Composition containing refrigerant, use of composition, refrigeration method using composition, and refrigeration unit and refrigerator containing composition

Abstract

To provide a novel low-GWP mixed refrigerant.SOLUTION: The present invention provides a composition comprising a refrigerant, where the refrigerant comprises component X, 1,1-difluoroethane (HFC-152a) and carbon dioxide (CO2), and the component X consists only of trans-1,2-difluoroethylene (HFO-1132(E)) and / or trifluoroethylene (HFO-1123).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to compositions comprising refrigerants, their uses, refrigeration methods employing same, and refrigeration devices and refrigerators including same. [Background technology]

[0002] Trifluoroethylene (HFO-1123) as a heat cycle working fluid that can replace R410A 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 comprising a refrigerant, the refrigerant comprises component X, 1,1-difluoroethane (HFC-152a) and carbon dioxide (CO2); The component X is trans-1,2-difluoroethylene (HFO-1132(E)) and / or trifluoroethylene. A composition consisting solely of fluoroethylene (HFO-1123). Section 2. The refrigerant may further comprise R32, In the above refrigerant, the total amount of components X, R32, HFC-152a, and CO2 is used as the basis. When the mass percentages are x, y, z, and a respectively (where 0 < a ≤ 10.0), for the components X, R32 and HFC - 152a, in a ternary composition diagram where the sum is (100 - a) mass%, the coordinates (x, y, z) are when 0 < a ≤ 4.75, point C (60.0, -a + 40.0, 0.0), point D (57.0, 0.0, -a + 43.0), point O (0.0, 0.0, -a + 100) point B (0.0, -0.0257a 2 + 0.3536a + 50.00, 0.0257a 2 - 1.3536a + 50.00) and point A (-a + 40.8, 59.2, 0.0) within the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting these five points respectively, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A), when 4.75 < a ≤ 10.0, point C (60.0, -a + 40.0, 0.0)), point D (57.0, 0.0, -a + 43.0), point O (0.0, 0.0, -a + 100) point B (0.0, -0.0137a2 + 0.4304a + 49.364, 0.0137a2 - 1.4304a + 50.636) and point A (-a + 40.8, 59.2, 0.0) within the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting these five points respectively, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A), The composition according to item 1. Item 3. In the refrigerant, when the mass percentages of components X, R32, HFC - 152a, and CO2, based on their total sum, are x, y, z, and a respectively (where 0 < a ≤ 10.0), for components X, R32 and HFC - 152a, In a three-component composition diagram in which the sum of HFC-152a and HFC-152b is (100-a) mass%, the coordinates (x, y, z) are: 0 <a≦4.75のとき、 Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a 2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E' (-0.0019a 2 -2.5595a+12.2, -0.0013a 2 -0.373a+34.7, 0.0032a 2 +1.9325a+53.1), Point F (0.0, -0.0102a 2 -3.0461a+47.6, 0.0102a 2 +2.0461a+52.4) Point B (0.0, -0.0257a 2 +0.3536a+50.00, 0.0257a 2 -1.3536a+50.00) and Point A (-a+40.8, 59.2, 0.0) Within the area enclosed by the straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the seven points above, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A). 4.75 <a≦10.0のとき、 Point C (60.0, -a+40.0, 0.0), Point D(57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F (0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883) Point B (0.0, -0.0137a 2 +0.4304a + 49.364, 0.0137a 2 -1.4304a + 50.636) and Point A (-a + 40.8, 59.2, 0.0) within the range of the figure surrounded by the straight lines CD, DE, EE’, EF, FB, BA, and AC connecting these six points respectively, or on the straight lines CD, DE, EF, FB, and BA (excluding points C, F, B, and A). The composition according to item 2. Item 4. In the refrigerant, when the mass percentages of component X, R32, HFC - 152a, and CO2, based on their total sum, are x, y, z, and a (where 0 < a ≤ 10.0) respectively, in the three - component composition diagram where the sum of component X, R32, and HFC - 152a is (100 - a) mass%, the coordinates (x, y, z) are When 0 < a ≤ 4.75, Point C (60.0, -a + 40.0, 0.0)), When 0 < a ≤ 4.75, Point C (60.0, -a + 40.0, 0.0))、 Point D (57.0, 0.0, -a + 43.0)、 Point E (-0.0046a 2 -3.3676a + 50.70, 0.0, 0.0046a 2 +2.3676a + 49.30)、 Point E’ (-0.0019a 2 -2.5595a + 12.2, -0.0013a 2 -0.373a + 34.7, 0.0032a 2 +1.9325a + 53.1)、and Point A’ (-a + 55.6, 44.4, 0.0) within the range of the figure surrounded by the straight lines CD, DE, EE’, and E’A’ connecting these five points respectively, or on the straight lines CD, DE, EE’, and E’A’, and When 4.75 < a < 10.0, Point C (60.0, -a + 40.0, 0.0)、 Point D(57.0, 0.0, -a + 43.0 Point E(0.0018a 2 -3.5313a + 51.333, 0.0, -0.0018a 2 +2.5313a + 48.667), Point F(0.0, -0.0188a 2 -2.9037a + 47.117, 0.0188a 2 +1.9037a + 52.883), Point B’(0.0, -0.0137a2 + 0.4304a + 31.164, 0.0137a2 - 1.4304a + 68.836), and Point A’(-a + 55.6, 44.4, 0.0) within the range of the figure surrounded by the straight lines CD, DE, EF, FB’ and B’A’ connecting these 6 points respectively or on the straight lines CD, DE, EF, and FA’ (excluding points C, F, and point A’), The composition according to item 2. Item 5. A composition containing a refrigerant, wherein the refrigerant contains component X, R32, HFC - 152a and CO2 wherein the component X consists of only HFO - 1132(E) and / or HFO - 1123, in the refrigerant, when the mass percentages of component X, R32 and HFC - 152a, and CO2 based on their total sum are x, y, z, and a (where 0 < a ≤ 10.0) respectively, in the three - component composition diagram where the sum of component X, R32 and HFC - 152a is (100 - a) mass%, the coordinates (x, y, z) are, when 0 < a ≤ 3.3, Point D’(0.0178a 2 -0.0285a + 58.3, -0.0455a 2 +0.4227a + 14.3, 0.0411a 2 -1.6206a + 42.7), Point D(57.0, 0.0, -a + 43.0), Point J (0.3041a2-8.5491a+28.2, 0.0, -0.3041a2+7.5491a+71.8), and Point K (0.254a 2 -6.6564a+19.2, 0.0568a 2 -1.2784a+9.0, -0.3108a 2 +6.9348a+71.8) Within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points above, or on the straight lines D'D, DJ, JK, and KD', 3.3 <a≦3.9のとき、 Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), Point D (57.0, 0.0, -a+43.0), Point J (-5.5a+21.45, 0.0, 4.5a+78.55) Point K (0.0, -9.0a+35.1, 8.0a+64.9) and Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) Within the area enclosed by the straight lines D'D, DJ, JK, KB" and B"D' connecting the above five points, or on the straight lines D'D, DJ, JK and B"D' (excluding points K and B"). 