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

Abstract

To provide a novel low-GWP mixed refrigerant.SOLUTION: A composition contains a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)) and propane, and the total content of HFO-1132(E) and propane is 99.5 mass% or more with respect to the total refrigerant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to compositions comprising refrigerants, uses thereof, and chillers having same and methods of operating such chillers. [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 contains trans-1,2-difluoroethylene (HFO-1132(E)) and propane, and the total content of HFO-1132(E) and propane is 99.5% by mass or more based on the total content of the refrigerant. is: Contains 25.0% by mass to 29.2% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 30.7% by mass to 38.9% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 43.5% by mass to 48.5% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 51.2% by mass to 56.3% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 61.4% by mass to 66.8% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 72.4% by mass to 75.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 20.6% by mass to 29.9% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 32.0% by mass to 37.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 42.2% by mass to 48.8% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 50.4% by mass to 57.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 62.3% by mass to 68.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 70.8% to 75.0% by mass of HFO-1132(E) based on the total of HFO-1132(E) and propane ; Contains 7.0% by mass to 9.7% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 10.4% by mass to 18.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 20.6% by mass to 29.4% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 31.3% by mass to 38.7% by mass of HFO-1132(E) based on the total of HFO-1132(E) and propane; or Contains 40.6% by mass to 48.5% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 50.8% by mass to 58.8% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; Contains 60.1% by mass to 69.2% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; or Contains 70.3% by mass to 75.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; composition. Section 2. Item 1, wherein the refrigerant further comprises at least one selected from the group consisting of 1,1-difluoroethylene (HFO-1132a) and 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124). Section 3. Item 3. The composition according to item 1 or 2, further comprising 0.1% by mass or less of water based on the total composition. . Section 4. Any of items 1 to 3 used as an alternative refrigerant to R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. The composition described in claim 1. Section 5. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E) and propane, The total content of HFO-1132(E) and propane is 99.5% by mass or more, and the total content of HFO-1132(E) and propane is 20.6 to 75.0% by mass. COP ratio based on R1234yf is 99% or more, and refrigeration capacity ratio based on R1234yf is 200% The composition for use in the refrigeration cycle operation of an air conditioner for an electric vehicle is as described above. Section 6. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), difluoroethylene (R32) and propane, the total content of HFO-1132(E), R32 and propane being 99.5 mass% or more relative to the total content of the refrigerants, The mass percentages of HFO-1132(E), R32 and propane based on the sum of these are x, y and In a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is 100% by mass, the coordinates (x, y, z) are: Point C(60.0, 40.0, 0.0), Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point R(10.0, 44.2, 45.8) Point A(55.7, 44.3, 55.8), Within the area of ​​the figure enclosed by the straight lines CP, PQ, QR, RA, and AC connecting the above five points, or on the straight lines CP, QR, and RA (however, points A, C, P, and Q are excluded), R410A replacement composition. Section 7. A composition containing a refrigerant, the refrigerant including HFO-1132(E), R32 and propane, the total content of HFO-1132(E), R32 and propane being 99.5 mass% or more relative to the total content of the refrigerants. can be, The mass percentages of HFO-1132(E), R32 and propane based on the sum of these are x, y and In a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is 100% by mass, the coordinates (x, y, z) are: Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point K(10.0, 21.9, 68.1) Point J(66.7, 22.1, 11.2) Within the area enclosed by the straight lines PQ, QK, KJ, and JP connecting the four points above, or on the straight lines JP, QK, and KJ. Compositions for replacing R1234yf and / or R404A. Section 8. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), R32, propane and carbon dioxide (CO2), the total content of the HFO-1132(E), R32, propane and CO2 being 99.5 mass% or more relative to the total content of the refrigerants, When the mass percentages of CO2, HFO-1132(E), R32 and propane based on the sum of these are a, x, y and z, respectively, the sum of HFO-1132(E), R32 and propane is (100-a) mass percentage. In the three-component composition diagram, the coordinates (x, y, z) are: 0.0 <a≦10.0のとき Point C'(60.0, -a+40.0, 0.0), Point D'(75.0, 0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point R'(10.0, 44.2, -a+45.8) Point A'(-a+55.7, 44.3, 0.0), Within the area enclosed by the straight lines C'D', D'Q', Q'R', R'A' and A'C' connecting the above five points, or on said straight lines C'D', Q'R' and R'A' (however, points A', C', D' and Q' are excluded), R410A replacement composition. Section 9. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), R32, propane and CO2; The total content of HFO-1132(E), R32 propane and CO2 is 99.5% of the total of the above refrigerants. % or more, When the mass percentages of CO2, HFO-1132(E), R32 and propane based on the sum of these are a, x, y and z, respectively, the sum of HFO-1132(E), R32 and propane is (100-a) mass percentage. In the three-component composition diagram, the coordinates (x, y, z) are: 0.0 <a≦0.5のとき Point J'( 66.7, 22.1,-a+11.2) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on said straight lines J'D', Q'K', and K'J', 0.5 <a≦10.0のとき Point J'( -0.0524a2+0.266a+66.58, 22.1, 0.0524a2-1.266a+11.32) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on the straight lines J'D', Q'K', and K'J' A composition for replacing R1234yf and / or R404A. Section 10. 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 items 1 to 9. Section 11. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of items 1 to 9. Section 12. 10. A refrigerator comprising the composition according to any one of items 1 to 9 as a working fluid. Section 13. Item 10. Use of the composition according to any one of items 1 to 9 as a working fluid in a refrigerator. 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. 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 (1) a refrigerant itself (a mixture of refrigerants) and The present invention includes at least: (1) a composition which further contains other components and can be used to obtain a working fluid for a refrigerating machine by mixing with at least a refrigerating machine oil; and (2) a working fluid for a refrigerating machine containing a refrigerating machine oil. In this specification, of these three aspects, the composition in (2) is referred to as a "refrigerant composition" to distinguish it from a refrigerant itself (including a mixture of refrigerants). Also, the working fluid for a refrigerating machine in (3) is referred to as a "refrigerating machine oil-containing working fluid" to distinguish it from the "refrigerant composition".

