosed by the lines C2D, DG, GH, HB, and BC2 connecting the above five points, or on the lines C2D and BC2 (excluding points D and B), Item 1. The composition according to item 1. Section 3. In the refrigerant, the coordinates (x, y, z) are: Point L (35.6, 36.8, 27.6), Point K (44.2, 23.4, 32.4), Point D2 (48.1, 18.7, 33.2), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments LK, KD2, D2D, DG, GH, HB', and B'L connecting the seven points above, or on the line segments LK, KD2, D2D, and B'L (excluding points D and B'), the line segments LK, D2D, DG, GH, HB' and B'L are straight lines, The coordinates (x, y, z) of the point on the line segment KD2 are (x, 0.01727x 2 -2.7828x+112.643, -0.01727x 2 +1.7828x-12.643), Item 1. The composition according to item 1. Section 4. In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DG, GH, HB' and B'P connecting the above 10 points, or on the line segments PO, ON', N'N, NM', M'D1, D1D and B'P (excluding points D and B'), the line segments PO, D1D, DG, GH, HB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), Item 1. The composition according to item 1. Section 5. In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B' (0.0, 36.6, 63.4) Within the area of ​​the figure enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB' and B'P respectively connecting the eleven points above, or on said line segments PO, ON', N'N, NM', M'D1, D1D, EE', E'F and B'P (however, points D, E and B' are excluded), the line segments PO, D1D, DE, FB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4) Item 1. The composition according to item 1. Section 6. In the refrigerant, the coordinates (x, y, z) are: Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B (0.0, 23.3, 76.7) Within the area enclosed by the line segments ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB and BO which respectively connect the above 10 points, or on said line segments ON', N'N, NM', M'D1, D1D, EE', E'F and BO (however, points D, E and B are excluded), The line segments D1D, DE, FB, and BO are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4) Item 1. The composition according to item 1. Section 7. The refrigerant further comprises: The composition according to any one of items 1 to 6, further comprising 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. Section 8. 8. The composition according to any one of items 1 to 7, wherein the refrigerant further contains 0.1% or less of moisture. Section 9. 9. The composition according to any one of items 1 to 8, wherein the total content of HFO-1132(E), R32 and HFO-1234yf is more than 99.5 mass% based on the total amount of the refrigerants. Section 10. A composition comprising a refrigerant, The refrigerant comprises: HFO-1132(E), R32 and R1234yf; 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; A composition comprising: Section 11. 1. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), R32 and R1234yf, and 0.1% or less water. Section 12. Item 12. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of items 1 to 11. Section 13. 12. A refrigeration device comprising the composition according to any one of items 1 to 11 as a working fluid. Section 14. A composition comprising a refrigerant, A composition, wherein the refrigerant contains 28±0.5 mass% of HFO-1132(E), 21.5±0.5 mass% of R32 and 50.5±0.5 mass% of HFO-1234yf, respectively, based on the sum of these. Section 15. A composition comprising a refrigerant, A composition, wherein the refrigerant contains HFO-1132(E), R32 and HFO-1234yf in amounts of 28±0.5 mass%, 21.5±0.5 mass% and 50.5±0.5 mass%, respectively, based on the total amount of these. A refrigeration device comprising as a working fluid. Section 16. A composition comprising a refrigerant, A composition, wherein the refrigerant contains HFO-1132(E), R32 and HFO-1234yf in amounts of 28±0.5 mass%, 21.5±0.5 mass% and 50.5±0.5 mass%, respectively, based on the total amount of these. A refrigeration method comprising the step of operating a refrigeration cycle using the above-mentioned. Effect of the Invention

[0006] The refrigerants of the present disclosure have a low GWP. [Brief description of the drawings]

[0007] [Figure 1] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Diagram 2] FIG. 2 is a diagram showing an apparatus used in the burning rate test of the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present inventors have conducted intensive research to solve the above problems and have found that various mixed refrigerants described below have the above properties.

[0009] The present disclosure has been completed as a result of further research based on such findings. The present disclosure includes the following embodiments. <Terminology> In this specification, the term "refrigerant" includes at least compounds assigned with a refrigerant number (ASHRAE number) beginning with R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and further 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 the structure of the compounds. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

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

[0011] In this specification, the term "substitution" when used in the context of "substituting" a first refrigerant with a second refrigerant means that, as a first type, equipment designed to operate using a first refrigerant can be operated under optimal conditions using a second refrigerant by only changing a few parts (at least one of refrigeration oil, gaskets, packing, expansion valves, dryers, and other parts) and adjusting the equipment as necessary. In other words, this type refers to operating the same equipment by "substituting" a refrigerant. The "substitution" of this type can be categorized into "drop-in substitution," "nearly drop-in substitution," and "retrofit," in order of the degree of change or adjustment required when replacing with the second refrigerant.

