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

Abstract

To solve the above-described problems, the present application provides a composition containing a refrigerant, the refrigerant containing: 2,3,3,3-tetrafluoro-1-propene (R1234yf) and / or 1,3,3,3-tetrafluoropropene (R1234ze); trans-1,2-difluoroethylene (HFO-1132(E)); and CO2, the content ratio of HFO-1132(E) being 30% by mass or less and the content ratio of CO2 being 10% by mass or less, based on the entire refrigerant.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition containing a refrigerant, use thereof, a refrigerator having the composition, and a method for operating the refrigerator. BACKGROUND

[0002] As a refrigerant, R404A, R134a, etc. are now used.

[0003] However, R404A has a global warming potential (GWP) of 3920, and R134a has a GWP of 1430, and as concerns about global warming are increasing, R32 having a GWP of 675 is being used more and more.

[0004] Various low-GWP mixed refrigerants capable of replacing R404A or R134a have also been proposed (Patent Literature 1).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: International Publication No. 2015 / 186557 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] The present application relates to a composition containing a refrigerant, use thereof, a refrigerator having the composition, and a method for operating the refrigerator.

[0010] TECHNICAL SOLUTION FOR SOLVING THE PROBLEMS

[0011] Item 1. A composition containing a refrigerant, wherein the refrigerant contains: 2,3,3,3-tetrafluoro-1-propene (R1234yf) and / or 1,3,3,3-tetrafluoropropene (R1234ze); trans-1,2-difluoroethylene (HFO-1132(E)); and CO2,

[0012] The proportion of HFO-1132(E) is 30 mass% or less, and the proportion of CO2 is 10 mass% or less, based on the entire refrigerant.

[0013] Item 2. The composition according to item 1, wherein the refrigerant contains R1234yf, and when the mass% of HFO-1132(E), R1234yf, and CO2, based on the total of them, are x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf, and CO2 is 100 mass%, the coordinates (x, y, z) are located on a straight line A connecting the following 3 points, respectively r＝0 B r＝0 , B r＝0 Or＝0 and O r＝0 A r＝0 within the range of the figure enclosed by the above-mentioned straight lines or on the above-mentioned straight lines,

[0014] point A r＝0 (30.0, 69.1, 0.9),

[0015] point B r＝0 (6.2, 83.8, 10.0),

[0016] point O r＝0 (30.0, 60.0, 10.0).

[0017] Item 3. The composition according to item 1, wherein the above-mentioned refrigerant contains R1234ze, and when mass% of HFO-1132(E), R1234ze and CO2 based on the total of them is x, y and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234ze and CO2 is 100 mass%, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines A r＝1 B r＝1 , B r＝1 O r＝1 and O r＝1 A r＝1 within the range of the figure enclosed by the above-mentioned straight lines or on the above-mentioned straight lines,

[0018] point A r＝1 (30.0, 62.9, 7.1),

[0019] point B r＝1 (23.1, 66.9, 10.0),

[0020] point O r＝1 (30.0, 60.0, 10.0).

[0021] Item 4. The composition according to item 1, wherein the above-mentioned refrigerant contains R1234yf and R1234ze, and when the ratio of R1234ze to the total of R1234yf and R1234ze is r (0 < r < 1), and mass% of the total of HFO-1132(E), R1234yf and R1234ze (R1234yf + R1234ze), and CO2 based on the total of them is x, y and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf + R1234ze and CO2 is 100 mass%, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines A r＝0 B r＝0 , B r＝0 O r＝0 within the range of the figure enclosed by the above-mentioned straight lines or on the above-mentioned straight lines.and O r＝0 A r＝0 within the range of the figure enclosed by or on the above-mentioned straight line,

[0022] point A r (30.0, -6.2r + 69.1, 6.2r + 0.9),

[0023] point B r (0.2r 2 + 16.7r + 6.2, -0.2r 2 - 16.7r + 83.8, 10.0),

[0024] point O r (30.0, 60.0, 10.0).

[0025] Item 5. The composition according to item 1, wherein the above-mentioned refrigerant contains R1234yf, and when the mass% of HFO-1132(E), R1234yf and CO2, based on the total of them, are x, y and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf and CO2 is 100 mass%, the coordinates (x, y, z) are located within the range of the figure enclosed by or on the line segment H r＝0 I r＝0 , I r＝0 J r＝0 , J r＝0 J2 r＝0 , J2 r＝0 K2 r＝0 , K2 r＝0 K r＝0 , K r＝0 Q r＝0 and Q r＝0 H r＝0 on the above-mentioned line segment H r＝0 I r＝0 , I r＝0 J r＝0 , J r＝0 K r＝0 and K r＝0 Q r＝0 (wherein the point H r＝0 and the point Q r＝0 are excluded),

[0026] point H r＝0 (12.2, 87.8, 0.0),

[0027] point I r＝0 (0.0, 98.1, 1.9),

[0028] point J r＝0 (0.0, 94.8, 5.2),

[0029] Point J2 r＝0 (10.0, 85.4, 4.6)

[0030] Point K2 r＝0 (20.0, 75.1, 4.9)

[0031] Point K r＝0 (30.0, 64.0, 6.0)

[0032] Click Q r＝0 (30.0, 70.0, 0.0),

[0033] Line segment I r＝0 J r＝0 K r＝0 Q r＝0 and Q r＝0 H r＝0 It is a straight line.

[0034] line segment H r＝0 I r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.0013x). 2 -0.8279x + 98.1, 0.0013x 2 -0.1721x+1.9) means,

[0035] line segment J r＝0 J2 r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.004x). 2 -0.9x + 94.8, 0.004x 2 -0.1x+5.2) means,

[0036] line segment J2 r＝0 K2 r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.006x). 2 -0.85x + 94.5, 0.006x 2 -0.15x+5.5) means,

[0037] line segment K2 r＝0 K r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.002x). 2 -1.01x + 96.1, 0.002x 2 +0.01x+3.9) represents.

[0038] Item 6. The composition according to item 1, wherein the above refrigerant contains R1234ze, and when mass% of HFO-1132(E), R1234ze and CO2 based on the total of them is x, y and z respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234ze and CO2 is 100 mass%, the coordinates (x, y, z) are located in a range of a figure surrounded by the following 7 points connected respectively r＝1 I r＝1 、 r＝1 J r＝1 、 r＝1 J2 r＝1 、 r＝1 K2 r＝1 、 r＝1 K r＝1 、 r＝1 Q r＝1 and Q r＝1 H r＝1 or in a range of a line segment H r＝1 I r＝1 、 r＝1 J r＝1 、 r＝1 K r＝1 and K r＝1 Q r＝1 above (wherein the point H r＝1 and the point Q r＝1 are excluded),

[0039] the point H r＝1 (22.7, 77.3, 0.0),

[0040] the point I r＝1 (0.0, 96.4, 3.6),

[0041] the point J r＝1 (0.0, 96.1, 3.9),

[0042] the point J2 r＝1 (10.0, 87.6, 2.4),

[0043] the point K2 r＝1 (20.0, 78.1, 1.9),

[0044] the point K r＝1 (30.0, 67.8, 2.2),

[0045] the point Q r＝1 (30.0, 70.0, 0.0),

[0046] the line segment I r＝1 J r＝1 , K r＝1 Qr＝1 and Q r＝1 H r＝1 is a straight line,

[0047] a point on the line segment H r＝1 I r＝1 is represented by (x, -0.003x 2 -0.7723x + 96.4, 0.003x 2 -0.2277x + 3.6),

[0048] a point on the line segment J r＝1 J2 r＝1 is represented by (x, -0.006x 2 -0.79x + 96.1, 0.006x 2 -0.21x + 3.9),

[0049] a point on the line segment J2 r＝1 K2 r＝1 is represented by (x, -0.002x 2 -0.89x + 96.7, 0.002x 2 -0.11x + 3.3),

[0050] a point on the line segment K2 r＝1 K r＝1 is represented by (x, -0.002x 2 -0.93x + 97.5, 0.002x 2 -0.07x + 2.5).