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

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

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

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

[0015] Pressures described in this specification are in units of absolute pressure unless otherwise specified.

[0016] 1. Refrigerant The refrigerant disclosed herein contains trans-1,2-difluoroethylene (HFO-1132(E)) and propane, and the total content of HFO-1132(E) and propane is 99.5% by mass based on the total content of the refrigerant. And that's it: (1) containing 25.0% by mass to 29.2% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane; (2) HFO-1132(E) is contained in an amount of 30.7% by mass to 38.9% by mass based on the total amount of HFO-1132(E) and propane; (3) HFO-1132(E) is contained in an amount of 43.5% by mass to 48.5% by mass based on the total amount of HFO-1132(E) and propane; (4) HFO-1132(E) is contained in an amount of 51.2% by mass to 56.3% by mass based on the total amount of HFO-1132(E) and propane; (5) HFO-1132(E) is contained in an amount of 61.4% by mass to 66.8% by mass based on the total amount of HFO-1132(E) and propane; (6) HFO-1132(E) is contained in an amount of 72.4% by mass to 75.0% by mass based on the total amount of HFO-1132(E) and propane; (7) HFO-1132(E) is contained in an amount of 20.6% by mass to 29.9% by mass based on the total amount of HFO-1132(E) and propane; (8) HFO-1132(E) is contained in an amount of 32.0% by mass to 37.0% by mass based on the total amount of HFO-1132(E) and propane; (9) HFO-1132(E) is contained in an amount of 42.2% by mass to 48.8% by mass based on the total amount of HFO-1132(E) and propane; (10) HFO-1132(E) is contained in an amount of 50.4% by mass to 57.0% by mass based on the total amount of HFO-1132(E) and propane; (11) HFO-1132(E) is contained in an amount of 62.3% by mass to 68.0% by mass based on the total amount of HFO-1132(E) and propane; (12) HFO-1132(E) is contained in an amount of 70.8% by mass to 75.0% by mass based on the total amount of HFO-1132(E) and propane; (13) HFO-1132(E) is contained in an amount of 7.0% by mass to 9.7% by mass based on the total amount of HFO-1132(E) and propane; (14) HFO-1132(E) is contained in an amount of 10.4% by mass to 18.0% by mass, based on the total amount of HFO-1132(E) and propane; (15) HFO-1132(E) is contained in an amount of 20.6% by mass to 29.4% by mass based on the total amount of HFO-1132(E) and propane; (16) HFO-1132(E) is contained in an amount of 31.3% by mass to 38.7% by mass based on the total amount of HFO-1132(E) and propane; or (17) HFO-1132(E) is contained in an amount of 40.6% by mass to 48.5% by mass based on the total amount of HFO-1132(E) and propane. (18) HFO-1132(E) is contained in an amount of 50.8% by mass to 58.8% by mass based on the total amount of HFO-1132(E) and propane; (19) HFO-1132(E) is contained in an amount of 60.1% by mass to 69.2% by mass based on the total amount of HFO-1132(E) and propane; or (20) The fuel contains 70.3% by mass to 75.0% by mass of HFO-1132(E), based on the total amount of HFO-1132(E) and propane.

[0017] The refrigerants of the present disclosure are low GWP refrigerant mixtures.

[0018] The refrigerant (1) has a refrigeration capacity ratio of 73% or more compared to R410A and a COP ratio of 103.25% or more compared to R410A. It is.

[0019] The refrigerant (2) has a refrigeration capacity ratio of 76% or more compared to R410A and a COP ratio of 102% or more compared to R410A.

[0020] The refrigerant (3) has a condensation glide of 5.0K or less and an ACOP ratio to R410 of 100.5% or more.

[0021] The refrigerant (4) has a condensation glide of 3.75K or less and an ACOP ratio of 99.5% or more relative to R410.

[0022] The refrigerant (5) has a condensation glide of 2.0K or less and an ACOP ratio of 98.75% or more relative to R410.

[0023] The refrigerant (6) has a refrigeration capacity of 95% or more compared to R410A, and the refrigerant temperature is 3 MPa and 150°C. No disproportionation reaction occurs.

[0024] The refrigerant of the present disclosure contains 99.5% or more of HFO-1132(E) and propane, and may further contain 0.5% by mass or less of at least one selected from HFO-1132a and R124.

[0025] The refrigerant disclosed herein contains 99.5% or more of HFO-1132(E) and propane, and contains 25.0% by mass to 75.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane, and further contains HFO-1132a and R124. An alternative refrigerant to R410A, comprising 0.5% by mass or less of at least one selected from the group consisting of This refrigerant has a refrigeration capacity of 73% or more compared to R410A, and the refrigerant is 3Mpa and 150℃. No disproportionation reaction occurs.

[0026] The refrigerant (7) has a refrigeration capacity ratio of 200% or more relative to R1234yf and a COP ratio of 102.0% or more relative to R1234yf. Above.

[0027] The refrigerant (8) has a condensation glide of 6.6K or less and a COP ratio relative to R1234yf of 101.5% or more.

[0028] The refrigerant (9) has a condensation glide of 5.6K or less and a COP ratio of 100.25% or more relative to R1234yf. be.