[0012] The second category, where equipment designed to operate with a second refrigerant is installed and used for the same application as an existing application of a first refrigerant, is also included in the term "substitution." This category refers to "substituting" a refrigerant to serve the same application.

[0013] In this specification, the term "refrigeration machine" refers to a device that removes heat from an object or space to lower its temperature below that of the surrounding air and maintains this low temperature. In other words, a refrigerator is a conversion device that obtains energy from the outside, performs work, and converts it into energy in order to transfer heat from a low temperature to a high temperature.

[0014] In this specification, the term "vehicle air conditioner" refers to a type of refrigeration device used in automobiles such as gasoline vehicles, hybrid vehicles, electric vehicles, hydrogen vehicles, etc. The term vehicle air conditioner refers to a refrigeration device consisting of a refrigeration cycle in which heat exchange is performed with a liquid refrigerant in an evaporator, the evaporated refrigerant gas is sucked into a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied in a condenser, and the refrigerant gas is further adiabatically expanded by passing through an expansion valve, and then supplied to the evaporator again as a liquid refrigerant.

[0015] In this specification, a refrigerant being "WCF mildly flammable" means that its worst case formulation for flammability (WCF) has a burning velocity of 10 cm / s or less according to the US ANSI / ASHRAE34-2013 standard.

[0016] In addition, in this specification, a refrigerant being ASHRAE mildly flammable (WCF & WCFF mildly flammable) means that the burning velocity of the WCF is 10 cm / s or less, and the worst case of fractionation for flammability (WCFF), identified by conducting leakage tests during storage, transportation, and use based on ANSI / ASHRAE34-2013 using the WCF, has a burning velocity of 10 cm / s or less, and the flammability classification of the U.S. ANSI / ASHRAE34-2013 standard is determined to be "2L class."

[0017] Pressures described in this specification are in units of absolute pressure unless otherwise specified.

[0018] 1. Refrigerant Refrigerants of this disclosure include HFO-1132(E), R32 and HFO-1234yf.

[0019] The refrigerants of the present disclosure are low GWP refrigerant mixtures.

[0020] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0021] <Requirements> When the mass percentages of HFO-1132(E), R32 and R1234yf based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C1 (52.0, 36.9, 11.1), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) The point is within the area surrounded by the straight lines C1D, DG, GH, HB', and B'C1 which respectively connect the five points, or is on the straight lines C1D and B'C1 (however, points D and B' are excluded).

[0022] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the boiling point is -40°C or lower, and the GWP is 160 or lower.

[0023] <Requirements> The coordinates (x,y,z) are Point C2 (49.1, 23.5, 27.4), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B (0.0, 23.3, 76.7) The point is within the area surrounded by the straight lines C2D, DG, GH, HB, and BC2 connecting the five points above, or is on the straight lines C2D and BC2 (excluding points D and B).

[0024] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the WCF is nonflammable, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0025] <Requirements> The coordinates (x,y,z) are Point L (35.6, 36.8, 27.6), Point K (44.2, 23.4, 32.4), Point D2 (48.1, 18.7, 33.2), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments LK, KD2, D2D, DG, GH, HB', and B'L connecting the seven points above, or on the line segments LK, KD2, D2D, and B'L (excluding points D and B'), the line segments LK, D2D, DG, GH, HB' and B'L are straight lines, The coordinates (x, y, z) of the point on the line segment KD2 are (x, 0.01727x 2 -2.7828x+112.643, -0.01727x 2 +1.7828x-12.643).

[0026] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the WCCF is nonflammable, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0027] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DG, GH, HB' and B'P connecting the above 10 points, or on the line segments PO, ON', N'N, NM', M'D1, D1D and B'P (excluding points D and B'), the line segments PO, D1D, DG, GH, HB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406).

[0028] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the WCCF is non-flammable, the refrigeration capacity (Cap) ratio to R1234yf is 150% or more, and the GWP is 250 or less.

[0029] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B' (0.0, 36.6, 63.4) Within the area of ​​the figure enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB' and B'P respectively connecting the eleven points above, or on said line segments PO, ON', N'N, NM', M'D1, D1D, EE', E'F and B'P (however, points D, E and B' are excluded), the line segments PO, D1D, DE, FB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4).