[0051] Item 7. The composition according to Item 1, wherein the above refrigerant contains R1234yf and R1234ze, provided that the ratio of R1234ze with respect to the total of R1234yf and R1234ze is r (0 < r < 1), provided that the mass% of the total of HFO-1132(E), R1234yf and R1234ze (R1234yf + R1234ze), and CO2, based on the total of them, is x, y and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf + R1234ze and CO2 is 100 mass%, the coordinates (x, y, z) are located on a line H r I r , I r J r , J r J2 r , J2 r K2 r , K2 r Kr , K r Q r and Q r H r the extent of the figure or above the line H r I r , I r J r , J r K r and K r Q r above (where the points H r and Q r are not included),

[0052] point H r (r 2 +9.5r+12.2,-r 2 -9.5r+87.8,0.0),

[0053] point I r (0.0,-0.6r 2 -1.1r+98.1,0.6r 2 +1.1r+1.9),

[0054] point J r (0.0,-0.6r 2 +1.9r+94.8,0.6r 2 -1.9r+5.2),

[0055] point J2 r (10.0,-0.4r 2 +2.6r+85.4,0.4r 2 -2.6r+4.6),

[0056] point K2 r (20.0,3.0r+75.1,-3.0r+4.9),

[0057] point K r (30.0,-0.4r 2 +4.2r+64.0,0.4r 2 -4.2r+6.0),

[0058] point Q r (70.0,30.0,0.0),

[0059] line segment I r J r , K r Q r and Q r H r are straight lines,

[0060] Line segment H r I r The coordinates (x,y,z) of a point on line segment H are given by (x,(0.003r 2 + 0.0013r - 0.0013)x 2 + (-0.102r 2 + 0.0464r - 0.8279)x + (-0.6r 2 + 1.1r + 98.1),(0.003r 2 - 0.0013r + 0.0013)x 2 + (-0.102r 2 + 0.0464r - 0.1721)x + (0.6r 2 + 1.1r + 1.9)).

[0061] Line segment J r J2 r The coordinates (x,y,z) of a point on line segment J are given by (x,(0.0068r 2 - 0.0034r - 0.004)x 2 + (0.06r 2 + 0.05r - 0.9)x + (-0.6r 2 + 1.9r + 94.8),(0.004r 2 - 0.002r + 0.004)x 2 + (-0.06r 2 - 0.05r - 0.1)x + (0.6r 2 - 1.9r + 5.2)).

[0062] Line segment J2 r K2 r The coordinates (x,y,z) of a point on line segment J2 are given by (x,(0.016r 2 - 0.012r - 0.006)x 2 + (-0.44r 2 + 0.4r - 0.85)x + (2.4r 2 - 0.2r + 94.5),(-0.016r 2 + 0.012r + 0.006)x 2 + (0.44r 2 - 0.4r - 0.15)x + (-2.4r 2 + 0.2r + 5.5).

[0063] Line segment K2 r K r The coordinates (x,y,z) of a point on line segment K2 are given by (x,(0.008r2 -0.008r-0.002)x 2 +(-0.44r 2 +0.52r-1.01)x+(5.6r 2 -4.2r+96.1),(-0.008r 2 +0.008r+0.002)x 2 +(0.44r 2 -0.52r+0.01)x+(-5.6r 2 +4.2r+3.9)) represents.

[0064] Item 8. The composition of any one of items 1 to 7, further comprising refrigeration oil, wherein the composition is used as a working fluid for a refrigeration unit.

[0065] Item 9. The composition of any one of items 1 to 4, which is used as an alternative refrigerant to R134a, R1234yf, and R404A.

[0066] Item 10. Use of the composition described in any one of items 1 to 4 as a refrigerant.

[0067] Item 11. A refrigerant for electric vehicles, comprising any one of items 5 to 7.

[0068] Item 12. A refrigeration machine comprising, as any one of items 1 to 8, the composition as the working fluid.

[0069] Item 13. A method of operating a refrigeration machine, the method comprising the step of circulating the composition described in any one of items 1 to 8 as a working fluid in the refrigeration machine.

[0070] Invention Effects

[0071] The refrigerant of this invention has a sufficiently low GWP. Attached Figure Description

[0072] Figure 1 It is a diagram showing the points and line segments of the refrigerant of the present invention in a three-component composition diagram where the sum of HFO-1132(E), R1234yf and CO2 is 100% by mass.

[0073] Figure 2 It is a diagram showing the points and line segments of the refrigerant of the present invention in a three-component composition diagram where the sum of HFO-1132(E), R1234ze and CO2 is 100% by mass.

[0074] Figure 3is a graph showing points and line segments of the refrigerant of the present application in an enlarged view of a ternary composition diagram in which the sum of HFO-1132(E), R1234yf, R1234ze, and CO2 is 100 mass%, assuming that the ratio of R1234ze with respect to the sum of R1234yf and R1234ze is r (0 < r < 1).

[0075] Figure 4 is a graph showing points and line segments of the refrigerant of the present application in a ternary composition diagram in which the sum of HFO-1132(E), R1234yf, and CO2 is 100 mass%.

[0076] Figure 5 is a graph showing points and line segments of the refrigerant of the present application in a ternary composition diagram in which the sum of HFO-1132(E), R1234ze, and CO2 is 100 mass%.

[0077] Figure 6 is a graph showing points and line segments of the refrigerant of the present application in an enlarged view of a ternary composition diagram in which the sum of HFO-1132(E), R1234yf, R1234ze, and CO2 is 100 mass%, assuming that the ratio of R1234ze with respect to the sum of R1234yf and R1234ze is r (0 < r < 1). DETAILED DESCRIPTION

[0078] The inventors of the present application have developed, through independent research, a refrigerant composition that has both a refrigeration capacity equivalent to that of R134a, R1234yf, R404A and a sufficiently small GWP. In addition, the inventors of the present application have also developed, through independent research, a refrigerant composition for use in an air conditioning device for an electric vehicle. The inventors of the present application have conducted intensive research and found that a refrigerant having the following composition has the above-mentioned properties: trans-1,2-difluoroethylene (HFO-1132(E)), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and / or 1,3,3,3-tetrafluoropropene (R1234ze), and CO2, and the proportion of trans-1,2-difluoroethylene (HFO-1132(E)) is 30 mass% or less based on the entire refrigerant, and the proportion of CO2 is 10 mass% or less based on the entire refrigerant.

[0079] The present application was completed based on the above insight and further repeated research. The present application includes the following embodiments.

[0080] <Definition of Terms>

[0081] In the present specification, the term "refrigerant" includes at least a compound labeled with a refrigerant number (ASHRAE number) beginning with R prescribed by ISO 817 (International Organization for Standardization) to indicate a refrigerant category, and also includes a substance having equivalent characteristics as a refrigerant, although not labeled with a refrigerant number. From the structural aspect of the compound, refrigerants are broadly classified into "fluorocarbon-based compounds" and "non-fluorocarbon-based compounds". The "fluorocarbon-based compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). As the "non-fluorocarbon-based compounds", there can be listed propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717), etc.

[0082] In the present specification, the term "refrigerant-containing composition" includes at least: (1) a refrigerant itself (including a mixture of refrigerants); (2) a composition further containing other components, and capable of being used to obtain a refrigeration working fluid by being mixed with at least a refrigeration oil; and (3) a refrigeration working fluid containing a refrigeration oil. In the present specification, among these three, the composition of (2) is distinguished from the refrigerant itself (including a mixture of refrigerants) and expressed as a "refrigerant composition". Also, the refrigeration working fluid of (3) is distinguished from the "refrigerant composition" and expressed as a "working fluid containing a refrigeration oil".

[0083] In the present specification, the term "substitute" is used in the context of "substituting" a first refrigerant with a second refrigerant, and as a first type, means that in a device designed to operate using a first refrigerant, it is possible to operate using a second refrigerant under optimal conditions by making only a small number of component (at least one of a refrigeration oil, a gasket, a packing, an expansion valve, a drier, and other components) changes and device adjustments as necessary. That is, this type means to "substitute" a refrigerant to operate the same device. As a way of "substitution" of this type, from small to large in terms of the degree of changes or adjustments required when replaced with a second refrigerant, there can be "drop in substitution", "nealy drop in substitution", and "retrofit", in order.

[0084] As a second type, a way of mounting a second refrigerant for use in order to use a device designed to operate using a second refrigerant for the same use as the existing use of a first refrigerant also belongs to the term "substitute". This type means to "substitute" a refrigerant to provide the same use.

[0085] In the present specification, the term "refrigerator" refers to an entire device that makes an object or a space become a temperature lower than a surrounding outside gas by taking away heat therefrom, and maintains the low temperature. In other words, the refrigerator refers to a conversion device that obtains energy from the outside and performs work in order to move heat from a side of a low temperature to a side of a high temperature, thereby performing energy conversion.

[0086] In the present specification, "vehicle-mounted air conditioning equipment" is one of refrigeration devices used for automobiles such as gasoline cars, hybrid cars, electric cars, and hydrogen-powered cars. The vehicle-mounted air conditioning equipment refers to a refrigeration device including a refrigeration cycle that uses an evaporator to perform heat exchange of liquid refrigerant, a compressor that sucks the evaporated refrigerant gas, a condenser that cools and liquefies the heat-insulated compressed refrigerant gas, and an expansion valve that performs heat-insulated expansion and then supplies the liquid refrigerant to the evaporator again.