[0029] The refrigerant (10) has a freezing capacity ratio to R1234yf of 250% or more and a COP ratio to R1234yf of 99.5% or more.

[0030] The refrigerant (11) has a condensation glide of 2.0K or less and a COP ratio of 99.1% or more relative to R1234yf. be.

[0031] The refrigerant (12) has a freezing capacity ratio of 280% or more relative to R1234yf, and does not undergo a disproportionation reaction even when the refrigerant reaches 3 MPa and 150°C.

[0032] The refrigerant disclosed herein contains 99.5% or more of HFO-1132(E) and propane, and contains 20.6% by mass to 75.0% by mass of HFO-1132(E) based on the total amount of HFO-1132(E) and propane, and further contains HFO-1132a and R124. An alternative refrigerant to R1234yf containing 0.5 mass% or less of at least one selected from the group consisting of This refrigerant has a refrigeration capacity ratio of 200% or more relative to R1234yf, and does not undergo disproportionation reactions even when the refrigerant reaches 3 MPa and 150°C.

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

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

[0035] The refrigerant (13) has a refrigeration capacity ratio of 100% or more compared to R404A and a COP ratio of 112.2% or more compared to R404A. Above.

[0036] The refrigerant (14) has a refrigeration capacity ratio of 103% or more compared to R404A and a COP ratio of 111% or more compared to R404A. It is.

[0037] The refrigerant (15) has a refrigeration capacity ratio of 112% or more to R404A and a discharge pressure ratio of 100% or more to R404A. Above.

[0038] The refrigerant (16) has a refrigeration capacity ratio of 122% or more compared to R404A and a COP ratio of 108.0% or more compared to R404A. Above.

[0039] The refrigerant (17) has a refrigeration capacity ratio of 131% or more compared to R404A and a COP ratio of 106.5% or more compared to R404A. Above.

[0040] The refrigerant (18) has a condensation glide of 4.0K or less and an ACOP ratio to R404 of 105% or more.

[0041] The refrigerant (19) has a refrigeration capacity ratio of 140% or more compared to R404A and a COP ratio of 104.2% or more compared to R404A. Above.

[0042] The refrigerant (20) has a refrigeration capacity ratio of 157% or more relative to R404A, and does not undergo disproportionation reaction even when the refrigerant reaches 3 MPa and 150°C.

[0043] The refrigerant of the present disclosure may be an alternative refrigerant to R404A that contains 99.5% or more of HFO-1132(E) and propane, contains 7.0% by mass to 75.0% by mass of HFO-1132(E) based on the total of HFO-1132(E) and propane, and contains 0.5% by mass or less of at least one selected from HFO-1132a and R124. The refrigerant does not undergo disproportionation even when its refrigeration capacity against R404A is 100% or more and the refrigerant reaches 3 MPa and 150°C.

[0044] In the refrigerant disclosed herein, the refrigerant comprises HFO-1132(E), difluoroethylene (R32), and propane, and the total content of the HFO-1132(E), R32, and propane is 99.5 mass% or more relative to the total content of the refrigerants; The mass percentages of HFO-1132(E), R32 and propane based on the sum of these are x, y and In a ternary composition diagram in which the sum of HFO-1132(E), R32 and propane is 100% by mass, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R410A is 70% or more, and the GWP is 300 or less. Point C(60.0, 40.0, 0.0), Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point R(10.0, 44.2, 45.8) Point A(55.7, 44.3, 55.8), The point A is within the area enclosed by the straight lines CP, PQ, QR, RA, and AC connecting the five points above, or is on the straight lines CP, QR, and RA (however, points A, C, P, and Q are excluded).

[0045] In the refrigerant disclosed herein, the refrigerant comprises HFO-1132(E), difluoroethylene (R32), and propane, and the total content of the HFO-1132(E), R32, and propane is 99.5 mass% or more relative to the total content of the refrigerants; The mass percentages of HFO-1132(E), R32 and propane based on the sum of these are x, y and In a ternary composition diagram where the sum of HFO-1132(E), R32 and propane is 100% by mass, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R1234yf is 197.5% or more, the refrigeration capacity (Cap) ratio to R404A is 110% or more, and the GWP is 150 or less. Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point K(10.0, 21.9, 68.1) Point J(66.7, 22.1, 11.2) It is within the area surrounded by the straight lines PQ, QK, KJ, and JP connecting these four points, or is on the straight lines JP, QK, and KJ.

[0046] In addition, the refrigerant disclosed herein has a boiling point of -40.0°C or lower, so it is suitable for heating using a heat pump. For example, the refrigerant of the present disclosure has an advantage that it is easy to use in a vehicle. For example, by using the refrigerant of the present disclosure to operate the refrigeration cycle of an in-vehicle air conditioner, it is possible to perform heating using a heat pump that consumes less power than an electric heater. Examples of in-vehicle air conditioners include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0047] In the refrigerant disclosed herein, the refrigerant is HFO-1132 (E), R32, propane and carbon dioxide (CO2). The total content of HFO-1132(E), R32, propane and CO2 in relation to the total of the above refrigerants is 99.5% by mass or more, When the mass percentages of CO2, HFO-1132(E), R32 and propane based on the sum of these are a, x, y and z, respectively, the sum of HFO-1132(E), R32 and propane is (100-a) mass percentage. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C, and the refrigeration capacity (Cap) ratio to R410A is 65.0% or more. And the GWP is 300 or less. 0.0 <a≦10.0のとき Point C'(60.0, -a+40.0, 0.0), Point D'(75.0, 0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point R'(10.0, 44.2, -a+45.8) Point A'(-a+55.7, 44.3, 0.0), It is within the area surrounded by the figure bounded by straight lines C'D', D'Q', Q'R', R'A', and A'C', connecting the five points above, or on said straight lines C'D', Q'R', and R'A' (but excluding points A', C', D', and Q').