[0030] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the WCCF is non-flammable, the refrigeration capacity (Cap) ratio to R1234yf is 150% or more, and the GWP is 160 or less.

[0031] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B (0.0, 23.3, 76.7) Within the area enclosed by the line segments ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB and BO which respectively connect the above 10 points, or on said line segments ON', N'N, NM', M'D1, D1D, EE', E'F and BO (however, points D, E and B are excluded), The line segments D1D, DE, FB, and BO are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4).

[0032] The refrigerant of the present disclosure may be a refrigerant that contains 28±0.5 mass% of HFO-1132(E), 21.5±0.5 mass% of R32, and 50.5±0.5 mass% of HFO-1234yf, respectively, based on the sum of these.

[0033] The refrigerant of the present disclosure can suppress the disproportionation reaction even when the refrigerant pressure in a local area of ​​the refrigeration cycle reaches 3 MPa and the refrigerant temperature reaches 150°C.

[0034] In addition, the refrigerant of the present disclosure has an advantage that it is easy to use in heating using a heat pump because the boiling point is −40.0° C. or less. For example, the refrigerant of the present disclosure has an advantage that, when used to operate the refrigeration cycle of an in-vehicle air conditioner, heating using a heat pump that consumes less power than an electric heater is possible. Examples of in-vehicle air conditioners include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0035] The refrigerant of the present disclosure may contain additional refrigerants in addition to HFO-1132(E), R32, and HFO-1234yf, as long as the above-mentioned properties and effects are not impaired. In this regard, in one embodiment, the refrigerant of the present disclosure preferably contains 99.5% by mass or more of HFO-1132(E), R32, and HFO-1234yf in total relative to the entire refrigerant, 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 refrigerant of the present disclosure may be substantially composed of only HFO-1132(E), R32, and HFO-1234yf, and in this case, the refrigerant of the present disclosure may be composed of only HFO-1132(E), R32, HFO-1234yf, and unavoidable impurities. The refrigerants of the present disclosure may consist solely of HFO-1132(E), R32 and HFO-1234yf.

[0036] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one type of additional refrigerant alone or two or more types of additional refrigerants.

[0037] Additional refrigerants include acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, 3,3,3-trifluoropropyne, and the like.

[0038] The compositions of the present disclosure include A composition comprising a refrigerant, The refrigerant comprises: HFO-1132(E), R32 and R1234yf; and Also included are compositions containing 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 0.01% by mass or less based on the total refrigerant.

[0039] 2. Refrigerant Composition The refrigerant composition of the present disclosure contains at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure. The refrigerant composition of the present disclosure can be further mixed with at least a refrigerating machine oil to obtain a working fluid for a refrigerating machine. The refrigerant composition of the present disclosure further contains at least one other component in addition to the refrigerant of the present disclosure. The refrigerant composition of the present disclosure may contain at least one of the following other components as necessary. As described above, when the refrigerant composition of the present disclosure is used as a working fluid in a refrigerator, it is usually mixed with at least a refrigerating machine oil. Therefore, the refrigerant composition of the present disclosure preferably does not substantially contain a refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure preferably has a refrigerating machine oil content of 1 mass% or less, more preferably 0.1 mass% or less, relative to the entire refrigerant composition.

[0040] 2.1 water The refrigerant composition of the present disclosure may contain a small amount of water. The water content in the refrigerant composition is preferably 0.1 mass% or less based on the entire refrigerant. By containing a small amount of water in the refrigerant composition, the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant are stabilized, and the oxidation of the unsaturated fluorocarbon compound is also less likely to occur, thereby improving the stability of the refrigerant composition.

[0041] Compositions of the present disclosure also include compositions comprising a refrigerant, the refrigerant including HFO-1132(E), R32, and R1234yf, and 0.1% or less water.

[0042] 2.2 tracer The tracer is added to the refrigerant compositions of the present disclosure in a detectable concentration so that if the refrigerant compositions of the present disclosure are diluted, contaminated, or otherwise altered, that alteration can be traced.

[0043] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0044] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0045] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N 2 O) and the like. Particularly preferred tracers are hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers.