3.9 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128) Point D (57.0, 0.0, -a+43.0), Point O(0.0, 0.0, -a+100) Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) within the range of the figure surrounded by the straight lines D’D, DO, OB”, and B”D’ connecting the four points respectively, or on the straight lines D’D, DO, and B”D’ (excluding the points O and B”), The composition according to item 2. Item 6. A composition containing a refrigerant, wherein the refrigerant contains component X, R32, HFC-152a, and CO2, component X consists only of HFO-1132(E) and / or HFO-1123, and in the refrigerant, when the mass percentages of component X, R32, HFC-152a, and CO2 based on their total sum are x, y, z, and a respectively (where 0 < a ≤ 10.0), in the ternary composition diagram where the sum of component X, R32, and HFC-152a is (100 - a) mass%, the coordinates (x, y, z) are when 0 < a ≤ 3.3, point D’ (0.0178a 2 - 0.0285a + 58.3, - 0.0455a 2 + 0.4227a + 14.3, 0.0411a 2 - 1.6206a + 42.7), when 3.3 < a ≤ 3.9, point D’ (58.4, 0.1667a + 17.95, - 1.1667a + 23.65), when 3.9 < a ≤ 7.7, point D’ (- 0.0047a 2 + 0.0815a + 58.153, 0.0004a 2 + 0.2245a + 17.719, 0.0043a 2 - 1.306a + 24.128), when 0 < a ≤ 7.7, point D(57.0, 0.0, - a + 43.0) point L (- 2.5455a + 25.876, 0.0, 1.5455a + 74.124) and point M (0.0027a2 - 2.2157a + 16.9, 0.0025a2 - 0.2916a + 8.5, - 0.0052a2 + 1.5073a + 74.6) Within the area enclosed by the straight lines D', D, DL, LM, and MD' connecting the four points above, or within the area enclosed by the straight lines D' on D, DL, LM, and MD' 7.7 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), Point D(38.0, 0.0, -a+62.0) Point L (-2.4345a+25.038, 0.0, 1.4345a+74.962) and Point M (0.0, -0.0198a 2 -2.1285a+23.961, 0.0198a 2 +1.1285a+76.039) Within the range of the figure surrounded by straight lines D'D, DL, LM, and MD' respectively connecting the four points above, or on the straight lines D'D, DL, LM, and MD'. Item 3. The composition according to item 2. Section 7. R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R 422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448 The composition according to any one of items 1 to 6, which is used as an alternative refrigerant to R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R474A, R479A, R502, R507, R513A, R1234yf or R1234ze. Section 8. a utilization side heat transport cycle for circulating a utilization side refrigerant; a heat source side heat transfer cycle for circulating a heat source side refrigerant; a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat source-side refrigerant, A refrigeration device, wherein the heat source side refrigerant is a composition according to any one of items 1 to 6. Section 9. Item 7. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of Items 1 to 6. Section 10. Item 7. A refrigerator comprising the composition according to any one of items 1 to 6 as a working fluid. Section 11. Use of HFO-1123, R32, R152a and CO2 to inhibit the disproportionation reaction of HFO-1132(E). 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 ternary diagram showing the composition of refrigerants of the present disclosure. [Diagram 3] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 4] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Diagram 5] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 6] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 7] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 8] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 9] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 10] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 11] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 12] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 13] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 14] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 15] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. [Figure 16] FIG. 2 is a ternary diagram showing the composition of refrigerants of the present disclosure. 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 having a refrigerant number (ASHRAE number) beginning with R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and further In addition, even if a refrigerant number has not yet been assigned, it includes refrigerants that have the same refrigerant properties as those refrigerants. In terms of the chemical structure, refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons. Contains 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 refrigerator used in automobiles such as gasoline vehicles, hybrid vehicles, electric vehicles, hydrogen vehicles, etc. The term vehicle air conditioner refers to a refrigerator 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 adiabatically expanded by passing through an expansion valve, and then supplied to the evaporator again as a liquid refrigerant.

[0015] Unless otherwise specified, the pressures described in this specification are in absolute units.

[0016] 1. Refrigerant The refrigerant of the present disclosure contains component X, HFC-152a, and CO2, and the component X consists of only trans-1,2-difluoroethylene (HFO-1132(E)) and / or trifluoroethylene (HFO-1123). The refrigerant of the present disclosure may further contain difluoromethane (R32). The refrigerant of the present disclosure is a low-GWP mixed refrigerant.