[0048] In the refrigerant of the present disclosure, the refrigerant includes HFO-1132(E), R32, propane and CO2, The total content of HFO-1132(E), R32 propane and CO2 is 99.5% by mass or more, When the mass percentages of CO2, HFO-1132(E), R32 and propane based on the sum of these are a, x, y and z, respectively, the sum of HFO-1132(E), R32 and propane is (100-a) mass percentage. In a three-component composition diagram in which the components are expressed in terms of percent by volume, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R1234yf is 185.0% or more, the refrigeration capacity (Cap) ratio to R404A is 103.7 or more, and the GWP is 150 or less. 0.0 <a≦0.5のとき Point J'( 66.7, 22.1,-a+11.2 ) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on said straight lines J'D', Q'K', and K'J', 0.5 <a≦10.0のとき Point J'( -0.0524a2+0.266a+66.58, 22.1, 0.0524a2-1.266a+11.32) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) It is within the area surrounded by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or is on said straight lines J'D', Q'K', and K'J'.

[0049] In addition, the refrigerant disclosed herein has a boiling point of -40.0°C or lower, so it is suitable for heating using a heat pump. For example, the refrigerant of the present disclosure has an advantage that it is easy to use in a vehicle. For example, by using the refrigerant of the present disclosure to operate the refrigeration cycle of an in-vehicle air conditioner, it is possible to perform heating using a heat pump that consumes less power than an electric heater. Examples of in-vehicle air conditioners include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0050] Furthermore, the refrigerant disclosed herein is a mixture of propane and HFO-1132(E) and / or R32, which are less flammable than propane, and / or CO2, but is not a non-flammable refrigerant or a slightly flammable refrigerant. Therefore, the refrigerant disclosed herein may be used as the heat source side refrigerant in a refrigeration system that includes a user-side heat transport cycle for circulating a user-side refrigerant, a heat source-side heat transport cycle for circulating a heat source-side refrigerant, and a cascade heat exchanger for exchanging heat between the user-side refrigerant and the heat source-side refrigerant.

[0051] The refrigerant of the present disclosure may contain, in addition to the above-mentioned refrigerants, an additional refrigerant within a range that does not impair the above-mentioned properties and effects. In this regard, in one embodiment, the refrigerant of the present disclosure contains a total of HFO-1132(E) and propane, and optionally R32 and / or CO2, in the total refrigerant. It is preferable that the refrigerant 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. The refrigerant of the present disclosure may be substantially composed of HFO-1132(E) and propane, and optionally R32 and / or CO2, in which case the refrigerant of the present disclosure may be composed of HFO-1132(E) and propane, and optionally R32 and / or CO2, and unavoidable impurities. The refrigerant of the present disclosure may be composed of HFO-1132(E) and propane, and optionally R32 and / or CO2.

[0052] 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.

[0053] Additional refrigerants include acetylene, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, CFC-1113, 3,3,3-trifluoropropyne, R152a, and the like.

[0054] 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 used by mixing it 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 a refrigerating machine oil content of 1 mass% or more relative to the entire refrigerant composition. It is preferably 0.1 mass % or less, and more preferably 0.1 mass % or less.

[0055] 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.

[0056] The compositions of the present disclosure include compositions comprising a refrigerant, the refrigerant being HFO-1132(E) and propane. Also included are compositions containing ethanol, optionally R32 and / or CO2, and 0.1% or less water.

[0057] 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.

[0058] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0059] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0060] 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). Particularly preferred are trifluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers.

[0061] As tracers, the following compounds are preferred: FC-14 (Tetrafluoromethane, CF4) HCC-40 (chloromethane, CH3Cl) HFC-23 (Trifluoromethane, CHF3) HFC-41 (fluoromethane, CH3F) HFC-125 (Pentafluoroethane, CF3CHF2) HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F) HFC-134 (1,1,2,2-Tetrafluoroethane, CHF2CHF2) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-152a (1,1-difluoroethane, CHF2CH3) HFC-152 (1,2-difluoroethane, CH2FCH2F) HFC-161 (Fluoroethane, CH3CH2F) HFC-245fa (1,1,1,3,3-Pentafluoropropane, CF3CH2CHF2) HFC-236fa (1,1,1,3,3,3-Hexafluoropropane, CF3CH2CF3) HFC-236ea (1,1,1,2,3,3-Hexafluoropropane, CF3CHFCHF2) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3) HCFC-22 (Chlorodifluoromethane, CHClF2) HCFC-31 (Chlorofluoromethane, CH2ClF) 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)

[0062] 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, or more. 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 preferably contain a total of about 30 ppm or more of tracer(s) based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain up to about 500 ppm, and more preferably up to about 300 ppm, of the total tracer based on the total refrigerant composition.

[0063] 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.

[0064] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0065] 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.

[0066] 2.4 Stabilizers The refrigerant composition of the present disclosure may contain one type of stabilizer alone, or may contain two or more types of stabilizers.

[0067] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0068] The stabilizers include, for example, nitro compounds, ethers, and amines.

[0069] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0070] An example of the ethers is 1,4-dioxane.

[0071] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine, diphenylamine, and the like.

[0072] Other examples include butylhydroxyxylene and benzotriazole.

[0073] 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.

[0074] 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.

[0075] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 3.1 Refrigerating machine oil The refrigerant 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0087] 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.