[0087] In the present specification, pressure indicates absolute pressure unless specifically limited.

[0088] 1. Refrigerant

[0089] 1.1 Refrigerant composition

[0090] The refrigerant of the present application is a mixed refrigerant containing R1234yf and / or R1234ze, and CO2, and contains 30 mass% or less of HFO-1132(E) based on the entire refrigerant, and the content ratio of CO2 based on the entire refrigerant is 10 mass% or less.

[0091] The GWP of the refrigerant of the present application is sufficiently small.

[0092] In addition, in the refrigerant of the present application, when the mass% of the sum of HFO-1132(E), R1234yf, and R1234ze (R1234yf + R1234ze) and the mass% of CO2 based on the sum thereof are x, y, and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R1234yf, and R1234ze and the sum of CO2 are 100 mass%, the coordinates (x, y, z) satisfy the following conditions, and the disproportionation reaction does not occur at 3 MPa and 150°C, and there is no need to take a disproportionation countermeasure for the equipment.

[0093] The refrigerant of the present application can be a refrigerant containing R1234yf, and in a ternary composition diagram in which the total of HFO-1132(E), R1234yf and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of a figure formed by connecting the following 3 points, or on the straight line A connecting the points r＝0 B r＝0 , B r＝0 O r＝0 and O r＝0 A r＝0 in the above-mentioned straight line,

[0094] Point A r＝0 (30.0, 69.1, 0.9),

[0095] Point B r＝0 (6.2, 83.8, 10.0),

[0096] Point O r＝0 (30.0, 60.0, 10.0).

[0097] In this case, the refrigerant of the present application has a refrigeration capacity ratio of 90% or more based on R404A.

[0098] The refrigerant of the present application can be a refrigerant containing R1234yf, and in a ternary composition diagram in which the total of HFO-1132(E), R1234yf and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of a figure formed by connecting the following 3 points, or on the straight line E connecting the points r＝0 F r＝0 , F r＝0 O r＝0 and O r＝0 E r＝0 in the above-mentioned straight line,

[0099] Point E r＝0 (30.0, 66.2, 3.8),

[0100] Point F r＝0 (13.4, 76.6, 10.0),

[0101] Point O r＝0 (30.0, 60.0, 10.0).

[0102] In this case, the refrigerant of the present application has a refrigeration capacity ratio of 100% or more based on R404A.

[0103] The refrigerant of the present application can be a refrigerant containing R1234ze, and when HFO-1132(E), R1234ze, and CO2 are x, y, and z in mass% based on the total of them, respectively, in a ternary composition diagram in which the total of HFO-1132(E), R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are within a range of a figure surrounded by straight lines A connecting the following 3 points, respectively, or on the straight lines, r＝1 B r＝1 , B r＝1 O r＝1 and O r＝1 A r＝1 ,

[0104] Point A r＝1 (30.0, 62.9, 7.1),

[0105] Point B r＝1 (23.1, 66.9, 10.0),

[0106] Point O r＝1 (30.0, 60.0, 10.0).

[0107] In this case, the refrigeration capacity ratio of the refrigerant of the present application based on R404A is 90% or more.

[0108] The refrigerant of the present application can contain 30.0 mass% of HFO-1132(E), 60.0 mass% of R1234ze, and 10.0 mass% of CO2, based on the total of HFO-1132(E), R1234ze, and CO2. In this case, the refrigeration capacity ratio of the refrigerant of the present application based on R404A is 100%.

[0109] The refrigerant of the present application can be a refrigerant in which when the ratio of R1234ze to the total of R1234yf and R1234ze is r (0 < r < 1), and the mass% of the total of HFO-1132(E), R1234yf, and R1234ze (R1234yf + R1234ze), and CO2, based on the total of them, is x, y, and z, respectively, in a ternary composition diagram in which the total of HFO-1132(E), R1234yf + R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are within a range of a figure surrounded by straight lines A connecting the following 3 points, respectively, or on the straight lines, r＝0 B r＝0 , B r＝0 O r＝0 and O r＝0 A r＝0 ,

[0110] Point A r (30.0, -6.2r + 69.1, 6.2r + 0.9),

[0111] Point B r (0.2r 2 + 16.7r + 6.2, -0.2r 2 - 16.7r + 83.8, 10.0),

[0112] Point O r (30.0, 60.0, 10.0).

[0113] In this case, the refrigeration capacity ratio of the refrigerant of the present application with respect to R404A is 90% or more.

[0114] The refrigerant of the present application can be a refrigerant in which, when the ratio of R1234ze with respect to the total of R1234yf and R1234ze is r (0 < r < 1), the total of HFO-1132(E), R1234yf and R1234ze (R1234yf + R1234ze), and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of the figure surrounded by connecting the following 3 points A r B r , B r O r and O r A r respectively, or on the above straight line, in a three-component composition diagram of HFO-1132(E), R1234yf + R1234ze and CO2.

[0115] Point E r (30.0, 0.4r 2 - 6.6r + 66.2, -0.4r 2 + 6.6r + 3.8),

[0116] Point F r (-1.2r 2 + 17.8r + 13.4, 1.2r 2 - 17.8r + 76.6, 10.0),

[0117] Point O r (30.0, 60.0, 10.0).

[0118] In this case, the refrigeration capacity ratio of the refrigerant of the present application with respect to R404A is 100% or more.

[0119] The refrigerant of the present application can be a refrigerant (Refrigerant A) containing R1234yf, and provided that HFO-1132(E), R1234yf and CO2 are x, y and z, respectively, in mass% based on the total of HFO-1132(E), R1234yf and CO2, when the coordinates (x, y, z) are in a three-component composition diagram in which the total of HFO-1132(E), R1234yf and CO2 is 100 mass%, the coordinates (x, y, z) are within a figure formed by connecting the following 7 points, respectively r＝0 I r＝0 、 r＝0 J r＝0 、 r＝0 J2 r＝0 、 r＝0 K2 r＝0 、 r＝0 K r＝0 、 r＝0 Q r＝0 and Q r＝0 H r＝0 or the range of the figure formed by the above line segment H r＝0 I r＝0 、 r＝0 J r＝0 、 r＝0 K r＝0 and K r＝0 Q r＝0 above (wherein the point H r＝0 and the point Q r＝0 are excluded),

[0120] the point H r＝0 (12.2, 87.8, 0.0),

[0121] the point I r＝0 (0.0, 98.1, 1.9),

[0122] the point J r＝0 (0.0, 94.8, 5.2),

[0123] the point J2 r＝0 (10.0, 85.4, 4.6),

[0124] the point K2 r＝0 (20.0, 75.1, 4.9),

[0125] the point K r＝0 (30.0, 64.0, 6.0),

[0126] the point Q r＝0 (30.0, 70.0, 0.0),

[0127] the line segment I r＝0 J r＝0 , K r＝0 Qr＝0 and Q r＝0 H r＝0 is a straight line,

[0128] a point on the line segment H r＝0 I r＝0 is represented by (x, -0.0013x 2 -0.8279x + 98.1, 0.0013x 2 -0.1721x + 1.9),

[0129] a point on the line segment J r＝0 J2 r＝0 is represented by (x, -0.004x 2 -0.9x + 94.8, 0.004x 2 -0.1x + 5.2),

[0130] a point on the line segment J2 r＝0 K2 r＝0 is represented by (x, -0.006x 2 -0.85x + 94.5, 0.006x 2 -0.15x + 5.5),

[0131] a point on the line segment K2 r＝0 K r＝0 is represented by (x, -0.002x 2 -1.01x + 96.1, 0.002x 2 + 0.01x + 3.9).

[0132] In this case, the boiling point of the refrigerant of the present application is -40°C or less, and the evaporation glide is 15 K or less. Due to this characteristic, the refrigerant is particularly suitable for a working fluid in an air conditioning device for an electric automobile.

[0133] The refrigerant of the present application can be a refrigerant (Refrigerant B) containing R1234ze, and when the mass% of HFO-1132(E), R1234ze, and CO2, based on the total of them, are x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are located on the line segment H r＝1 I r＝1 , I r＝1 J r＝1 , J r＝1 J2 r＝1 , J2 r＝1 K2 r＝1 , K2r＝1 K r＝1 K r＝1 Q r＝1 and Q r＝1 H r＝1 Within the area of ​​the enclosed figure or the aforementioned line segment H r＝1 I r＝1 I r＝1 J r＝1 J r＝1 K r＝1 and K r＝1 Q r＝1 Above (excluding point H) r＝1 and point Q r＝1 ),

[0134] Point H r＝1 (22.7,77.3,0.0)

[0135] Point I r＝1 (0.0, 96.4, 3.6)

[0136] Point J r＝1 (0.0, 96.1, 3.9)

[0137] Point J2 r＝1 (10.0, 87.6, 2.4)

[0138] Point K2 r＝1 (20.0, 78.1, 1.9)

[0139] Point K r＝1 (30.0, 67.8, 2.2)

[0140] Click Q r＝1 (30.0, 70.0, 0.0),

[0141] Line segment I r＝1 J r＝1 K r＝1 Q r＝1 and Q r＝1 H r＝1 It is a straight line.