[0017] In the refrigerant of the present disclosure, when the mass percentages of component X, R32, HFC-152a, and CO2 based on their total sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in a ternary composition diagram where the total sum of component X, R32, and HFC-152a is (100 - a) mass%, when the coordinates (x, y, z)

[0018] meet the following requirements, no disproportionation reaction occurs at 5 MPa and 150 °C, and the GWP is less than 400. <Requirements> When 0 < a ≤ 4.75, inside the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting the five points of point C (60.0, -a + 40.0, 0.0), <Requirements> point D (57.0, 0.0, -a + 43.0), point O (0.0, 0.0, -a + 100), point B (0.0, -0.0257a + 0.3536a + 50.00, 0.0257a - 1.3536a + 50.00), and 2 point A (-a + 40.8, 59.2, 0.0) 2 (excluding points C, O, B, and A), or on the straight lines CD, DO, and BA, When 4.75 < a ≤ 10.0, inside the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting the five points of point C (60.0, -a + 40.0, 0.0), point D (57.0, 0.0, -a + 43.0), Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point O (0.0, 0.0, -a+100) Point B (0.0, -0.0137a2+0.4304a+49.364, 0.0137a2-1.4304a+50.636) and Point A (-a+40.8, 59.2, 0.0) The point A is within the area bounded by the straight lines CD, DO, OB, BA, and AC connecting the five points above, or is on the straight lines CD, DO, and BA (excluding points C, O, B, and A).

[0019] In the refrigerant disclosed herein, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 400 or less, and the refrigeration capacity (Cap) ratio to R410A is 70% or more.

[0020] <Requirements> 0 <a≦4.75のとき、 Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a 2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E' (-0.0019a 2 -2.5595a+12.2, -0.0013a 2 -0.373a+34.7, 0.0032a 2 +1.9325a+53.1), Point F (0.0, -0.0102a 2 -3.0461a+47.6, 0.0102a 2 +2.0461a+52.4) Point B (0.0, -0.0257a 2 +0.3536a+50.00, 0.0257a 2 -1.3536a+50.00) and Point A (-a+40.8, 59.2, 0.0) Within the area enclosed by the straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the seven points above, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A). 4.75 <a≦10.0のとき、 Point C (60.0, -a+40.0, 0.0), Point D(57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F (0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883) Point B (0.0, -0.0137a 2 +0.4304a+49.364, 0.0137a 2 -1.4304a+50.636) and Point A (-a+40.8, 59.2, 0.0) Within the area of ​​the shape enclosed by the straight lines CD, DE, EE', EF, FB, BA, and AC connecting the six points above, or It lies on the straight lines CD, DE, EF, FB and BA (excluding points C, F, B and A).

[0021] In the refrigerant disclosed herein, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity (Cap) ratio to R410A is 70% or more.

[0022] <Requirements> 0 <a≦4.75のとき、 Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E' (-0.0019a 2 -2.5595a+12.2, -0.0013a 2 -0.373a+34.7, 0.0032a 2 +1.9325a+53.1), and Point A' (-a+55.6, 44.4, 0.0) The object is located within the area surrounded by the straight lines CD, DE, EE', and E'A' connecting the five points above, or on said straight lines CD, DE, EE', and E'A', 4.75 <a<10.0のとき、 Point C (60.0, -a+40.0, 0.0), Point D(57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F(0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883), Point B'(0.0, -0.0137a2+0.4304a+31.164, 0.0137a2-1.4304a+68.836), and Point A' (-a+55.6, 44.4, 0.0) The point A is within the area surrounded by the straight lines CD, DE, EF, FB', and B'A' connecting the six points above, or on the straight lines CD, DE, EF, and FA' (excluding points C, F, and A').

[0023] In the refrigerant disclosed herein, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less.

[0024] <Requirements> 0 <a≦3.3のとき、 Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), Point D (57.0, 0.0, -a+43.0), Point J (0.3041a2-8.5491a+28.2, 0.0, -0.3041a2+7.5491a+71.8), and Point K (0.254a 2 -6.6564a+19.2, 0.0568a 2 -1.2784a+9.0, -0.3108a 2 +6.9348a+71.8) Within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points above, or on the straight lines D'D, DJ, JK, and KD', 3.3 <a≦3.9のとき、 Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), Point D (57.0, 0.0, -a+43.0), Point J (-5.5a+21.45, 0.0, 4.5a+78.55) Point K (0.0, -9.0a+35.1, 8.0a+64.9) and Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) Within the area enclosed by the straight lines D'D, DJ, JK, KB" and B"D' connecting the above five points, or on the straight lines D'D, DJ, JK and B"D' (excluding points K and B"). 3.9 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2-1.306a+24.128) Point D (57.0, 0.0, -a+43.0), Point O(0.0, 0.0, -a+100) Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) The area is within the shape enclosed by straight lines D'D, DO, OB'', and B''D' connecting these four points, or is on said straight lines D'D, DO, and B''D' (excluding point O and point B'').

[0025] The refrigerant of the present disclosure may comprise component X and HFC-152a. The refrigerant may further comprise R32.

[0026] In the above embodiment, the refrigerant of the present disclosure is a mixture of components X, R32 and HFC-152a, and CO2. The mass percentages based on the total of these are x, y, z, and a (where 0 <a≦10.0)とす In this case, in a three-component composition diagram in which the sum of component X, R32 and HFC-152a is (100-a) mass%, When the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R404A is 70% or more.