[0046] As tracers, the following compounds are preferred: FC-14 (Tetrafluoromethane, CF 4 ) HCC-40 (chloromethane, CH 3 Cl) HFC-23 (Trifluoromethane, CHF 3 ) HFC-41 (fluoromethane, CH 3 Cl) HFC-125 (Pentafluoroethane, CF 3 CHF 2 ) HFC-134a (1,1,1,2-tetrafluoroethane, CF 3 CH 2 F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF 2 CHF 2 ) HFC-143a (1,1,1-trifluoroethane, CF 3 CH 3 ) HFC-143 (1,1,2-trifluoroethane, CHF 2 CH 2 F) HFC-152a (1,1-difluoroethane, CHF 2 CH 3 ) HFC-152 (1,2-difluoroethane, CH 2 FCH 2 F) HFC-161 (fluoroethane, CH 3 CH 2 F) HFC-245fa (1,1,1,3,3-pentafluoropropane, CF 3 CH 2 CHF 2 ) HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF 3 CH 2 CF 3 ) HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF 3 CHFCHF 2 ) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF 3 CHFCF 3 ) HCFC-22 (chlorodifluoromethane, CHClF 2 ) HCFC-31 (chlorofluoromethane, CH 2 ClF) CFC-1113 (chlorotrifluoroethylene, CF 2 =CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF 3 O.C.H.F. 2 ) HFE-134a (trifluoromethyl-fluoromethyl ether, CF 3 OCH 2 F) HFE-143a (trifluoromethyl ether, CF 3 OCH 3 ) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF 3 OCHFCF 3 ) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF 3 OCH2CF 3 )

[0047] The refrigerant compositions of the present disclosure may contain a total of about 10 parts per million (ppm) of tracer(s) based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 1000 ppm or less of tracer(s) based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 30 ppm or more of tracer(s) based on the total refrigerant composition, more preferably about 50 ppm or more of tracer(s). The refrigerant compositions of the present disclosure may contain a total of about 500 ppm or less of tracer(s) based on the total refrigerant composition, and may contain a total of about 300 ppm or less of tracer(s).

[0048] 2.3 UV fluorescent dye The refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone, or may contain two or more types of ultraviolet fluorescent dyes.

[0049] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0050] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, and derivatives thereof. As the ultraviolet fluorescent dye, either or both of naphthalimide and coumarin are particularly preferred.

[0051] 2.4 Stabilizer The refrigerant composition of the present disclosure may contain one type of stabilizer alone, or may contain two or more types of stabilizers.

[0052] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0053] The stabilizers include, for example, nitro compounds, ethers, and amines.

[0054] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0055] An example of the ethers is 1,4-dioxane.

[0056] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine, diphenylamine, and the like.

[0057] Other examples include butylhydroxyxylene and benzotriazole.

[0058] The stabilizer content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, based on the total mass of the refrigerant, and is preferably 5% by mass or less, and more preferably 2% by mass or less, based on the total mass of the refrigerant.

[0059] 2.5 Polymerization Inhibitor The refrigerant composition of the present disclosure may contain one type of polymerization inhibitor alone, or may contain two or more types of polymerization inhibitors.

[0060] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0061] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0062] The content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the refrigerant, and is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the refrigerant.

[0063] 3. Working fluid containing refrigeration oil The refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and a refrigerating machine oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerating machine oil-containing working fluid of the present disclosure is obtained by mixing the refrigerating machine oil used in the compressor of the refrigerator with the refrigerant or the refrigerant composition. The refrigerating machine oil-containing working fluid generally contains 10% by mass or more of the refrigerating machine oil. The refrigerating machine oil-containing working fluid generally contains 50% by mass or less of the refrigerating machine oil.

[0064] 3.1 Refrigerating machine oil The composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oils.

[0065] The refrigerating machine oil is not particularly limited and can be appropriately selected from commonly used refrigerating machine oils. In this case, if necessary, a refrigerating machine oil having superior miscibility with the mixture and an effect of improving the stability of the mixture can be appropriately selected.

[0066] The base oil of the refrigerating machine oil is preferably at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE).

[0067] The refrigeration oil may further contain an additive in addition to the base oil. The additive may be at least one selected from the group consisting of an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, a rust inhibitor, an oiliness agent, and an antifoaming agent.

[0068] From the viewpoint of lubrication, a refrigeration oil having a kinetic viscosity at 40° C. of 5 cSt or more is preferable. In addition, from the viewpoint of lubrication, a refrigerating machine oil having a kinetic viscosity at 40° C. of 400 cSt or less is preferable.

[0069] The refrigerating machine oil-containing working fluid of the present disclosure may further contain at least one additive, if necessary. Examples of the additive include the following compatibilizers.