[0142] line segment H r＝1 I r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.003x). 2 -0.7723x + 96.4, 0.003x 2 -0.2277x+3.6) means,

[0143] line segment J r＝1 J2 r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.006x).2 -0.79x + 96.1, 0.006x 2 -0.21x + 3.9) represents,

[0144] line segment J2 r＝1 K2 r＝1 The coordinates (x, y, z) of the point on the line segment are represented by (x, -0.002x 2 -0.89x + 96.7, 0.002x 2 -0.11x + 3.3) represents,

[0145] line segment K2 r＝1 K r＝1 The coordinates (x, y, z) of the point on the line segment are represented by (x, -0.002x 2 -0.93x + 97.5, 0.002x 2 -0.07x + 2.5) represents.

[0146] In this case, the boiling point of the refrigerant of the present application is -40°C or lower, and the evaporation glide is 15 K or lower. Due to this characteristic, the refrigerant is particularly suitable for a working fluid in an air conditioning device for an electric automobile.

[0147] The refrigerant of the present application can be a refrigerant (Refrigerant C) that, when the ratio of R1234ze with respect to the total of R1234yf and R1234ze is r (0 < r < 1), the total of HFO-1132(E), R1234yf and R1234ze (R1234yf + R1234ze), and CO2 is 100 mass%, the mass% of HFO-1132(E), R1234yf + R1234ze, and CO2 with respect to the total thereof is x, y, and z, respectively, in a three-component composition diagram, the coordinates (x, y, z) are within the range of a figure enclosed by line segments H r I r , I r J r , J r J2 r , J2 r K2 r , K2 r K r , K r Q r and Q r H r or the above line segment H r I r , I r J r , J r K r and K r Qr upper (wherein point H r and point Q r ),

[0148] point H r (r 2 +9.5r+12.2,-r 2 -9.5r+87.8,0.0)、

[0149] point I r (0.0,-0.6r 2 -1.1r+98.1,0.6r 2 +1.1r+1.9)、

[0150] point J r (0.0,-0.6r 2 +1.9r+94.8,0.6r 2 -1.9r+5.2)、

[0151] point J2 r (10.0,-0.4r 2 +2.6r+85.4,0.4r 2 -2.6r+4.6)、

[0152] point K2 r (20.0,3.0r+75.1,-3.0r+4.9)、

[0153] point K r (30.0,-0.4r 2 +4.2r+64.0,0.4r 2 -4.2r+6.0)、

[0154] point Q r (70.0,30.0,0.0),

[0155] line segment I r J r , K r Q r and Q r H r are straight lines,

[0156] the coordinates (x, y, z) of the points on line segment H r I r are given by (x, (-0.003r 2 +0.0013r-0.0013)x 2 +(0.102r 2 -0.0464r-0.8279)x+(-0.6r 2-0.0013r + 0.0013)x 2 -0.0013r + 0.0013)x 2 +(-0.102r 2 +0.0464r - 0.1721)x + (0.6r 2 +1.1r + 1.9)) represents,

[0157] The coordinates (x, y, z) of the points on the segment J r J2 r are represented by (x, (0.0068r 2 -0.0034r - 0.004)x 2 +(0.06r 2 +0.05r - 0.9)x + (-0.6r 2 +1.9r + 94.8), (0.004r 2 -0.002r + 0.004)x 2 +(-0.06r 2 -0.05r - 0.1)x + (0.6r 2 -1.9r + 5.2)),

[0158] The coordinates (x, y, z) of the points on the segment J2 r K2 r are represented by (x, (0.016r 2 -0.012r - 0.006)x 2 +(-0.44r 2 +0.4r - 0.85)x + (2.4r 2 -0.2r + 94.5), (-0.016r 2 +0.012r + 0.006)x 2 +(0.44r 2 -0.4r - 0.15)x + (-2.4r 2 +0.2r + 5.5)),

[0159] The coordinates (x, y, z) of the points on the segment K2 r K r are represented by (x, (0.008r 2 -0.008r - 0.002)x 2 +(-0.44r 2 +0.52r - 1.01)x + (5.6r 2 -4.2r + 96.1), (-0.008r 2 +0.008r + 0.002)x 2 +(0.44r 2-0.52r + 0.01)x + (-5.6r 2 + 4.2r + 3.9)) represents.

[0160] In this case, the boiling point of the refrigerant of the present application is -40°C or lower, and the evaporation glide is 15 K or lower. Due to this characteristic, the refrigerant is particularly suitable for a working fluid in an air conditioning device for an electric vehicle.

[0161] In addition, the refrigerant A, the refrigerant B, and the refrigerant C have an advantage that they are easily used in heating using a heat pump because the boiling point is -40.0°C or lower. For example, the above-mentioned refrigerant of the present application has an advantage that heating can be performed using a heat pump with less power consumption than an electric heater, by a refrigeration cycle for operating an on-vehicle air conditioning device. As the on-vehicle air conditioning device, a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen-powered vehicle, or the like can be exemplified.

[0162] In the refrigerant of the present application, in a range not impairing the above-mentioned characteristics and effects, in addition to HFO-1132(E), R1234yf, R1234ze, and CO2, other additional refrigerants can be contained. From this point of view, the refrigerant of the present application preferably contains 99.5 mass% or more of HFO-1132(E), R1234yf, R1234ze, and CO2, more preferably 99.75 mass% or more, and further preferably 99.9 mass% or more, in total with respect to the refrigerant.

[0163] As the additional refrigerant, there is no particular limitation, and a wide selection can be made. In the mixed refrigerant, one kind alone or two or more kinds can be contained as the additional refrigerant.

[0164] As the additional refrigerant, acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFC-152a, HFC-161, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, 3,3,3-trifluoropropynyl, or the like can be exemplified.

[0165] The total amount of the additional refrigerant is preferably 0.5 mass% or less, more preferably 0.25 mass% or less, further preferably 0.1 mass% or less, and most preferably 0.01 mass% or less, with respect to the refrigerant as a whole.

[0166] 1.2 Use

[0167] The refrigerant of the present application is preferably used as a working fluid in a refrigerator.

[0168] The composition of the present application is suitable for use as a replacement refrigerant for R404A in the above-described certain aspect.

[0169] The composition of the present application is suitable for use as a refrigerant for air conditioning equipment of an electric automobile in the above-described certain aspect.

[0170] 2. Refrigerant composition

[0171] The refrigerant composition of the present application contains at least the refrigerant of the present application and can be used for the same use as the refrigerant of the present application. In addition, the refrigerant composition of the present application can also be used for obtaining a working fluid for a refrigerator by mixing at least with a refrigerator oil.

[0172] The refrigerant composition of the present application contains at least the refrigerant of the present application and can be used for the same use as the refrigerant of the present application. In addition, the refrigerant composition of the present application can also be used for obtaining a working fluid for a refrigerator by mixing at least with a refrigerator oil.

[0173] 2.1 Water

[0174] The refrigerant composition of the present application can contain a trace amount of water. The proportion of water in the refrigerant composition is preferably 0.1 mass% or less with respect to the entire refrigerant. By containing a trace amount of water in the refrigerant composition, the intramolecular double bond of the unsaturated fluorocarbon compound that can be contained in the refrigerant is stabilized, and oxidation of the unsaturated fluorocarbon compound is also less likely to occur, so that the stability of the refrigerant composition is improved.

[0175] 2.2 Tracer

[0176] In order to be able to trace changes in the refrigerant composition of the present application in the event of dilution, contamination, and any other changes, a tracer can be added to the refrigerant composition of the present application at a detectable concentration.

[0177] The refrigerant composition of the present application can contain one or two or more types of tracers.

[0178] The tracer is not particularly limited and can be appropriately selected from commonly used tracers. It is preferable to select a compound that is unlikely to form impurities that are inevitably mixed in the refrigerant of the present application as the tracer.

[0179] As the tracer, for example, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorine-containing ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and the like can be exemplified. As the tracer, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, fluorocarbons, hydrochlorocarbons, fluorocarbons and fluorine-containing ethers are particularly preferred.

[0180] As the above-mentioned tracer, the following compounds are particularly preferred.