[0027] <Requirements> 0 <a≦3.3のとき、 Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), 3.3 <a≦3.9のとき、 Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), 3.9 <a≦7.7のとき、 Point D' (-0.0047a2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), 0 <a≦7.7のとき、 Point D(57.0, 0.0, -a+43.0) Point L (-2.5455a+25.876, 0.0, 1.5455a+74.124) and Point M (0.0027a2-2.2157a+16.9, 0.0025a2-0.2916a+8.5, -0.0052a2+1.5073a+74.6) The distance is within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' respectively connecting the four points above, or is on the straight lines D'D, DL, LM, and MD'. 7.7 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), Point D(38.0, 0.0, -a+62.0) Point L (-2.4345a+25.038, 0.0, 1.4345a+74.962) and Point M (0.0, -0.0198a 2 -2.1285a+23.961, 0.0198a 2 +1.1285a+76.039) It is within the range of the figure surrounded by straight lines D'D, DL, LM, and MD' respectively connecting these four points, or is on said straight lines D'D, DL, LM, and MD'.

[0028] The refrigerant of the present disclosure may contain 10% by mass or more of HFO-1132(E) based on the total amount of the refrigerant. It may contain 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more.

[0029] The refrigerant of the present disclosure may contain 10 mass% or more of R32 based on the entire refrigerant, and 20 mass% or more of R32 based on the entire refrigerant. % or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more.

[0030] The refrigerant of the present disclosure may contain 10 mass % or more of R152a based on the entire refrigerant, and 20 mass % or less of R152a based on the entire refrigerant. It may contain 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0031] The refrigerant of the present disclosure may contain component X in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, based on the entire refrigerant.

[0032] The refrigerant of the present disclosure may contain an additional refrigerant in addition to the component X, R32, HFC-152a, and CO2, within the range that does not impair the above-mentioned properties and effects. In the present disclosure, the refrigerant contains the sum of component X, R32 and HFC-152a, and CO2 in the entire refrigerant. The refrigerant of the present disclosure preferably contains 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. In this case, the refrigerant of the present disclosure may consist essentially of components X, R32, HFC-152a, CO2, and unavoidable impurities. The refrigerant of the present disclosure may consist essentially of components X, R32, HFC-152a, and CO2. stomach.

[0033] 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.

[0034] Additional refrigerants include methylamine, acetylene, 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.

[0035] 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 contains 1 mass % or more of refrigerating machine oil relative to the entire refrigerant composition. It is preferably 0.1 mass % or less, and more preferably 0.1 mass % or less.

[0036] 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 total amount of the refrigerant. This stabilizes the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant, and also makes the unsaturated fluorocarbon compound less susceptible to oxidation, thereby improving the stability of the refrigerant composition.

[0037] The compositions of the present disclosure include compositions comprising a refrigerant, the refrigerant being component X, R32 and R1234yf. Also included are compositions containing 0.1% or less water.

[0038] 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.

[0039] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0040] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0041] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Polyfluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are particularly preferred.

[0042] As tracers, the following compounds are preferred: FC-14 (Tetrafluoromethane, CF4) HCC-40 (chloromethane, CH3Cl) HFC-23 (Trifluoromethane, CHF3) HFC-41 (fluoromethane, CH3Cl) HFC-125 (Pentafluoroethane, CF3CHF2) HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F) HFC-134 (1,1,2,2-Tetrafluoroethane, CHF2CHF2) HFC-143a (1,1,1-trifluoroethane, CF3CH3) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-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)

[0043] 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).

[0044] 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.

[0045] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0046] 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.

[0047] 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.

[0048] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0049] The stabilizers include, for example, nitro compounds, ethers, and amines.

[0050] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0051] An example of the ethers is 1,4-dioxane.

[0052] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine, diphenylamine, and the like.

[0053] Other examples include butylhydroxyxylene and benzotriazole.

[0054] The content of the stabilizer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total amount of the refrigerant. % or less, and more preferably 2 mass % or less.

[0055] 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.

[0056] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0057] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, and hydroquinone. Examples of such benzenediamines include dimethyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] The refrigerating machine oil is not particularly limited and can be appropriately selected from among commonly used refrigerating machine oils. In that case, it is necessary to take into consideration the miscibility and compatibility with the mixture. A refrigerating machine oil having superior properties in terms of improving the stability of the mixture can be appropriately selected.

[0062] Examples of base oils for refrigeration oils include polyalkylene glycols (PAGs), polyol ethers, etc. At least one selected from the group consisting of polyvinyl ether (POE) and polyvinyl ether (PVE) is preferred.

[0063] 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.

[0064] From the viewpoint of lubrication, a refrigerating machine oil having a kinetic viscosity of 5 cSt or more at 40° C. is preferable. Also, a refrigerating machine oil having a kinetic viscosity of 400 cSt or less at 40° C. is preferable from the viewpoint of lubrication.

[0065] 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.

[0066] 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.

[0067] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0068] 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.

[0069] The refrigerants, refrigerant compositions, and refrigerating machine oil-containing working fluids disclosed herein are R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R440A, R441B, R442C, R442D, R443A, R444A, R445A, R446A, R447A, R447B, R448A, R449A, R450A, R451A, R452A, R453A, R454A, R455A, R456A, R457A, R458A, R459A, R460A, R461A, R462A, R463A, R464A, R465A, R466A, R467A, R468A, R469A, R470A, R471A, R472A, R473A, R474A, R475A, R476A, R477A, ​​R478A, R479A, R480A, R481A, R482A, R483A, R484A, R485A, R486A, R487A, R488A, R489A, R490A, R491A, R492A, R493A, R494A, R495A, R496A, R497A, R498A It can be used as an alternative refrigerant to R34A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R474A, R479A, R502, R507, R513A, R1234yf or R1234ze.

[0070] 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.

[0071] Specifically, a method of operating a refrigerator of the present disclosure includes circulating a refrigerant of the present disclosure in the refrigerator.