[0088] 3.3 Purpose The refrigerant, refrigerant composition, or refrigerating machine oil-containing working fluid of the present disclosure is R12, R22, R134a, R It can be used as an alternative refrigerant to 404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze.

[0089] 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.

[0090] Specifically, a method of operating a refrigerator of the present disclosure includes circulating a refrigerant of the present disclosure in the refrigerator.

[0091] 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.

[0092] 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 3.0 MPa and the refrigerant temperature is 150° C., is achieved. Obtained.

[0093] 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.

[0094] 6. Use for inhibiting disproportionation reactions The use of the present disclosure includes the disproportionation of HFO-1132(E) with propane, and / or R32, and / or CO2. The use of HFO-1132(E) and propane for inhibiting a disproportionation reaction, This is done by mixing R2, R32, and / or CO2 in the refrigerant mixing ratio of the present disclosure.

[0095] When used to inhibit a disproportionation reaction according to the present disclosure, the effect is particularly that the disproportionation reaction of HFO-1132(E) does not occur even when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0096] 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

[0097] The present disclosure will be described in more detail below by way of examples, although the present disclosure is not limited to these examples.

[0098] A mixed refrigerant was prepared by mixing HFO-1132(E), propane, and / or R32, and / or RCO2 in the mass % shown in each table, based on the sum of these.

[0099] 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: 3 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. .

[0100] [Table 1]

[0101] From the results in Table 1 and Figure 1, in the case of a mixture of HFO-1132(E), R32, and propane, the disproportionation reaction does not occur below the disproportionation limit line shown in the triangular diagram in Figure 1, even when the refrigerant reaches 3 MPa and 150°C. It becomes clear that...

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] From the results in Tables 2, 3, and 4 and Figures 2, 3, and 4, it can be seen that in a mixture of HFO-1132(E), R32, propane, and CO2, no disproportionation reaction occurs below the disproportionation limit lines shown in the triangular diagrams in Figures 2, 3, and 4, even when the refrigerant reaches 3 MPa and 150°C.

[0106] HFO-1132(E), propane, and / or R32, and / or CO2 are used as the sum of these. A mixed refrigerant was prepared by mixing the components in the amounts shown in each table by mass percentage.

[0107] The physical properties of each of these mixed refrigerants were evaluated using the following test methods and conditions.

[0108] The GWP of HFO-1132(E) is set to 1, and the GWPs of propane, R32, and CO2 are based on the GWPs set by the IPCC (Intergovernmental Panel on Climate Change). The GWP of the mixed refrigerant was evaluated based on the values ​​in the Fourth Assessment Report of the Panel on Climate Change. In addition, the COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were calculated using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions by performing theoretical calculations of the refrigeration cycle of the mixed refrigerant. The physical property data for HFO-1132(E) was determined from actual measurements. <Compared to R410A> Evaporation temperature: 5℃ Condensation temperature 45℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70% <Compared to R1234yf> Evaporation temperature -30℃ Condensation temperature 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency 70% <Compared to R404A> Evaporation temperature -40℃ Condensation temperature 40℃ Superheat temperature 20K Supercooling temperature 0K Compressor efficiency 70%

[0109] The coefficient of performance (COP) was calculated using the following formula. COP = (refrigeration capacity) / power consumption

[0110] In Tables 1 and 2, "COP ratio," "refrigerating capacity ratio," and "discharge pressure ratio" indicate the ratio (%) relative to R410A.

[0111] [Table 5]

[0112] [Table 6]

[0113] The results in Tables 5 and 6 reveal the following:

[0114] The refrigerant (1) has a refrigeration capacity ratio of 73% or more compared to R410A and a COP ratio of 103.25% or more compared to R410A. It is.

[0115] The refrigerant (2) has a refrigeration capacity ratio of 76% or more compared to R410A and a COP ratio of 102% or more compared to R410A. The refrigerant (3) has a condensation glide of 5.0K or less and an ACOP ratio to R410 of 100.5% or more.

[0116] The refrigerant (4) has a condensation glide of 3.75K or less and an ACOP ratio of 99.5% or more relative to R410.

[0117] The refrigerant (5) has a condensation glide of 2.0K or less and an ACOP ratio of 98.75% or more relative to R410.

[0118] The refrigerant (6) has a refrigeration capacity of 95% or more compared to R410A, and the refrigerant temperature is 3 MPa and 150°C. No disproportionation reaction occurs.

[0119] Furthermore, the effects of the inclusion of various impurities were evaluated as shown in Table 7.

[0120] [Table 7]

[0121] From the results in Table 7, it can be seen that the refrigerant of the present disclosure may be an alternative refrigerant to R410A that contains 99.5% or more of HFO-1132(E) and propane, contains 25.0% to 75% by mass of HFO-1132(E) relative to the total of HFO-1132(E) and propane, and contains 0.5% by mass or less of at least one selected from the group consisting of HFO-1132a and R124. This refrigerant has a refrigeration capacity ratio of 73% or more relative to R410A, and does not undergo disproportionation reaction even when the refrigerant reaches 3 MPa and 150°C.

[0122] From the results in Table 7, it can be seen that the refrigerant of the present disclosure contains 99.5% or more of HFO-1132(E) and propane, and may further contain 0.5% by mass or less of at least one selected from HFO-1132a and R124. It turns out that...

[0123] HFO-1132(E) and propane are shown in Tables 8 and 9, respectively, based on their sum. A mixed refrigerant was prepared by mixing the above components at the above mass %.

[0124] [Table 8]

[0125] [Table 9]

[0126] The various physical properties of each of these mixed refrigerants were evaluated using the same test methods and conditions as above.