[0181] FC-14 (tetrafluoromethane, CF4)

[0182] HCC-40 (chloromethane, CH3Cl)

[0183] HFC-23 (trifluoromethane, CHF3)

[0184] HFC-41 (fluoromethane, CH3F)

[0185] HFC-125 (pentafluoroethane, CF3CHF2)

[0186] HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)

[0187] HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)

[0188] HFC-143a (1,1,1-trifluoroethane, CF3CH3)

[0189] HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)

[0190] HFC-152a (1,1-difluoroethane, CHF2CH3)

[0191] HFC-152 (1,2-difluoroethane, CH2FCH2F)

[0192] HFC-161 (fluoroethane, CH3CH2F)

[0193] HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)

[0194] HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)

[0195] HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)

[0196] HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)

[0197] HCFC-22 (Chlorodifluoromethane, CHClF2)

[0198] HCFC-31 (Chlorofluoromethane, CH2ClF)

[0199] CFC-1113 (Chlorotrifluoroethylene, CF2=CCIF)

[0200] HFE-125 (Trifluoromethyl-difluoromethyl ether, CF3OCHF2)

[0201] HFE-134a (Trifluoromethyl-fluoromethyl ether, CF3OCH2F)

[0202] HFE-143a (Trifluoromethyl-methyl ether, CF3OCH3)

[0203] HFE-227ea (Trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)

[0204] HFE-236fa (Trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0205] The tracer compounds can be present in the refrigerant composition at a combined concentration of from about 10 parts per million (ppm) by weight to about 1000 ppm by weight. Preferably, the tracer compounds are present in the refrigerant composition at a combined concentration of from about 30 ppm by weight to about 500 ppm by weight, and most preferably, the tracer compounds are present in the refrigerant composition at a combined concentration of from about 50 ppm by weight to about 300 ppm by weight.

[0206] 2.3 Ultraviolet fluorescent dye

[0207] In the refrigerant composition of the present application, as the ultraviolet fluorescent dye, one kind alone can be contained, or two or more kinds can be contained.

[0208] As the ultraviolet fluorescent dye, there is no particular limitation, and it can be appropriately selected from among the ultraviolet fluorescent dyes that are generally used.

[0209] As the ultraviolet fluorescent dye, for example, naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, benzoxanthene, and fluorescein, and derivatives thereof can be exemplified. As the ultraviolet fluorescent dye, either one or both of naphthalimide and coumarin are particularly preferred.

[0210] 2.4 Stabilizer

[0211] The refrigerant composition of the present application can contain one or more kinds of stabilizers.

[0212] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0213] Examples of the stabilizer include nitro compounds, ethers, and amines.

[0214] Examples of the nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0215] Examples of the ethers include 1,4-dioxane.

[0216] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0217] Examples of the stabilizer also include butylated hydroxytoluene and benzotriazole.

[0218] The content ratio of the stabilizer is not particularly limited and is generally preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, relative to the entire refrigerant.

[0219] 2.5 Polymerization inhibitor

[0220] The refrigerant composition of the present application can contain one or more kinds of polymerization inhibitors.

[0221] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0222] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tertiary butyl phenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0223] The content ratio of the polymerization inhibitor is not particularly limited and is generally preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, relative to the entire refrigerant.

[0224] 3. Working fluid containing refrigeration oil

[0225] The working fluid containing the refrigeration oil of the present application contains at least the refrigerant or the refrigerant composition of the present application and the refrigeration oil and can be used as a working fluid in a refrigeration machine. Specifically, the working fluid containing the refrigeration oil of the present application is obtained by mixing the refrigeration oil used in the compressor of the refrigeration machine and the refrigerant or the refrigerant composition with each other. The working fluid containing the refrigeration oil generally contains 10 to 50% by mass of the refrigeration oil.

[0226] 3.1 Refrigeration oil

[0227] In the composition of the present application, one kind of refrigerant oil alone or two or more kinds of refrigerant oils can be contained.

[0228] The refrigerant oil is not particularly limited, and can be appropriately selected from generally used refrigerant oils. At this time, as needed, a refrigerant oil more excellent in terms of effects such as improvement in miscibility with the above mixture and stability of the above mixture can be appropriately selected.

[0229] As the base oil of the refrigerant oil, for example, at least one kind selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferred.

[0230] In the refrigerant oil, in addition to the base oil, an additive can be contained. The additive can be at least one kind selected from the group consisting of an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, an antirust agent, an oiliness agent, and an antifoaming agent.

[0231] As the refrigerant oil, from the aspect of lubrication, a refrigerant oil having a kinematic viscosity at 40°C of 5 to 400 cSt is preferred.

[0232] In the working fluid of the present application containing a refrigerant oil, at least one kind of additive can be further contained as needed. As the additive, for example, the following compatibilizers and the like can be exemplified.

[0233] 3.2 Compatibilizer

[0234] In the working fluid of the present application containing a refrigerant oil, one kind of compatibilizer alone or two or more kinds of compatibilizers can be contained.

[0235] The compatibilizer is not particularly limited, and can be appropriately selected from generally used compatibilizers.

[0236] As the compatibilizer, for example, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorinated hydrocarbon, ester, lactone, aryl ether, fluorine-containing ether, and 1,1,1-trifluoroalkane, and the like can be exemplified. As the compatibilizer, polyoxyalkylene glycol ether is particularly preferred.

[0237] 4. Method of operating a refrigeration machine

[0238] The operation method of the refrigerator of the present application is a method of operating a refrigerator using the refrigerant of the present application.

[0239] Specifically, the operation method of the refrigerator of the present application includes a step of circulating the refrigerant of the present application in a refrigerator.

[0240] The above describes embodiments, but it should be understood that the modes and details can be variously changed without departing from the gist and scope of the claimed invention.

[0241] Embodiments

[0242] The following describes embodiments in more detail, but the present invention is not limited to these embodiments.

[0243] For HFO-1132(E), R-1234yf, and R-1234ze, these were mixed at the mass% shown in Table 1, respectively, based on the total, to prepare mixed refrigerants.

[0244] For each of these mixed refrigerants, the presence or absence of disproportionation was examined under the following test method and test conditions.

[0245] Test method

[0246] The mixed refrigerant to be tested was transferred and filled into a test container, and after heating to 150°C, a voltage was applied to the Pt wire in the container to cause it to melt, thereby supplying 30 J of energy to the mixed refrigerant. The presence or absence of disproportionation was determined by a sharp rise in pressure and temperature in the device.

[0247] Test conditions

[0248] Test container: 38 cc SUS container

[0249] Test temperature: 150°C

[0250] Pressure: 3 MPa

[0251] Determination criteria

[0252] "Not exploded": the temperature or pressure after the Pt wire melted was less than 2 times, and no sharp disproportionation occurred.

[0253] "Exploded": the temperature or pressure after the Pt wire melted was 2 times or more, and sharp disproportionation occurred.

[0254] [Table 1]

[0255]

[0256] According to the results of Table 1, it was determined that the refrigerant of the present invention did not undergo disproportionation within the region shown in the triangular diagram shown below. Figures 1 to 6

[0257] ​HFO-1132(E), R1234yf, R1234ze, and CO2 were mixed at the mass% shown in Tables 1 to 6, respectively, based on the total of them, to prepare a mixed refrigerant.

[0258] The GWP of each mixed refrigerant was evaluated based on the value of the fourth report of IPCC (Intergovernmental Panel on Climate Change). The GWP of HFO-1132(E) was not described, but it was set to 1 based on HFO-1132a (GWP = 1 or less), HFO-1123 (GWP = 0.3, described in Patent Literature 1).

[0259] For each mixed refrigerant of Tables 1 to 4, the discharge pressure, the condensation glide, the coefficient of performance (COP) ratio based on R404A, and the refrigeration capacity ratio were calculated, respectively. The cycle performance of each mixed refrigerant was calculated by performing theoretical calculation of the refrigeration cycle of the mixed refrigerant under the following conditions, using the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) of the National Institute of Science and Technology (NIST).

[0260] Herein, the property data of HFO-1132(E) was calculated using the measured value.

[0261] Evaporation temperature: -40°C

[0262] Condensation temperature: 40°C

[0263] Superheat: 20 K

[0264] Subcooling: 0 K

[0265] E comp (Compressor work amount): 0.7 kWh

[0266] The evaluation results are shown in Tables 1 to 4 together with the GWP of each mixed refrigerant.

[0267] [Table 2]

[0268]

[0269] [Table 3]

[0270]

[0271] [Table 4]

[0272]

[0273] [Table 5]

[0274]

[0275] The COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant of Tables 5 to 6 were found by performing theoretical calculation of the refrigeration cycle of the mixed refrigerant under the following conditions using the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) of the National Institute of Science and Technology (NIST). As for the property data of HFO-1132(E), the measured values were used.