[0072] 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.

[0073] In the method for suppressing the disproportionation reaction disclosed herein, the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring, particularly when the refrigerant pressure is 5.0 MPa and the refrigerant temperature is 150° C., is achieved. Obtained.

[0074] 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.

[0075] 7. Use for inhibiting disproportionation reactions The disclosed use is the use of HFO-1123, R32, R152a and CO2 to inhibit the disproportionation reaction of HFO-1132(E), wherein the inhibition of the disproportionation reaction is This is done by mixing HFO-1132(E) to obtain the refrigerant mixing ratio of the present disclosure.

[0076] 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 5.0 MPa and the refrigerant temperature is 150°C.

[0077] 8. Refrigeration equipment The refrigeration device of the present disclosure comprises: a utilization side heat transport cycle for circulating a utilization side refrigerant; a heat source side heat transfer cycle for circulating a heat source side refrigerant; a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat source-side refrigerant, The heat source side refrigerant is the composition described in 1. above.

[0078] 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

[0079] The present disclosure will be described in more detail below by way of examples, although the present disclosure is not limited to these examples.

[0080] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, R152a, and CO2 in the mass percentages shown in Table 1, based on the total sum of these.

[0081] 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 the test vessel, heated to 150°C, and then the Pt wire in the vessel was By applying a voltage to melt the refrigerant composition, 30 J of energy was given to the refrigerant composition. The presence or absence of this was judged by a sudden increase in pressure and temperature inside the device. Test conditions Test container: 38cc SUS container Test temperature: 150℃ Pressure: 5 MPa Judgment criteria "Non-explosive": The temperature or pressure after Pt filament melting is less than twice as high, and a rapid disproportionation reaction does not occur. not present. "Explosion": The temperature or pressure after Pt filament melting reached more than double the normal level, causing a sudden disproportionation reaction. .

[0082]

Table 1

[0083]

Table 2

[0084]

Table 3

[0085] From the results of Tables 1 to 3, it can be seen that the refrigerant of the present disclosure does not disproportionate within the region shown in the triangular diagram shown in FIGS. 1 to 19.

[0086] Taking the GWP of HFO-1132(E) as 1, the GWPs of R32 and HFO-1234yf were evaluated based on the values in the 4th Report of the IPCC (Intergovernmental Panel on Climate Change) for the GWP of the mixed refrigerant. Also for the COP, refrigerating capacity, discharge temperature and boiling point of the mixed refrigerant, the theoretical calculation of the refrigeration cycle of the mixed refrigerant was carried out using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions and obtained. The physical property data of HFO-1132(E) was obtained based on measured values. <When comparing with R410A in terms of performance> Evaporation temperature: 5°C Condensation temperature: 45°C Superheat temperature: 5 K Subcooling temperature: 5 K Compressor efficiency: 70% <When comparing with HFO-1234yf in terms of performance> Evaporation temperature: -30°C Condensation temperature: 30°C Superheat temperature: 5 K Subcooling temperature: 5K Compressor efficiency: 70% <When comparing with R404A in terms of performance> Evaporation temperature: -40°C Condensation temperature: 40°C Superheat temperature: 20K Subcooling temperature: 0K Compressor efficiency: 70%

[0087] In the following table, "COP ratio" and "refrigerating capacity ratio" indicate the ratio (%) with respect to each specified refrigerant. In the table, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa). Table In the table, "power consumption (%)" indicates the electrical energy used for the electric vehicle to run, and is expressed as the ratio to the power consumption when the refrigerant is HFO-1234yf. In the table, "heating power consumption (%)" indicates the electrical energy used for the electric vehicle to operate the heating, and is expressed as the ratio to the power consumption when the refrigerant is HFO-1234yf. In the following table, "driving range (with)" indicates the relative ratio (%) of the driving range when driving with heating with respect to the case where the driving range without heating (heating power consumption is 0) is set to 100% in an electric vehicle equipped with a secondary battery with a certain electric capacity.

[0088] In the following table, "driving range (with)" indicates the relative ratio (%) of the driving range when driving with heating with respect to the case where the driving range without heating (heating power consumption is 0) is set to 100% in an electric vehicle equipped with a secondary battery with a certain electric capacity. It is represented as such.

[0089] For the heating method, an electric heater method was used for heating with a refrigerant whose boiling point exceeds -40°C, and a heat pump method was used for heating with a refrigerant whose boiling point is -40°C or lower.

[0090] The power consumption during heating was obtained by the following formula. Note that the heating COP means "heating efficiency". It means. Power consumption during heating = Heating capacity / Heating COP

[0091] 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).

[0092] On the other hand, in the case of heat pumps, Refprop 10.0 (manufactured by 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.

[0093] The coefficient of performance (COP) was calculated using the following formula. COP = (refrigeration capacity or heating capacity) / power consumption

[0094] [Table 4]

[0095] [Table 5]

[0096] [Table 6]

[0097] [Table 7]

[0098] [Table 8]

[0099] [Table 9]

[0100] [Table 10]

[0101] The coordinates of each point were determined based on the least squares method as follows.