[0127] In Tables 8 and 9, "COP ratio" and "refrigeration capacity ratio" are the ratios (% ) is shown.

[0128] The results in Tables 8 and 9 reveal the following:

[0129] The refrigerant (7) has a refrigeration capacity ratio of 200% or more relative to R1234yf and a COP ratio of 102.0% or more relative to R1234yf. Above.

[0130] The refrigerant (8) has a condensation glide of 6.6K or less and a COP ratio relative to R1234yf of 101.5% or more.

[0131] The refrigerant (9) has a condensation glide of 5.6K or less and a COP ratio of 100.25% or more relative to R1234yf. be.

[0132] The refrigerant (10) has a freezing capacity ratio to R1234yf of 250% or more and a COP ratio to R1234yf of 99.5% or more.

[0133] The refrigerant (11) has a condensation glide of 2.0K or less and a COP ratio of 99.1% or more relative to R1234yf. be.

[0134] The refrigerant (12) has a freezing capacity ratio of 280% or more relative to R1234yf, and does not undergo a disproportionation reaction even when the refrigerant reaches 3 MPa and 150°C.

[0135] Furthermore, the effects of the inclusion of various impurities were evaluated as shown in Table 6.

[0136] [Table 10]

[0137] From the results in Table 6, it can be seen that the refrigerant of the present disclosure may be an alternative refrigerant to R1234yf that contains 99.5% or more of HFO-1132(E) and propane, contains 20.6% by mass to 75.0% by mass of HFO-1132(E) relative to the total of HFO-1132(E) and propane, and contains 0.5% by mass or less of at least one selected from the group consisting of HFO-1132a and R124. This refrigerant has a refrigeration capacity ratio of 200% or more relative to R1234yf, or In addition, even when the refrigerant reaches 3 MPa and 150°C, no disproportionation reaction occurs.

[0138] From the results in Table 10, the refrigerant of the present disclosure contains 99.5% or more of HFO-1132(E) and propane, and may further contain 0.5% by mass or less of at least one selected from HFO-1132a and R124. It becomes clear that...

[0139] HFO-1132(E) and propane are shown in Tables 7 and 8, respectively, based on their sum. A mixed refrigerant was prepared by mixing the above components at the above mass %.

[0140] [Table 11]

[0141] [Table 12]

[0142] For each of these mixed refrigerants, various physical properties were measured using the same test methods and conditions as above. was evaluated.

[0143] In addition, in Tables 11 and 12, "COP ratio," "refrigerating capacity ratio," and "discharge pressure ratio" indicate the ratio (%) to R404A.

[0144] The results in Tables 11 and 12 reveal the following:

[0145] The refrigerant (13) has a refrigeration capacity ratio of 100% or more compared to R404A and a COP ratio of 112.2% or more compared to R404A. Above.

[0146] The refrigerant (14) has a refrigeration capacity ratio of 103% or more compared to R404A and a COP ratio of 111% or more compared to R404A. It is.

[0147] The refrigerant (15) has a refrigeration capacity ratio to R404A of 112% or more and a discharge pressure ratio to R404A of 100% or less.

[0148] The refrigerant (16) has a refrigeration capacity ratio of 122% or more compared to R404A and a COP ratio of 108.0% or more compared to R404A. Above.

[0149] The refrigerant (17) has a refrigeration capacity ratio of 131% or more compared to R404A and a COP ratio of 106.5% or more compared to R404A. Above.

[0150] The refrigerant (18) has a condensation glide of 4.0K or less and an ACOP ratio to R404 of 105% or more.

[0151] The refrigerant (19) has a refrigeration capacity ratio of 140% or more compared to R404A and a COP ratio of 104.2% or more compared to R404A. Above.

[0152] The refrigerant (20) has a refrigeration capacity ratio of 157% or more relative to R404A, and does not undergo disproportionation reaction even when the refrigerant reaches 3 MPa and 150°C.

[0153] Furthermore, the effects of the inclusion of various impurities were evaluated as shown in Table 13.

[0154] [Table 13]

[0155] From the results in Table 13, it can be seen that the refrigerant of the present disclosure may be an alternative refrigerant to R404A that contains 99.5% or more of HFO-1132(E) and propane, contains 7.0% to 75% by mass of HFO-1132(E) relative to the total of HFO-1132(E) and propane, and contains 0.5% by mass or less of at least one selected from the group consisting of HFO-1132a, R143a, R134a, R124, and R152a. This refrigerant has a refrigeration capacity greater than that of R404A. Even if the pressure ratio is 100% or more and the refrigerant temperature is 3 MPa and 150°C, no disproportionation reaction occurs.

[0156] From the results in Table 13, the refrigerant of the present disclosure further contains 1,1-difluoroethylene (HFO-1132a). and 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124). It is understood that the composition may contain at least one of the above.

[0157] The components were mixed in the ratios shown in Table 10, and the acid content (acid component) and appearance of the resulting compositions were evaluated as follows.

[0158] In the stability test of the composition, the analysis of the acid content in the gas was carried out by the following method. The gas remaining in the tube after cooling was completely solidified using liquid nitrogen. The tube was then opened and gradually thawed, and the gas was collected in a Tedlar bag. 5 g of pure water was poured into the Tedlar bag, and the acid content was extracted into the pure water while being in close contact with the collected gas. The extract was detected by ion chromatography, and the content (ppm by mass) of fluoride ions (F-) was measured.