[0070] 3.2 Compatibilizer The refrigerating machine oil-containing working fluid of the present disclosure may contain one type of compatibilizer alone or two or more types.

[0071] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0072] Examples of the compatibilizer include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes, etc. As the compatibilizer, polyoxyalkylene glycol ethers are particularly preferred.

[0073] 4. How to operate a refrigerator The method of operating a refrigerator according to the present disclosure is a method of operating a refrigerator using the refrigerant according to the present disclosure.

[0074] Specifically, a method of operating a refrigerator of the present disclosure includes circulating a refrigerant of the present disclosure in the refrigerator.

[0075] 5. Method for suppressing disproportionation reaction The method for suppressing a disproportionation reaction disclosed herein is a method for suppressing a disproportionation reaction of HFO-1132(E), comprising a step of operating a refrigeration cycle using the refrigerant disclosed herein.

[0076] The method for suppressing a disproportionation reaction disclosed herein has the particular advantage 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.

[0077] According to the method for suppressing a disproportionation reaction disclosed herein, it becomes possible to operate a refrigeration cycle while suppressing a disproportionation reaction even in a refrigerator that is not particularly provided with a means for suppressing a disproportionation reaction.

[0078] 6. Use for inhibiting disproportionation reactions The use of the present disclosure is the use of R32 and HFO-1234yf to suppress the disproportionation reaction of HFO-1132(E), and the suppression of the disproportionation reaction is carried out by mixing HFO-1132(E), R32, and HFO-1234yf in a mixing ratio of the refrigerant of the present disclosure.

[0079] When used to inhibit a disproportionation reaction according to the present disclosure, the effect is particularly 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.

[0080] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0081] The present disclosure will be described in more detail below by way of examples, although the present disclosure is not limited to these examples.

[0082] A mixed refrigerant was prepared by mixing HFO-1132(E), R32 and HFO-1234yf in the mass percentages shown in Table 1, based on the total sum of these.

[0083] Each of these mixed refrigerants was examined for the presence or absence of a disproportionation reaction using the following test method and conditions. Test Method The refrigerant composition to be tested was transferred and filled into a test vessel and heated to 150°C, after which a voltage was applied to a Pt wire in the vessel to melt it, thereby giving the refrigerant composition 30 J of energy. The presence or absence of a disproportionation reaction was judged by a sudden increase in pressure and temperature in the apparatus. Test conditions Test container: 38cc SUS container Test temperature: 150℃ Pressure: 3 MPa Judgment criteria "No explosion": The temperature or pressure after Pt filament melting is less than twice as high, and no rapid disproportionation reaction occurs. "Explosion": The temperature or pressure after Pt filament melting reached more than double the normal level, causing a rapid disproportionation reaction.

[0084] [Table 1]

[0085] The results in Table 1 show that the refrigerant of the present disclosure does not undergo disproportionation within the region shown in the ternary diagram in FIG.

[0086] The burning rate test was performed as follows using the apparatus shown in Figure 2. First, the mixed refrigerant used had a purity of 99.5% or more, and was degassed by repeating cycles of freezing, pumping, and thawing until no trace of air was observed on the vacuum gauge. The burning rate was measured by the closed method. The initial temperature was ambient temperature. Ignition was performed by generating an electric spark between the electrodes at the center of the sample cell. The duration of the discharge was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The flame propagation state was visualized by the Schlieren method. A cylindrical container (inner diameter: 155 mm, length: 198 mm) with two light-transmitting acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of the flame were recorded with a high-speed digital video camera at a framing speed of 600 fps and stored in a PC. The burning velocity (Su (cm / s)) is expressed as the volume of unburned gas consumed by a unit area of ​​the flame surface per unit time, and is calculated using the following formula: Su=Sb*ρu / ρb Sb: flame propagation speed (cm / s) ρu: Adiabatic flame temperature (unburned) ρb: Adiabatic flame temperature (burned) Where: Sb was obtained from the Schlieren video image, ρu was the measured temperature, and ρb was calculated from the heat of combustion and the specific heat at constant pressure of the combustion gas. The results are shown in Table 2.

[0087] [Table 2]

[0088] The results in Table 2 show that the refrigerants disclosed herein are WCF non-flammable or WCFF non-flammable within the region shown in the triangular diagram in FIG.