[0102] [Table 11]

[0103] [Table 12]

[0104] [Table 13]

[0105] [Table 14]

[0106] [Table 15]

[0107] [Table 16]

[0108] From the above results, it is clear that the refrigerants disclosed in this disclosure, HFO-1132(E), R32, HFC-152a, and CO2 When the mass percentages based on the sum of these are x, y, z, and a (where 0 < a ≤ 10.0), in a ternary composition diagram where the sum of HFO - 1132(E), R32, and HFC - 152a is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that disproportionation reaction does not occur at 5 MPa and 150 °C, and the GWP is 400 or less. <Requirement> When 0 < a ≤ 4.75, point C (60.0, -a + 40.0, 0.0), point D (57.0, 0.0, -a + 43.0), point O (0.0, 0.0, -a + 100) point B (0.0, -0.0257a 2 + 0.3536a + 50.00, 0.0257a 2 - 1.3536a + 50.00) and point A (-a + 40.8, 59.2, 0.0) within the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting these five points respectively, or on the straight lines CD , DO, and BA (excluding points C, O, B, and A), When 4.75 < a ≤ 10.0, point C (60.0, -a + 40.0, 0.0)), point D (57.0, 0.0, -a + 43.0), point O (0.0, 0.0, -a + 100) point B (0.0, -0.0137a2 + 0.4304a + 49.364, 0.0137a2 - 1.4304a + 50.636) and point A (-a + 40.8, 59.2, 0.0) within the range of the figure surrounded by the straight lines CD, DO, OB, BA, and AC connecting these five points respectively, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A).

[0109] In the refrigerant of the present disclosure, when the coordinates (x, y, z) satisfy the following requirements, it is found that disproportionation reaction does not occur at 5 MPa and 150 °C, the GWP is 400 or less, and the refrigeration capacity (Cap) ratio to R410A is 70% or more.

[0110] <Requirements> In the refrigerant, when the mass percentages of component X, R32, HFC-152a, and CO2, based on their total sum, are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in the ternary composition diagram where the total sum of component X, R32, and HFC-152a is (100 - a) mass%, the coordinates (x, y, z) are when 0 < a ≤ 4.75, point C (60.0, -a + 40.0, 0.0)), point D (57.0, 0.0, -a + 43.0), point E (-0.0046a - 3.3676a + 50.70, 0.0, 0.0046a + 2.3676a + 49.30), 2 point E’ (-0.0019a 2 - 2.5595a + 12.2, -0.0013a - 0.373a + 34.7, 0.0032a 2 + 1.9325a + 53.1), 2 point F (0.0, -0.0102a 2 - 3.0461a + 47.6, 0.0102a + 2.0461a + 52.4) 2 point B (0.0, -0.0257a 2 + 0.3536a + 50.00, 0.0257a + 1.3536a + 50.00) and 2 point A (-a + 40.8, 59.2, 0.0) 2 within the range of the figure surrounded by the straight lines CD, DE, EE’, E’F, FB, BA, and AC connecting these seven points respectively, or on the straight lines CD, DE, EE’, E’F, and BA (excluding point C, point F, point B, and point A) ​​4.75 <a≦10.0のとき、 Point C (60.0, -a+40.0, 0.0), Point D(57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F (0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883) Point B (0.0, -0.0137a 2 +0.4304a+49.364, 0.0137a 2 -1.4304a+50.636) and Point A (-a+40.8, 59.2, 0.0) Within the area of ​​the shape enclosed by the straight lines CD, DE, EE', EF, FB, BA, and AC connecting the six points above, or On the straight lines CD, DE, EF, FB and BA (excluding points C, F, B and A) .

[0111] In the refrigerant disclosed herein, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity (Cap) ratio to R410A is 70% or more.

[0112] <Requirements> 0 <a≦4.75のとき、 Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a 2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E' (-0.0019a 2 -2.5595a+12.2, -0.0013a 2-0.373a+34.7, 0.0032a 2 +1.9325a+53.1), and Point A' (-a+55.6, 44.4, 0.0) The object is located within the area surrounded by the straight lines CD, DE, EE', and E'A' connecting the five points above, or on said straight lines CD, DE, EE', and E'A', 4.75 <a<10.0のとき、 Point C (60.0, -a+40.0, 0.0), Point D(57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F(0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883), Point B'(0.0, -0.0137a2+0.4304a+31.164, 0.0137a2-1.4304a+68.836), and Point A' (-a+55.6, 44.4, 0.0) It is within the area surrounded by the straight lines CD, DE, EF, FB', and B'A' connecting the six points above, or on the straight lines CD, DE, EF, and FA' (however, points C, F, and A' are excluded).

[0113] The above test results show that in the refrigerant disclosed herein, similar effects can be obtained by using HFO-1132(E) and / or HFO-1123 instead of HFO-1132(E).

[0114] [Table 17]

[0115] [Table 18]

[0116] [Table 19]

[0117] [Table 20]

[0118] [Table 21]

[0119] [Table 22]

[0120] [Table 23]

[0121] [Table 24]

[0122] [Table 25]

[0123] [Table 26]

[0124] [Table 27]

[0125] The coordinates of each point were determined based on the least squares method as follows.

[0126] [Table 28]

[0127] [Table 29]

[0128] [Table 30]

[0129] From the above results, in the refrigerant disclosed in the present disclosure, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 5 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less. It turns out to be below.

[0130] <Requirements> 0 <a≦3.3のとき、 Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), Point D (57.0, 0.0, -a+43.0), Point J (0.3041a2-8.5491a+28.2, 0.0, -0.3041a2+7.5491a+71.8), and Point K (0.254a 2 -6.6564a+19.2, 0.0568a 2 -1.2784a+9.0, -0.3108a 2 +6.9348a+71.8) Within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points above, or on the straight lines D'D, DJ, JK, and KD', 3.3 <a≦3.9のとき、 Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), Point D (57.0, 0.0, -a+43.0), Point J (-5.5a+21.45, 0.0, 4.5a+78.55) Point K (0.0, -9.0a+35.1, 8.0a+64.9) and Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) The area is within the shape enclosed by the straight lines D'D, DJ, JK, KB" and B"D' connecting the above five points, or is on the straight lines D'D, DJ, JK and B"D' (excluding points K and B"). 3.9 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128) Point D (57.0, 0.0, -a+43.0), Point O(0.0, 0.0, -a+100) Point B” (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) The area is within the shape enclosed by straight lines D'D, DO, OB'', and B''D' connecting these four points, or is on said straight lines D'D, DO, and B''D' (excluding point O and point B'').