[0276]

[0277] In the following tables, "COP ratio" and "refrigeration capacity ratio" indicate the ratio (%) with respect to R1234yf.

[0278] In the table, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa). In the table, "power consumption (%)" indicates the electric energy used by the electric automobile for running, and is indicated by the ratio to the power consumption when the refrigerant is HFO-1234yf. In the table, "heating consumption (%)" indicates the electric energy used by the electric automobile for running the heating, and is indicated by the ratio to the power consumption when the refrigerant is HFO-1234yf.

[0279] In the following table, "drivable distance (with)" indicates the drivable distance when the heating is performed in the electric automobile equipped with a secondary battery having a certain electric capacity, in relative ratio (%) when the drivable distance (without) when the heating is not performed (the power consumption for the heating is 0) is set to 100%.

[0280] As for the heating method, in the refrigerant having a boiling point greater than -40°C, the heating is performed by the electric heater method, and in the refrigerant having a boiling point of -40°C or less, the heating is performed by the heat pump method.

[0281] The power consumption at the time of the heating use was found using the following formula. In the formula, heating COP means "heating efficiency".

[0282] Power consumption in heating use = heating capacity / heating COP

[0283] As for the heating efficiency, the heating COP = 1 in the case of the electric heater, and the same amount of power as the motive power is consumed in heating. That is, the power consumption in heating is E = E / (1+COP).

[0284] On the other hand, in the case of the heat pump, Refprop 9.0 (NIST) was used, and theoretical calculation of the refrigeration cycle of the mixed refrigerant was performed under the following conditions, whereby the heating COP was found.

[0285]

[0286] The distance that can be traveled was found using the following equation.

[0287] Distance that can be traveled = (battery capacity) / (power consumption in motive power + power consumption in heating)

[0288] These values are shown in the following table together with the GWP for each mixed refrigerant. In the table, the specific COP and the specific refrigeration capacity are shown as the ratio to HFO-1234yf.

[0289] The coefficient of performance (COP) was found using the following equation.

[0290] COP = (refrigeration capacity or heating capacity) / power consumption

[0291] [Table 6]

[0292]

[0293] [Table 7]

[0294]

[0295] From these results, the following was determined.

[0296] contains R1234yf, and when the mass% of HFO-1132(E), R1234yf, and CO2, based on the total of these, are x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf, and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines A r＝0 B r＝0 , B r＝0 O r＝0 and O r＝0 A r＝0 or on the above straight lines,

[0297] Point A r＝0 (30.0, 69.1, 0.9),

[0298] point B r＝0 (6.2, 83.8, 10.0),

[0299] point O r＝0 (30.0, 60.0, 10.0),

[0300] In this case, the refrigerant of the present application has a refrigerating capacity ratio of 90% or more on the basis of R404A.

[0301] contains R1234yf, and in a ternary composition diagram in which the sum of HFO-1132(E), R1234yf, and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of a figure formed by connecting the following 3 points, or on the above straight line E r＝0 F r＝0 , F r＝0 O r＝0 and O r＝0 E r＝0 formed by the above 3 points,

[0302] point E r＝0 (30.0, 66.2, 3.8),

[0303] point F r＝0 (13.4, 76.6, 10.0),

[0304] point O r＝0 (30.0, 60.0, 10.0),

[0305] In this case, the refrigerant of the present application has a refrigerating capacity ratio of 100% or more on the basis of R404A.

[0306] contains R1234ze, and when the mass% of HFO-1132(E), R1234ze, and CO2, on the basis of the sum thereof, are x, y, and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of a figure formed by connecting the following 3 points, or on the above straight line A r＝1 B r＝1 , B r＝1 O r＝1 and O r＝1 A r＝1 formed by the above 3 points,

[0307] point A r＝1 (30.0, 62.9, 7.1),

[0308] point B r＝1 (23.1, 66.9, 10.0),

[0309] Point A r＝1 (30.0, 60.0, 10.0),

[0310] In this case, the refrigerant of the present application has a freezing capacity ratio of 90% or more on the basis of R404A.

[0311] When the total of HFO-1132(E), R1234ze, and CO2 is taken as a basis, and HFO-1132(E) is contained at 30.0 mass%, R1234ze at 60.0 mass%, and CO2 at 10.0 mass%, the refrigerant of the present application has a freezing capacity ratio of 100% on the basis of R404A.

[0312] When the ratio of R1234ze to the total of R1234yf and R1234ze is taken as r (0 < r < 1), and the mass% of the total of HFO-1132(E), R1234yf, and R1234ze (R1234yf + R1234ze), and CO2, on the basis of the total, is taken as x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234yf + R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are within the range of the figure formed by connecting the following 3 points, or on the above straight line A r＝0 B r＝0 , B r＝0 O r＝0 and O r＝0 A r＝0 In this case, the refrigerant of the present application has a freezing capacity ratio of 90% or more on the basis of R404A.

[0313] Point A r (30.0, 60.0, 10.0),

[0314] Point B r (0.2r 2 + 16.7r + 6.2, -0.2r 2 - 16.7r + 83.8, 10.0),

[0315] Point A r (30.0, 60.0, 10.0),

[0316] In this case, the refrigerant of the present application has a freezing capacity ratio of 90% or more on the basis of R404A.

[0317] When the ratio of R1234ze to the total of R1234yf and R1234ze is r (0 < r < 1), and the mass% of the total of HFO-1132(E), R1234yf and R1234ze (R1234yf + R1234ze), and CO2, based on their total, is x, y and z, respectively, in a ternary composition diagram in which the total of HFO-1132(E), R1234yf + R1234ze and CO2 is 100 mass%, the coordinates (x, y, z) are located in the range of the figure formed by connecting the following 3 points, or on the straight line A connecting the points r B r , B r O r and O r A r ,

[0318] Point E r (30.0, 0.4r 2 -6.6r + 66.2, -0.4r 2 + 6.6r + 3.8),

[0319] Point F r (-1.2r 2 + 17.8r + 13.4, 1.2r 2 - 17.8r + 76.6, 10.0),

[0320] Point O r (30.0, 60.0, 10.0),

[0321] In this case, the refrigeration capacity ratio of the refrigerant of the present application, based on R404A, is 100% or more.

[0322] contains R1234yf, and the mass% of HFO-1132(E), R1234yf and CO2, based on their total, is x, y and z, respectively, in a ternary composition diagram in which the total of HFO-1132(E), R1234yf and CO2 is 100 mass%, the coordinates (x, y, z) are located in the range of the line segment H connecting the following 7 points, or on the line segment H r＝0 I r＝0 , I r＝0 J r＝0 , J r＝0 J2 r＝0 , J2 r＝ OK2 r＝0 , K2 r＝0 K r＝0 , K r＝0 Q r＝0 and Q r＝0 H r＝0the range of the figure enclosed or the line segment H r＝0 I r＝0 、 r＝0 J r＝0 、 r＝0 K r＝0 and K r＝0 Q r＝0 above (where the points H r＝0 and Q r＝0 are not included),

[0323] point H r＝0 (12.2, 87.8, 0.0),

[0324] point I r＝0 (0.0, 98.1, 1.9),

[0325] point J r＝0 (0.0, 94.8, 5.2),

[0326] point J2 r＝0 (10.0, 85.4, 4.6),

[0327] point K2 r＝0 (20.0, 75.1, 4.9),

[0328] point K r＝0 (30.0, 64.0, 6.0),

[0329] point Q r＝0 (30.0, 70.0, 0.0),

[0330] line segment I r＝0 J r＝0 , K r＝0 Q r＝0 and Q r＝0 H r＝0 are straight lines,

[0331] the coordinates (x, y, z) of the points on the line segment H r＝0 I r＝0 are represented by (x, -0.0013x 2 -0.8279x + 98.1, 0.0013x 2 -0.1721x + 1.9),

[0332] the coordinates (x, y, z) of the points on the line segment J r＝0 J2 r＝0 are represented by (x, -0.004x 2 -0.9x + 94.8, 0.004x 2 -0.1x + 5.2),

[0333] line segment J2r＝0 K2 r＝0 The coordinates (x, y, z) of the point on K2 are represented by (x, -0.006x 2 -0.85x + 94.5, 0.006x 2 -0.15x + 5.5),

[0334] K2 r＝0 K r＝0 The coordinates (x, y, z) of the point on K2 are represented by (x, -0.002x 2 -1.01x + 96.1, 0.002x 2 + 0.01x + 3.9),

[0335] In this case, the boiling point of the refrigerant of the present application is -40°C or lower, and the evaporation glide is 15 K or lower. Due to this characteristic, the refrigerant is particularly suitable for a working fluid in an air conditioning device for an electric automobile.