[0089] The GWP of HFO-1132(E) was set to 1, and the GWP of R32 and HFO-1234yf were evaluated based on the values ​​in the Fourth Assessment Report of the IPCC (Intergovernmental Panel on Climate Change). The COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were calculated 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 9.0). The physical property data of HFO-1132(E) was obtained from actual measurements. Evaporation temperature -30℃ Condensation temperature 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70%

[0090] In the following tables, "COP ratio" and "refrigeration capacity ratio" indicate the ratio (%) to R1234yf. In the table, "boiling point (℃)" refers to the temperature at which the liquid phase of the mixed refrigerant reaches atmospheric pressure (101.33 kPa). In the table, "power consumption (%)" refers to the electrical energy used to run the electric vehicle, and is expressed as a ratio to the electrical energy consumed when the refrigerant is HFO-1234yf. In the table, "heating power consumption (%)" refers to the electrical energy used to operate the heater in the electric vehicle, and is expressed as a ratio to the electrical energy consumed when the refrigerant is HFO-1234yf.

[0091] In the table below, "Driving distance (with)" refers to the relative percentage (%) of the driving distance when driven with heating in an electric vehicle equipped with a secondary battery of a certain electric capacity, with the driving distance (without) when driven without heating (heating power consumption is 0) being taken as 100%.

[0092] The heating method used was an electric heater system for heating refrigerants with a boiling point above -40°C, and a heat pump system for heating refrigerants with a boiling point below -40°C.

[0093] The amount of power consumed during heating was calculated using the following formula. Note that heating COP means "heating efficiency." Power consumption when heating = Heating capacity / Heating COP

[0094] Regarding heating efficiency, in the case of an electric heater, the heating COP is 1, and the same amount of electricity is consumed for heating as for power. In other words, the power consumption for heating is E=E / (1+COP).

[0095] On the other hand, in the case of heat pumps, Refprop 9.0 (NIST) was used to perform theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions to obtain the heating COP. Evaporation temperature -30℃ Condensation temperature 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70% The driving distance was calculated using the following formula. Driving distance = (battery capacity) / (power consumption + power consumption for heating) These values ​​are shown in the table below along with the GWP for each mixed refrigerant. Note that the specific COP and specific refrigeration capacity are shown as a percentage relative to HFO-1234y.

[0096] The coefficient of performance (COP) was calculated using the following formula. COP = (refrigeration capacity or heating capacity) / power consumption

[0097] [Table 3]

[0098] [Table 4]

[0099] [Table 5]

[0100] [Table 6]

[0101] [Table 7]

[0102] [Table 8]

[0103] The coordinates on the line segments JK, MN, NO, and EF were calculated based on the least squares method as follows. The coordinates on M'D1 can be expressed by the same formula as the coordinates on MN shown in Table 9.

[0104] [Table 9]

[0105] From these results, it can be seen that in the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on the sum of these are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0106] <Requirements> When the mass percentages of HFO-1132(E), R32 and R1234yf based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C1 (52.0, 36.9, 11.1), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) The point is within the area surrounded by the straight lines C1D, DG, GH, HB', and B'C1 which respectively connect the five points, or is on the straight lines C1D and B'C1 (however, points D and B' are excluded).

[0107] In the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the boiling point is -40°C or lower, and the GWP is 160 or lower.

[0108] <Requirements> The coordinates (x,y,z) are Point C2 (49.1, 23.5, 27.4), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B (0.0, 23.3, 76.7) The point is within the area surrounded by the straight lines C2D, DG, GH, HB, and BC2 connecting these five points, or is on said straight lines C2D and BC2 (excluding points D and B).

[0109] Furthermore, in the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, 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, the WCF is nonflammable, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0110] <Requirements> The coordinates (x,y,z) are Point L (35.6, 36.8, 27.6), Point K (44.2, 23.4, 32.4), Point D2 (48.1, 18.7, 33.2), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments LK, KD2, D2D, DG, GH, HB', and B'L connecting the seven points above, or on the line segments LK, KD2, D2D, and B'L (excluding points D and B'), the line segments LK, D2D, DG, GH, HB' and B'L are straight lines, The coordinates (x, y, z) of the point on the line segment KD2 are (x, 0.01727x2 -2.7828x+112.643, -0.01727x 2 +1.7828x-12.643).

[0111] Furthermore, in the refrigerant disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, 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, the WCCF is nonflammable, the boiling point is -40°C or lower, and the GWP is 250 or lower.

[0112] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) Within the area enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DG, GH, HB' and B'P connecting the above 10 points, or on the line segments PO, ON', N'N, NM', M'D1, D1D and B'P (excluding points D and B'), the line segments PO, D1D, DG, GH, HB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2-8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406).