[0131] The above test results show that in the refrigerant disclosed herein, similar effects can be obtained by using HFO-1132(E) and / or HFO-1123 instead of HFO-1132(E).

[0132] [Table 31]

[0133] [Table 32]

[0134] [Table 33]

[0135] [Table 34]

[0136] [Table 35]

[0137] [Table 36]

[0138] [Table 37]

[0139] The coordinates of each point were determined based on the least squares method as follows.

[0140] [Table 38]

[0141] In the above embodiment, the refrigerants of the present disclosure are HFO-1132(E), R32 and HFC-152a, as well as CO2. The mass percentages based on the sum of these are x, y, z, and a (where 0 <a≦10.0 ), the total of HFO-1132(E), R32 and HFC-152a is (100-a)% by mass. In the figure, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 5 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R404A is 70% or more. It turns out that this is what will happen.

[0142] <Requirements> 0 <a≦3.3のとき、 Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), 3.3 <a≦3.9のとき、 Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), 3.9 <a≦7.7のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), 0 <a≦7.7のとき、 Point D(57.0, 0.0, -a+43.0) Point L (-2.5455a+25.876, 0.0, 1.5455a+74.124) and Point M (0.0027a2-2.2157a+16.9, 0.0025a2-0.2916a+8.5, -0.0052a2+1.5073a+74.6) The distance is within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' respectively connecting the four points above, or is on the straight lines D'D, DL, LM, and MD'. 7.7 <a≦10.0のとき、 Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), Point D(38.0, 0.0, -a+62.0) Point L (-2.4345a+25.038, 0.0, 1.4345a+74.962) and Point M (0.0, -0.0198a 2 -2.1285a+23.961, 0.0198a 2+1.1285a+76.039) It is within the range of the figure surrounded by straight lines D'D, DL, LM, and MD' respectively connecting these four points, or is on said straight lines D'D, DL, LM, and MD'.

[0143] The above test results show that in the refrigerant disclosed herein, similar effects can be obtained by using HFO-1132(E) and / or HFO-1123 instead of HFO-1132(E).

Claims

1. A composition comprising a refrigerant, The refrigerant is a mixture of component X, 1,1-difluoroethane (HFC-152a) and carbon dioxide (CO 2 ), The component X is trans-1,2-difluoroethylene (HFO-1132(E)) and / or trifluoroethylene. A composition consisting solely of fluoroethylene (HFO-1123).

2. The refrigerant may further comprise R32, In the refrigerant, component X, R32 and HFC-152a, and CO 2 The sum of these is the standard When the mass percentages of components X, R32 are x, y, z, and a (where 0<a≦10.0), In a three-component composition diagram in which the sum of HFC-152a and HFC-152b is (100-a) mass%, the coordinates (x, y, z) are: When 0<a≦4.75, Point C (60.0, -a+40.0, 0.0), Point D (57.0, 0.0, -a+43.0), Point O (0.0, 0.0, -a+100) Point B (0.0, -0.0257a 2 +0.3536a+50.00, 0.0257a 2 -1.3536a+50.00) and Point A (-a+40.8, 59.2, 0.0) Within the area bounded by the straight lines CD, DO, OB, BA, and AC connecting the five points above, or on said straight lines CD, DO, and BA (excluding points C, O, B, and A), When 4.75<a≦10.0, Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point O (0.0, 0.0, -a+100) Point B (0.0, -0.0137a2+0.4304a+49.364, 0.0137a2-1.4304a+50.636) and Point A (-a+40.8, 59.2, 0.0) Within the area bounded by the lines CD, DO, OB, BA, and AC connecting the above five points, or on the lines CD, DO, and BA (excluding points C, O, B, and A), The composition of claim 1.

3. In the refrigerant, component X, R32 and HFC-152a, and CO 2 The sum of these is the standard When the mass percentages of components X, R32 are x, y, z, and a (where 0<a≦10.0), In a three-component composition diagram in which the sum of HFC-152a and HFC-152b is (100-a) mass%, the coordinates (x, y, z) are: When 0<a≦4.75, Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a 2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E’ (-0.0019a 2 -2.5595a + 12.2, -0.0013a 2 -0.373a + 34.7, 0.0032a 2 +1.9325a + 53.1), Point F (0.0, -0.0102a 2 -3.0461a+47.6, 0.0102a 2 +2.0461a+52.4) Point B (0.0, -0.0257a 2 +0.3536a+50.00, 0.0257a 2 -1.3536a+50.00) and Point A (-a+40.8, 59.2, 0.0) Within the area enclosed by the straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the seven points above, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A). When 4.75<a≦10.0, Point C (60.0, -a+40.0, 0.0), Point D (57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F (0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883) Point B (0.0, -0.0137a 2 +0.4304a+49.364, 0.0137a 2 -1.4304a+50.636) and Point A (-a+40.8, 59.2, 0.0) Within the area enclosed by the lines CD, DE, EE', EF, FB, BA, and AC connecting the six points above, or On the straight lines CD, DE, EF, FB and BA (excluding points C, F, B and A) The composition of claim 2.