[0336] containing R1234ze, and when mass% of HFO-1132(E), R1234ze, and CO2 based on the total of them is x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are within a figure enclosed by the line segments H r＝1 I r＝1 , I r＝1 J r＝1 , J r＝1 J2 r＝1 , J2 r＝ 1K2 r＝1 , K2 r＝1 K r＝1 , K r＝1 Q r＝1 and Q r＝1 H r＝1 or the above line segments H r＝1 I r＝1 , I r＝1 J r＝1 , J r＝1 K r＝1 and K r＝1 Q r＝1 on Q (wherein the point H r＝1 and the point Q r＝1 ) are not included,

[0337] the point H r＝1 (22.7, 77.3, 0.0),

[0338] the point I r＝1 (0.0, 96.4, 3.6),

[0339] Point J r＝1 (0.0, 96.1, 3.9),

[0340] Point J2 r＝1 (10.0, 87.6, 2.4),

[0341] Point K2 r＝1 (20.0, 78.1, 1.9),

[0342] Point K r＝1 (30.0, 67.8, 2.2),

[0343] Point Q r＝1 (30.0, 70.0, 0.0),

[0344] Line segment I r＝1 J r＝1 , K r＝1 Q r＝1 and Q r＝1 H r＝1 is a straight line,

[0345] Line segment H r＝1 I r＝1 The coordinates (x, y, z) of the points on the line segment J 2 -0.7723x + 96.4, 0.003x 2 -0.2277x + 3.6),

[0346] Line segment J r＝1 J2 r＝1 The coordinates (x, y, z) of the points on the line segment J2 2 -0.79x + 96.1, 0.006x 2 -0.21x + 3.9),

[0347] Line segment J2 r＝1 K2 r＝1 The coordinates (x, y, z) of the points on the line segment K2 2 -0.89x + 96.7, 0.002x 2 -0.11x + 3.3),

[0348] Line segment K2 r＝1 K r＝1 The coordinates (x, y, z) of the points on the line segment K 2 -0.93x + 97.5, 0.002x 2 -0.07x + 2.5),

[0349] In this case, the boiling point of the refrigerant of the present invention is below -40°C, and the evaporation slip is below 15K. Due to this property, the refrigerant is particularly suitable as a working fluid in air-conditioning equipment for electric vehicles.

[0350] When the ratio of R1234ze to the sum of R1234yf and R1234ze is r (0 < r < 1), and when the mass percentages of HFO-1132(E), R1234yf + R1234ze, and CO2 based on their sum are x, y, and z respectively, in a ternary composition diagram where the sum of HFO-1132(E), R1234yf + R1234ze, and CO2 is 100 mass%, the coordinates (x, y, z) are located within the figure enclosed by connecting the following 7 points in sequence: H r I r 、I r J r 、J r J2 r 、J2 r K2 r 、K2 r K r 、K r Q r 和Q r H r 所围成的图形的范围内或上述线段H r I r 、I r J r 、J r K r 和K r Q r 上(其中,不包括点H r 和点Q r ),

[0351] 点H r (r 2 +9.5r + 12.2, -r 2 -9.5r + 87.8, 0.0),

[0352] 点I r (0.0, -0.6r 2 -1.1r + 98.1, 0.6r 2 +1.1r + 1.9),

[0353] 点J r (0.0, -0.6r 2 +1.9r + 94.8, 0.6r 2 -1.9r + 5.2),

[0354] Point J2 r (10.0, -0.4r 2 + 2.6r + 85.4, 0.4r 2 - 2.6r + 4.6),

[0355] Point K2 r (20.0, 3.0r + 75.1, -3.0r + 4.9),

[0356] Point K r (30.0, -0.4r 2 + 4.2r + 64.0, 0.4r 2 - 4.2r + 6.0),

[0357] Point Q r (70.0, 30.0, 0.0),

[0358] Line segment I r J r , K r Q r and Q r H r are straight lines,

[0359] Line segment H r I r is defined by the coordinates (x, y, z) of the points on it being represented by (x, (-0.003r 2 + 0.0013r - 0.0013)x 2 + (0.102r 2 - 0.0464r - 0.8279)x + (-0.6r 2 - 1.1r + 98.1), (0.003r 2 - 0.0013r + 0.0013)x 2 + (-0.102r 2 + 0.0464r - 0.1721)x + (0.6r 2 + 1.1r + 1.9)),

[0360] Line segment J r J2 r is defined by the coordinates (x, y, z) of the points on it being represented by (x, (0.0068r 2 - 0.0034r - 0.004)x 2 + (0.06r 2 + 0.05r - 0.9)x + (-0.6r 2 + 1.9r + 94.8), (0.004r 2 - 0.002r + 0.004)x 2 + (-0.06r 2-0.05r - 0.1)x + (0.6r 2 -1.9r + 5.2)) represents,

[0361] Line segment J2 r K2 r The coordinates (x, y, z) of the points on the line segment are represented by (x, (0.016r 2 -0.012r - 0.006)x 2 + (-0.44r 2 + 0.4r - 0.85)x + (2.4r 2 - 0.2r + 94.5), (-0.016r 2 + 0.012r + 0.006)x 2 + (0.44r 2 - 0.4r - 0.15)x + (-2.4r 2 + 0.2r + 5.5)) represents,

[0362] Line segment K2 r K r The coordinates (x, y, z) of the points on the line segment are represented by (x, (0.008r 2 -0.008r - 0.002)x 2 + (-0.44r 2 + 0.52r - 1.01)x + (5.6r 2 - 4.2r + 96.1), (-0.008r 2 + 0.008r + 0.002)x 2 + (0.44r 2 - 0.52r + 0.01)x + (-5.6r 2 + 4.2r + 3.9)) represents,

[0363] In this case, the boiling point of the refrigerant of the present application is -40°C or less, and the evaporation glide is 15 K or less. Due to this characteristic, the refrigerant is particularly suitable for working fluid in air conditioning equipment for electric vehicles.

[0364] The coordinates of each point are determined by finding an approximate expression for each point based on the above table. The calculation is performed as shown in Tables 8 to 16, for example.

[0365] [Table 8]

[0366]

[0367] [Table 9]

[0368]

[0369] [Table 10]

[0370]

[0371] [table 11]

[0372]

[0373] [table 12]

[0374]

[0375] [table 13]

[0376]

[0377] [table 14]

[0378]

[0379] [table 15]

[0380]

[0381] [table 16]

[0382]

Claims

1. A composition containing a refrigerant, characterized in that: The refrigerant contains 2,3,3,3-tetrafluoro-1-propene (R1234yf); trans-1,2-difluoroethylene (HFO-1132(E)); and CO2, and optionally 1,3,3,3-tetrafluoropropene (R1234ze), the total amount of which accounts for more than 99.5% by mass of the total refrigerant. Let the mass percentages of HFO-1132(E), R1234yf, and CO2, based on their sum, be x, y, and z, respectively. In a three-component composition diagram where the sum of HFO-1132(E), R1234yf, and CO2 is 100% by mass, the coordinates (x, y, z) lie on the straight line A connecting the following three points. r＝0 B r＝0 B r＝0 O r＝0 and O r＝0 A r＝0 Within the area enclosed by the figure or on the straight line, Point A r＝0 (30.0, 69.1, 0.9) Point B r＝0 (6.2, 83.8, 10.0) Point O r＝0 (30.0, 60.0, 10.0).

2. A composition containing a refrigerant, characterized in that: The refrigerant contains R1234ze; HFO-1132(E); and CO2, as well as optional R1234yf, the total amount of which accounts for more than 99.5% by mass of the total refrigerant. Let x, y, and z be the mass percentages of HFO-1132(E), R1234ze, and CO2, based on their sum. In a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and CO2 is 100% by mass, the coordinates (x, y, z) lie on the straight line A connecting the following three points. r＝1 B r＝1 B r＝1 O r＝1 and O r＝1 A r＝1 Within the area enclosed by the figure or on the straight line, Point A r＝1 (30.0, 62.9, 7.1) Point B r＝1 (23.1, 66.9, 10.0) Point O r＝1 (30.0, 60.0, 10.0).