[0113] Furthermore, in the refrigerants disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, 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, the WCCF is non-flammable, the refrigeration capacity (Cap) ratio to R1234yf is 150% or more, and the GWP is 250 or less.

[0114] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B' (0.0, 36.6, 63.4) Within the area of ​​the figure enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB' and B'P respectively connecting the eleven points above, or on said line segments PO, ON', N'N, NM', M'D1, D1D, EE', E'F and B'P (however, points D, E and B' are excluded), the line segments PO, D1D, DE, FB' and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4).

[0115] Furthermore, in the refrigerants disclosed herein, when the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, 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, the WCCF is non-flammable, the refrigeration capacity (Cap) ratio to R1234yf is 150% or more, and the GWP is 160 or less.

[0116] <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B (0.0, 23.3, 76.7) Within the area enclosed by the line segments ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB and BO which respectively connect the above 10 points, or on said line segments ON', N'N, NM', M'D1, D1D, EE', E'F and BO (however, points D, E and B are excluded), The line segments D1D, DE, FB, and BO are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4).

[0117] Furthermore, as shown in Table 10, the refrigerant of the present disclosure exhibits the desired effects even when it contains certain additional compounds.

[0118] [Table 10]

[0119] Furthermore, when the refrigerant of the present disclosure is subjected to a stability test under the following conditions, it is found that, as shown in Table 11, when the refrigerant contains a specified proportion of moisture, the generation of solids is suppressed.

[0120] <Sample preparation> A predetermined amount of water was added to the 1,2-difluoroethylene to adjust the water content relative to the 1,2-difluoroethylene to 10, 100, 1000, or 2000 ppm by mass. The 1,2-difluoroethylene with the water content adjusted as described above was sealed in a container, and oxygen was blown into the container to adjust the amount of oxygen relative to the 1,2-difluoroethylene to be as shown in Table 11, based on the 1,2-difluoroethylene. In this manner, each fluoroethylene composition shown in Table 11, in which the water content and oxygen content were adjusted to a predetermined ratio, was obtained.

[0121] Each of the fluoroethylene compositions shown in Table 11, which did not contain water and had the oxygen content adjusted to a predetermined ratio, was obtained in the same manner as in the above examples, except that no water or no oxygen was added to the 1,2-difluoroethylene used above.

[0122] <Evaluation method> (Fluoroethylene stability test) A stability test was carried out on each of the fluoroethylene compositions obtained in the above Examples and Comparative Examples as follows. The fluoroethylene composition was added to a glass tube (ID 8 mmΦ x OD 12 mmΦ x L 300 mm) with one side heat-sealed so that the content of 1,2-difluoroethylene was 0.01 mol. The tube was sealed by heat sealing. The tube was placed in a thermostatic chamber under an atmosphere of 150°C and kept in this state for one week. Thereafter, the tube was removed from the thermostatic chamber and cooled, and the appearance was checked and the acid content in the gas in the tube was analyzed to evaluate the stability of the fluoroethylene.

[0123] In the stability test of fluoroethylene, the analysis of the acid content in the gas was carried out by the following method. After the above cooling, the tube was cooled with liquid nitrogen to completely solidify the gas remaining in the tube. The tube was then opened and gradually thawed, and the gas was collected in a Tedlar bag. 5 g of pure water was poured into the Tedlar bag, and the acid content was extracted into the pure water while being in close contact with the collected gas. The extract was detected by ion chromatography, and the fluoride ion (F-) content (ppm by mass) was measured.

[0124] [Table 11] [Explanation of symbols]

[0125] 1: Sample cell 2: High-speed camera 3: Xenon lamp 4: Collimating lens 5: Collimating lens 6: Ring filter

Claims

1. A composition containing a refrigerant used to operate an automotive air conditioner, the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoropropene (HFO-1234yf); When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point C1 (52.0, 36.9, 11.1), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) The point is within the area enclosed by the lines C1D, DG, GH, HB', and B'C1 connecting the five points above, or on the lines C1D and B'C1 (excluding points D and B'), The refrigerant further at least one additional refrigerant selected from the group consisting of acetylene, HFO-1132a, HFO-1141, HFO-1123, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, and 3,3,3-trifluoropropyne; Contains 99.5% by mass or more of HFO-1132(E), R32 and HFO-1234yf in total refrigerant. composition.