[0159] [Table 14]

[0160] As shown in Table 14, in the presence of 0.01 mol% or more of oxygen, the generation of oxidative decomposition products can be confirmed. Furthermore, in the presence of 0.01 mol% or more of oxygen, when the amount of water added is at least 10 ppm by mass, the generation of oxidative decomposition products is suppressed. It is also found that in the presence of 0.01 mol% or more of oxygen, when the amount of water added is less than 2000 ppm by mass, the generation of solids is suppressed.

[0161] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and propane in the mass percentages shown in Tables 15 and 16, respectively, based on the sum of these.

[0162] [Table 15]

[0163] [Table 16]

[0164] As shown in Tables 15 and 16 and Figure 5, when the mass percentages of HFO-1132(E), R32 and propane based on their sum are x, y and z, respectively, in a ternary composition diagram where the sum of HFO-1132(E), R32 and propane is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the refrigerant will not undergo disproportionation reactions at 3 MPa and 150°C, its refrigeration capacity (Cap) ratio to R410A will be 70% or more, and its GWP will be 300 or less. Point C(60.0, 40.0, 0.0), Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point R(10.0, 44.2, 45.8) Point A(55.7, 44.3, 55.8), The point A is within the area enclosed by the straight lines CP, PQ, QR, RA, and AC connecting the five points above, or is on the straight lines CP, QR, and RA (however, points A, C, P, and Q are excluded).

[0165] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and propane in the mass percentages shown in Tables 17 and 18, respectively, based on the sum of these.

[0166] [Table 17]

[0167] [Table 18]

[0168] As shown in Tables 17 and 18 and Figure 6, When the mass percentages of HFO-1132(E), R32 and propane based on their total sum are x, y and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32 and propane is 100 mass%, When the coordinates (x, y, z) satisfy the following requirements, the refrigerant does not undergo disproportionation reactions at 3 MPa and 150°C, the refrigerant's refrigeration capacity (Cap) ratio to R1234yf is 197.5% or more, and the GWP is 150 or less. Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point K(10.0, 21.9, 68.1) Point J(66.7, 22.1, 11.2) It is within the area surrounded by the straight lines PQ, QK, KJ, and JP connecting these four points, or is on the straight lines JP, QK, and KJ.

[0169] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and propane in the mass percentages shown in Tables 19 and 20, respectively, based on the sum of these.

[0170] [Table 19]

[0171] [Table 20]

[0172] As shown in Tables 19 and 20 and Figure 7, When the mass percentages of HFO-1132(E), R32 and propane based on their total sum are x, y and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32 and propane is 100 mass%, When the coordinates (x, y, z) satisfy the following requirements, the refrigerant does not undergo disproportionation reactions at 3 MPa and 150°C, the refrigerant's refrigeration capacity (Cap) ratio to R404A is 110% or more, and the GWP is 150 or less. Point P(73.1, 5.0, 21.9) Point Q(10.0, 5.0, 85.0) Point K(10.0, 21.9, 68.1) Point J(66.7, 22.1, 11.2) It is within the area surrounded by the straight lines PQ, QK, KJ, and JP connecting these four points, or is on the straight lines JP, QK, and KJ.

[0173] HFO-1132(E), R32, propane and CO2 are listed in Tables 21, 22 and Mixed refrigerants were prepared by mixing the components in the amounts shown in Tables 21 and 22 in the mass percentages shown in Tables 23 and 24.

[0174] [Table 21]

[0175] [Table 22]

[0176] [Table 23]

[0177] Furthermore, with CO2 = a% by mass, the points in the ternary diagram where x = E-HFO-1132, y = R32, and z = propane were determined by the least squares method as shown in Table 22.

[0178] [Table 24]

[0179] From Tables 21 to 23 and Figures 7 to 9, Trans-1,2-difluoroethylene (HFO-1132(E)), Difluoroethylene (R32), Pro Including refrigerants such as bromine and carbon dioxide (CO2), HFO-1132(E), R32 propane, etc., relative to the total of the above refrigerants. When the content of HFO-1132(E), R32 and CO2 is 99.5% by mass or more, and CO2 is a% by mass, the mass percentages of HFO-1132(E), R32 and propane based on their total sum are x, y and z, respectively, in a ternary composition diagram in which the total of HFO-1132(E), R32 and propane is (100-a)% by mass, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R410A is 65.0% or more, and the GWP is 300 or less. 0.0 <a≦10.0のとき Point C'(60.0, -a+40.0, 0.0), Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point R'(10.0, 44.2, -a+45.8) Point A'(-a+55.7, 44.3, 0.0), Within the area enclosed by the straight lines C'D', D'Q', Q'R', R'A', and A'C' connecting the five points above, or on the straight lines C'D', Q'R', and R'A' (however, points A', C', D', and Q' are excluded). .

[0180] HFO-1132(E), R32, propane and CO2 are listed in Tables 25, 26 and Mixed refrigerants were prepared by mixing the components in the amounts shown in Tables 27 and 28 in the mass percentages shown in Tables 27 and 28, respectively.

[0181] [Table 25]

[0182] [Table 26]

[0183] [Table 27]

[0184] Furthermore, with CO2 = a% by mass, the points in the ternary diagram where x = E-HFO-1132, y = R32, and z = propane were determined by the least squares method as shown in Table 22.