3. A composition containing a refrigerant, characterized in that: The refrigerant contains R1234yf and R1234ze; HFO-1132(E); and CO2, and the total amount of the above refrigerants accounts for more than 99.5% by mass of the total refrigerant. The ratio of the refrigerant R1234ze to the sum of R1234yf and R1234ze is r. When 0 < r < 1, in a ternary composition diagram where the sum of HFO-1132(E), R1234yf + R1234ze, and CO2 is 100% by mass, if the mass percentages of HFO-1132(E), R1234yf + R1234ze, and CO2 based on their sum are x, y, and z respectively, the coordinates (x, y, z) are located within the figure enclosed by connecting the following three points in sequence: r＝0 B r＝0 , B r＝0 O r＝0 and O r＝0 A r＝0 or on the straight line connecting them. Point A r (30.0, -6.2r + 69.1, 6.2r + 0.9) Point B r (0.2r 2 +16.7r + 6.2, -0.2r 2 -16.7r + 83.8, 10.0), Point O r (30.0, 60.0, 10.0).

4. A composition containing a refrigerant, characterized in that: The refrigerant contains R1234yf; HFO-1132(E); and CO2, as well as optional R1234ze, the total amount of which accounts for more than 99.5% by mass of the total refrigerant. Let x, y, and z be the mass percentages of HFO-1132(E), R1234yf, and CO2, based on their sum. In a three-component composition diagram where the sum of HFO-1132(E), R1234yf, and CO2 is 100% by mass, the coordinates (x, y, z) lie on the line segment H connecting the following seven points. r＝0 I r＝0 I r＝0 J r＝0 J r＝0 J2 r＝0 J2 r＝0 K2 r＝0 K2 r＝0 K r＝0 K r＝0 Q r＝0 and Q r＝ 0H r＝0 Within the area of ​​the enclosed figure or the line segment H r＝0 I r＝0 I r＝0 J r＝0 J r＝0 K r＝0 and K r＝0 Q r＝0 Above, excluding point H r＝0 and point Q r＝0 , Point H r＝0 (12.2, 87.8, 0.0) Point I r＝0 (0.0,98.1,1.9), Point J r＝0 (0.0, 94.8, 5.2) Point J2 r＝0 (10.0, 85.4, 4.6) Point K2 r＝0 (20.0, 75.1, 4.9) Point K r＝0 (30.0, 64.0, 6.0) Click Q r＝0 (30.0, 70.0, 0.0), Line segment I r＝0 J r＝0 K r＝0 Q r＝0 and Q r＝0 H r＝0 It is a straight line. line segment H r＝0 I r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.0013x). 2 -0.8279x + 98.1, 0.0013x 2 -0.1721x+1.9) means, line segment J r＝0 J2 r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.004x). 2 -0.9x + 94.8, 0.004x 2 -0.1x+5.2) means, line segment J2 r＝0 K2 r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.006x). 2 -0.85x + 94.5, 0.006x 2 -0.15x+5.5) means, line segment K2 r＝0 K r＝0 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.002x). 2 -1.01x + 96.1, 0.002x 2 +0.01x+3.9) represents.

5. A composition containing a refrigerant, characterized in that: The refrigerant contains R1234ze; HFO-1132(E); and CO2, as well as optional R1234yf, the total amount of which accounts for more than 99.5% by mass of the total refrigerant. Let x, y, and z be the mass percentages of HFO-1132(E), R1234ze, and CO2, based on their sum. In a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and CO2 is 100% by mass, the coordinates (x, y, z) lie on the line segment H connecting the following seven points. r＝1 I r＝1 I r＝1 J r＝1 J r＝1 J2 r＝1 J2 r＝1 K2 r＝1 K2 r＝1 K r＝1 K r＝1 Q r＝1 and Q r＝ 1H r＝1 Within the area of ​​the enclosed figure or the line segment H r＝1 I r＝1 I r＝1 J r＝1 J r＝1 K r＝1 and K r＝1 Q r＝1 Above, excluding point H r＝1 and point Q r＝1 , Point H r＝1 (22.7,77.3,0.0) Point I r＝1 (0.0,96.4,3.6), Point J r＝1 (0.0, 96.1, 3.9) Point J2 r＝1 (10.0, 87.6, 2.4) Point K2 r＝1 (20.0, 78.1, 1.9) Point K r＝1 (30.0, 67.8, 2.2) Click Q r＝1 (30.0, 70.0, 0.0), Line segment I r＝1 J r＝1 K r＝1 Q r＝1 and Q r＝1 H r＝1 It is a straight line. line segment H r＝1 I r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.003x). 2 -0.7723x + 96.4, 0.003x 2 -0.2277x+3.6) means, line segment J r＝1 J2 r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.006x). 2 -0.79x + 96.1, 0.006x 2 -0.21x+3.9) means, line segment J2 r＝1 K2 r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.002x). 2 -0.89x + 96.7, 0.002x 2 -0.11x+3.3) means, line segment K2 r＝1 K r＝1 The coordinates (x, y, z) of a point on the x-axis are given by (x, -0.002x). 2 -0.93x + 97.5, 0.002x 2 -0.07x+2.5) represents.

6. A composition containing a refrigerant, characterized in that: The refrigerant contains R1234yf and R1234ze; HFO-1132(E); and CO2, and the total amount of the above refrigerants accounts for more than 99.5% by mass of the total refrigerant. The ratio of the refrigerant R1234ze to the sum of R1234yf and R1234ze is r. When 0 < r < 1, in a three-component composition diagram where the sum of HFO-1132(E), R1234yf + R1234ze, and CO2 is 100% by mass, and the mass percentages of HFO-1132(E), R1234yf + R1234ze, and CO2 based on their sum are x, y, and z respectively, the coordinates (x, y, z) are located within the figure enclosed by connecting the following 7 points in sequence: H r I r 、I r J r 、J r J2 r 、J2 r K2 r 、K2 r K r 、K r Q r 和Q r H r or on the line segment H r I r 、I r J r 、J r K r 和K r Q r excluding the points H r and Q r , Point H r (r 2 +9.5r + 12.2, -r 2 -9.5r + 87.8, 0.0), Point I r (0.0, -0.6r) 2 -1.1r+98.1,0.6r 2 +1.1r+1.9), Point J r (0.0, -0.6r) 2 +1.9r +94.8, 0.6r 2 -1.9r+5.2), Point J2 r (10.0, -0.4r) 2 +2.6r +85.4, 0.4r 2 -2.6r+4.6), Point K2 r (20.0,3.0r+75.1,-3.0r+4.9), Point K r (30.0, -0.4r) 2 +4.2r +64.0, 0.4r 2 -4.2r+6.0), Click Q r (70.0, 30.0, 0.0), Line segment I r J r K r Q r and Q r H r It is a straight line. line segment H r I r The coordinates (x, y, z) of a point on the x-axis are given by (x, (-0.003r). 2 +0.0013r-0.0013)x 2 +(0.102r 2 -0.0464r-0.8279)x+(-0.6r 2 -1.1r+98.1),(0.003r 2 -0.0013r+0.0013)x 2 +(-0.102r 2 +0.0464r-0.1721)x+(0.6r 2 +1.1r+1.9)) means, line segment J r J2 r The coordinates (x, y, z) of a point on the x-axis are given by (x, (0.0068r). 2 -0.0034r-0.004)x 2 +(0.06r 2 +0.05r-0.9)x+(-0.6r 2 +1.9r+94.8),(0.004r 2 -0.002r+0.004)x 2 +(-0.06r 2 -0.05r-0.1)x+(0.6r 2 -1.9r+5.2)) means, line segment J2 r K2 r The coordinates (x, y, z) of a point on the x-axis are given by (x, (0.016r). 2 -0.012r-0.006)x 2 +(-0.44r 2 +0.4r-0.85)x+(2.4r 2 -0.2r+94.5),(-0.016r 2 +0.012r+0.006)x 2 +(0.44r 2 -0.4r-0.15)x+(-2.4r 2 +0.2r+5.5)) means, line segment K2 r K r The coordinates (x, y, z) of a point on the x-axis are given by (x, (0.008r). 2 -0.008r-0.002)x 2 +(-0.44r 2 +0.52r-1.01)x+(5.6r 2 -4.2r+96.1),(-0.008r 2 +0.008r+0.002)x 2 +(0.44r 2 -0.52r+0.01)x+(-5.6r 2 +4.2r+3.9)) represents.

7. The composition according to any one of claims 1 to 6, characterized in that: It also contains refrigeration oil, and the composition is used as a working fluid for refrigeration machines.

8. The composition according to any one of claims 1 to 3, characterized in that: It is used as an alternative refrigerant to R134a, R1234yf, and R404A.

9. Use of the composition according to any one of claims 1 to 3 as a refrigerant.

10. A refrigerant for electric vehicles, characterized in that: The composition comprising any one of claims 4 to 6.

11. A refrigeration unit, characterized in that: The composition comprising any one of claims 1 to 7 is used as the working fluid.

12. A method for operating a refrigeration unit, characterized in that: The method includes the step of circulating the composition of any one of claims 1 to 7 as a working fluid in a refrigeration unit.

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