2. In the refrigerant, the coordinates (x, y, z) are: Point C2 (49.1, 23.5, 27.4), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B (0.0, 23.3, 76.7) Within the area of ​​the figure enclosed by the lines C2D, DG, GH, HB, and BC2 connecting the five points above, or on the lines C2D and BC2 (excluding points D and B), The composition of claim 1.

3. In the refrigerant, the coordinates (x, y, z) are: Point L (35.6, 36.8, 27.6), Point K (44.2, 23.4, 32.4), Point D2 (48.1, 18.7, 33.2), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) The point D and the point B' are excluded from the figure enclosed by the line segments LK, KD2, D2D, DG, GH, HB', and B'L connecting the seven points above, or are on the line segments LK, KD2, D2D, and B'L. the line segments LK, D2D, DG, GH, HB', and B'L are straight lines, The coordinates (x, y, z) of the point on the line segment KD2 are (x, 0.01727x 2 -2.7828x+112.643, -0.01727x 2 +1.7828x-12.643), The composition of claim 1.

4. In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point G (12.2, 0.0, 87.8) Point H (0.0, 8.2, 91.8) and Point B' (0.0, 36.6, 63.4) The points are within the area of ​​the shape enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DG, GH, HB' and B'P connecting the above 10 points, or are on the line segments PO, ON', N'N, NM', M'D1, D1D and B'P (excluding points D and B'), the line segments PO, D1D, DG, GH, HB', and B'P are straight lines; The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406) The composition of claim 1.

5. In the refrigerant, the coordinates (x, y, z) are: Point P (22.6, 36.8, 40.6), Point O (25.7, 23.4, 50.9, Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B' (0.0, 36.6, 63.4) The points are within the area of ​​the shape enclosed by the line segments PO, ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB' and B'P connecting the above 11 points, or are on the line segments PO, ON', N'N, NM', M'D1, D1D, EE', E'F and B'P (excluding points D, E and B'), the line segments PO, D1D, DE, FB', and B'P are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4) The composition of claim 1.

6. In the refrigerant, the coordinates (x, y, z) are: Point O (25.7, 23.4, 50.9), Point N' (28.4, 16.7, 54.9), Point N (32.4, 10.0, 57.6), Point M' (39.2, 5.0, 55.8), Point D1 (44.5, 2.2, 53.3), Point D (44.0, 0.0, 56.0), Point E (22.4, 0.0, 77.6) Point E' (11.2, 7.4, 81.4) Point F (0.0, 15.6, 84.4) and Point B (0.0, 23.3, 76.7) The points are within the area enclosed by the line segments ON', N'N, NM', M'D1, D1D, DE, EE', E'F, FB and BO connecting the above ten points, or are on the line segments ON', N'N, NM', M'D1, D1D, EE', E'F and BO (excluding points D, E and B), the line segments D1D, DE, FB, and BO are straight lines, The coordinates (x, y, z) of the points on the line segments ON' and N'N are (x, 0.1204x 2 -8.9935x+175.03, -0.1204x 2 +7.9935x-75.03), The coordinates (x, y, z) of the points on the line segments NM' and M'D1 are (x, 0.01792x 2 -2.019x+56.594 , -0.01792x 2 +1.019x+43.406), The coordinates (x, y, z) of the points on the line segments EE' and E'F are (x, 0.0032x 2 -0.7679x+15.6 , -0.0032x 2 -0.2321x+84.4) The composition of claim 1.

7. The composition according to any one of claims 1 to 6, wherein the refrigerant further contains 0.1% by mass or less of water.

8. A refrigeration method comprising the step of operating a refrigeration cycle using the composition according to any one of claims 1 to 6.

9. A refrigeration device comprising the composition of any one of claims 1 to 6 as a working fluid.

10. A composition comprising a refrigerant, The refrigerant contains HFO-1132(E), R32, and HFO-1234yf in amounts of 28±0.5 mass%, 21.5±0.5 mass%, and 50.5±0.5 mass%, respectively, based on the total amount of these refrigerants; The refrigerant further comprises: at least one additional refrigerant selected from the group consisting of acetylene, HFO-1132a, HFO-1141, HFO-1123, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, and 3,3,3-trifluoropropyne; A composition comprising 99.5 mass% or more of HFO-1132(E), R32, and HFO-1234yf in total, based on the total amount of the refrigerant.

11. The composition of claim 10, wherein the refrigerant further contains less than 0.1% by mass of water.

12. The composition described in any one of claims 1 to 6, wherein the automotive air conditioning equipment is an air conditioning equipment for a hybrid vehicle and / or an electric vehicle.

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