4. In the refrigerant, component X, R32 and HFC-152a, and CO 2 The sum of these is the standard When the mass percentages of components X, R32 are x, y, z, and a (where 0<a≦10.0), In a three-component composition diagram in which the sum of HFC-152a and HFC-152b is (100-a) mass%, the coordinates (x, y, z) are: When 0<a≦4.75, Point C (60.0, -a+40.0, 0.0)), Point D (57.0, 0.0, -a+43.0), Point E (-0.0046a 2 -3.3676a+50.70, 0.0, 0.0046a 2 +2.3676a+49.30), Point E' (-0.0019a 2 -2.5595a+12.2, -0.0013a 2 -0.373a+34.7, 0.0032a 2 +1.9325a+53.1), and Point A' (-a+55.6, 44.4, 0.0) The object is located within the area surrounded by the straight lines CD, DE, EE', and E'A' connecting the five points above, or on said straight lines CD, DE, EE', and E'A', When 4.75<a<10.0, Point C (60.0, -a+40.0, 0.0), Point D (57.0, 0.0, -a+43.0 Point E (0.0018a 2 -3.5313a+51.333, 0.0, -0.0018a 2 +2.5313a+48.667), Point F(0.0, -0.0188a 2 -2.9037a+47.117, 0.0188a 2 +1.9037a+52.883), Point B'(0.0, -0.0137a2+0.4304a+31.164, 0.0137a2-1.4304a+68.836), and Point A' (-a+55.6, 44.4, 0.0) Within the area enclosed by the straight lines CD, DE, EF, FB', and B'A' connecting the six points above, or on the straight lines CD, DE, EF, and FA' (excluding points C, F, and A'), The composition of claim 2.

5. A composition comprising a refrigerant, The refrigerant is selected from the group consisting of component X, R32, HFC-152a and CO 2 Includes said component X consists exclusively of HFO-1132(E) and / or HFO-1123, In the refrigerant, component X, R32 and HFC-152a, and CO 2 The sum of these is the standard When the mass percentages of components X, R32 are x, y, z, and a (where 0<a≦10.0), In a three-component composition diagram in which the sum of HFC-152a and HFC-152b is (100-a) mass%, the coordinates (x, y, z) are: When 0<a≦3.3, Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), Point D (57.0, 0.0, -a+43.0), Point J (0.3041a2-8.5491a+28.2, 0.0, -0.3041a2+7.5491a+71.8), and Point K (0.254a 2 -6.6564a+19.2, 0.0568a 2 -1.2784a+9.0, -0.3108a 2 +6.9348a+71.8) Within the range of the figure enclosed by straight lines D'D, DJ, JK, and KD' respectively connecting the four points above, or on said straight lines D'D, DJ, JK, and KD', When 3.3<a≦3.9, Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), Point D (57.0, 0.0, -a+43.0), Point J (-5.5a+21.45, 0.0, 4.5a+78.55) Point K (0.0, -9.0a+35.1, 8.0a+64.9) and Point B" (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) Within the area or in front of the figure enclosed by the straight lines D'D, DJ, JK, KB" and B"D' connecting the five points It is on the lines D'D, DJ, JK and B"D' (excluding points K and B"). When 3.9<a≦10.0, Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128) Point D (57.0, 0.0, -a+43.0), Point O (0.0, 0.0, -a+100) Point B" (0.0, 0.0018a 2 +0.2025a+4.6993, -0.018a 2 -1.2025a+95.301) Within the area enclosed by the straight lines D'D, DO, OB", and B"D' connecting the four points above, or on the straight lines D'D, DO, and B"D' (excluding points O and B"). The composition of claim 2.

6. A composition comprising a refrigerant, The refrigerant is selected from the group consisting of component X, R32, HFC-152a and CO 2 Including, The component X consists of only HFO-1132(E) and / or HFO-1123, and the refrigerant contains component X, R32, HFC-152a, and CO 2 Let x, y, z, and a (where 0 < a ≦ 10.0) be the mass percentages based on the sum of these components, respectively. In a 3-component composition diagram in which the sum of component X, R32, and HFC-152a is (100 - a) mass%, the coordinates (x, y, z) are as follows: When 0<a≦3.3, Point D' (0.0178a 2 -0.0285a+58.3, -0.0455a 2 +0.4227a+14.3, 0.0411a 2 -1.6206a+42.7), When 3.3<a≦3.9, Point D' (58.4, 0.1667a+17.95, -1.1667a+23.65), When 3.9<a≦7.7, Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), When 0<a≦7.7, Point D(57.0, 0.0, -a+43.0) Point L (-2.5455a+25.876, 0.0, 1.5455a+74.124) and Point M (0.0027a2-2.2157a+16.9, 0.0025a2-0.2916a+8.5, -0.0052a2+1.5073a+74.6) The distance is within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' respectively connecting the four points above, or is on the straight lines D'D, DL, LM, and MD'. When 7.7<a≦10.0, Point D' (-0.0047a 2 +0.0815a+58.153, 0.0004a 2 +0.2245a+17.719, 0.0043a 2 -1.306a+24.128), Point D(38.0, 0.0, -a+62.0) Point L (-2.4345a+25.038, 0.0, 1.4345a+74.962) and Point M (0.0, -0.0198a 2 -2.1285a+23.961, 0.0198a 2 +1.1285a+76.039) Within the range of the figure surrounded by straight lines D'D, DL, LM, and MD' respectively connecting the four points above, or on the straight lines D'D, DL, LM, and MD'. The composition of claim 2.

7. R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R 422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A 7. The composition according to claim 1, which is used as an alternative refrigerant to R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R474A, R479A, R502, R507, R513A, R1234yf or R1234ze.

8. a utilization side heat transport cycle for circulating a utilization side refrigerant; a heat source side heat transfer cycle for circulating a heat source side refrigerant; a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat source-side refrigerant, A refrigeration device, wherein the heat source side refrigerant is the composition according to any one of claims 1 to 6.

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

10. A refrigerator comprising the composition according to any one of claims 1 to 6 as a working fluid.

11. HFO-1123, R32, R152a and CO 2 Use of HFO-1132(E) to inhibit the disproportionation reaction of HFO-1132(E).

Images