[0185] [Table 28]

[0186] From Tables 25 to 28 and Figures 10 to 12, Trans-1,2-difluoroethylene (HFO-1132(E)), Difluoroethylene (R32), Pro Including refrigerants such as bromine and carbon dioxide (CO2), HFO-1132(E), R32 propane, etc., relative to the total of the above refrigerants. When the content of HFO-1132(E), R32 and CO2 is 99.5% by mass or more and CO2 is a% by mass, the mass percentages of HFO-1132(E), R32 and propane based on their total sum are x, y and z, respectively, in a ternary composition diagram in which the total sum of HFO-1132(E), R32 and propane is (100-a)% by mass, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R1234yf is 185.0% or more, and the GWP is 150 or less. 0.0 <a≦0.5のとき Point J'( 66.7, 22.1,-a+11.2 ) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on said straight lines J'D', Q'K', and K'J', 0.5 <a≦10.0のとき Point J'( -0.0524a2+0.266a+66.58, 22.1, 0.0524a2-1.266a+11.32) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) It is within the area surrounded by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or is on said straight lines J'D', Q'K', and K'J'.

[0187] HFO-1132(E), R32, propane and CO2 are listed in Tables 25, 26 and Mixed refrigerants were prepared by mixing the components in the amounts shown in Tables 27 and 28 in the mass percentages shown in Tables 27 and 28, respectively.

[0188] [Table 29]

[0189] [Table 30]

[0190] [Table 31]

[0191] From Tables 28 and 29 to 31 and Figures 11 to 12, trans-1,2-difluoroethylene ethylene (HFO-1132(E)), difluoroethylene (R32), propane and carbon dioxide (CO2) The content of HFO-1132(E), R32, propane and CO2 in the total of the refrigerants is 99.5% by mass or more, and when CO2 is a% by mass, the mass percentages of HFO-1132(E), R32 and propane based on their total sum are x, y and z, respectively, and in a ternary composition diagram in which the total of HFO-1132(E), R32 and propane is (100-a)% by mass, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the refrigeration capacity (Cap) ratio to R404A is 103.7 or more, and the GWP is 150 or less. 0.0 <a≦0.5のときPoint J'( 66.7, 22.1,-a+11.2 ) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on said straight lines J'D', Q'K', and K'J', 0.5 <a≦10.0のときPoint J'( -0.0524a2+0.266a+66.58, 22.1, 0.0524a2-1.266a+11.32) Point D'(75.0, 0.0, -a+25.0) Point Q'(10.0, 0.0, -a+90.0) Point K'(10.0, 21.9, -a+68.1) It is within the area surrounded by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or is on said straight lines J'D', Q'K', and K'J'.

Claims

1. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), difluoroethylene (R32) and propane, the total content of HFO-1132(E), R32 and propane being 99.5 mass% or more relative to the total content of the refrigerants, When the mass percentages of HFO-1132(E), R32 and propane based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is 100 mass%, the coordinates (x, y, z) are as follows: Point C (60.0, 40.0, 0.0), Point P (73.1, 5.0, 21.9) Point Q (10.0, 5.0, 85.0) Point R (10.0, 44.2, 45.8) Point A (55.7, 44.3, 55.8), Within the area of ​​the figure enclosed by the straight lines CP, PQ, QR, RA, and AC connecting the five points above, or on the straight lines CP, QR, and RA (however, points A, C, P, and Q are excluded), R410A replacement composition.

2. A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E), R32 and propane, the total content of HFO-1132(E), R32 and propane being 99.5 mass% or more relative to the total content of the refrigerants, When the mass percentages of HFO-1132(E), R32 and propane based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is 100 mass%, the coordinates (x, y, z) are as follows: Point P (73.1, 5.0, 21.9) Point Q (10.0, 5.0, 85.0) Point K (10.0, 21.9, 68.1) Point J (66.7, 22.1, 11.2) Within the area enclosed by the straight lines PQ, QK, KJ, and JP respectively connecting the four points above, or on said straight lines JP, QK, and KJ. Compositions for replacing R1234yf and / or R404A.

3. A composition comprising a refrigerant, the refrigerant being HFO-1132(E), R32, propane and carbon dioxide (CO 2 ) based on the total of the above refrigerants, HFO-1132(E), R32, propane and CO 2 The total content is 99.5% by mass or more, CO 2 In a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is (100-a) mass%, the coordinates (x, y, z) are: When 0.0<a≦10.0 Point C' (60.0, -a+40.0, 0.0), Point D' (75.0, 0, -a+25.0) Point Q' (10.0, 0.0, -a+90.0) Point R' (10.0, 44.2, -a+45.8) Point A' (-a+55.7, 44.3, 0.0), Within the area enclosed by the straight lines C'D', D'Q', Q'R', R'A' and A'C' connecting the five points, or on said straight lines C'D', Q'R' and R'A' (however, points A', C', D' and Q' are excluded), R410A replacement composition.

4. A composition comprising a refrigerant, the refrigerant being HFO-1132(E), R32, propane and CO 2 and based on the total of the refrigerants, HFO-1132(E), R32 propane and CO 2 The total content is 99.5% by mass or more, CO 2 In a three-component composition diagram in which the sum of HFO-1132(E), R32 and propane is (100-a) mass%, the coordinates (x, y, z) are: When 0.0<a≦0.5 Point J' ( 66.7, 22.1,-a+11.2) Point D' (75.0, 0.0, -a+25.0) Point Q' (10.0, 0.0, -a+90.0) Point K' (10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on said straight lines J'D', Q'K', and K'J', When 0.5<a≦10.0 Point J' (-0.0524a2+0.266a+66.58, 22.1, 0.0524a2-1.266a+11.32) Point D' (75.0, 0.0, -a+25.0) Point Q' (10.0, 0.0, -a+90.0) Point K' (10.0, 21.9, -a+68.1) Within the area enclosed by the straight lines J'D', D'Q', Q'K', and K'J' connecting the four points above, or on the straight lines J'D', Q'K', and K'J' Compositions for replacing R1234yf and / or R404A.

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