Composition containing refrigerant, use of the same, refrigerator having the same, and method for operating the refrigerator
Patent Information
- Application Number
- JP2024010638
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-09-02
- Filing Date
- 2024-01-29
- Publication Date
- 2025-10-16
Abstract
Description
[Technical field]
[0001] The present disclosure relates to compositions containing refrigerants, uses thereof, and chillers having same and methods of operating such chillers. [Background technology]
[0002] Trifluoroethylene (HFO-1123) as a heat cycle working fluid that can replace R410A A working fluid for heat cycles containing 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 being 1,1-difluoroethane (R152a) and difluoroethane (R152b). The refrigerant contains 99.5 mass% or more of perfluoromethane (R32) and / or X, and X is , trans-1,2-difluoroethylene (HFO-1132(E)) and / or trifluoroethylene (HFO-1123). Section 2. A composition comprising a refrigerant, the refrigerant being 1,1-difluoroethane (R152a) and tran. 1,2-difluoroethylene (HFO-1132(E)) and / or difluoromethane (R32) The composition according to item 1, comprising a total of 99.5 mass% or more of the total refrigerant. Section 3. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point Q (83.7, 16.3, 0.0), Point R (80.2, 0.0, 19.8) Point O (0.0, 0.0, 100.0) and Point P (0.0, 100.0, 0.0) Within the area of the figure enclosed by the straight lines QR, RO, OP, and PQ connecting the four points above, or on the straight lines QR, RO, and OP (however, points Q, O, P, and the straight line PQ are excluded), Item 3. The composition according to item 2. Section 4. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point O (0.0, 0.0, 100.0) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) Within the area of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the above five points respectively, or on said straight lines CD, DO, OB, and BA (however, points C, O, and A are excluded), Item 3. The composition according to item 2. Section 5. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The points are located within the area enclosed by the line segments CD, DE, EE', E'F, FB, BA, and AC connecting the seven points above, or on the line segments CD, DE, EE', E'F, FB, and BA (excluding points C and A), and the line segments CD, DE, FB, BA, and AC are straight lines. The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6). Item 3. The composition according to item 2. Section 6. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point C (54.0, 46.0, 0.0), Point G (40.8, 8.1, 51.1), Point G' (26.5, 20.7, 52.8) Point H' (12.2, 34.7, 53.1) Point H (0.0, 47.6, 52.4) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The points are located within the area of the figure enclosed by the line segments CG, GG', G'H', H'H, HB, BA, and AC connecting the seven points above, or on the line segments CG, GG', G'H', H'H, HB, and BA (excluding points C and A), and the line segments CG, H'H, HB, BA, and AC are straight lines, The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249), Item 3. The composition according to item 2. Section 7. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point C' (53.4, 43.8, 2.8), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) and Point B' (0.0, 32.0, 68.0) (It lies within the area of the figure enclosed by the line segments C'D, DE, EE', E'F, FB' and B'C' respectively connecting the six points above, or on said line segments C'D, EE', E'F, FB' and B'C'), and the line segments C'D, DE, FB' and B'C' are straight lines, The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6). Item 3. The composition according to item 2. Section 8. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point C' (53.4, 43.8, 2.8) Point G (40.8, 8.1, 51.1), Point G' (26.5, 20.7, 52.8) Point H' (12.2, 34.7, 53.1) The points are within the range of a figure enclosed by line segments C'G, GG', G'H', and H'C' respectively connecting the four points above, or are on said line segments C'G, GG', G'H', and H'C', and the line segments C'G and H'C' are straight lines, and the coordinates (x, y, z) of the points on said line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249). Item 3. The composition according to item 2. Section 9. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point D' (43.0, 14.3, 42.7), Point D (38.0, 0.0, 62.0), Point J (28.3, 0.0, 71.7) Point K (19.3, 9.0, 71.7) Within the area enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points, or within the area enclosed by the straight line D On 'D, DJ, JK and KD' Item 3. The composition according to item 2. Section 10. In the refrigerant, the total amount of R152a, R32 and HFO-1132(E) is 99.5 mass % of the total refrigerant. % or more, and when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, the sum of HFO-1132(E), R32 and R152a is 100 mass%. In the figure, the coordinates (x, y, z) are Point D' (43.0, 14.3, 42.7) Point D (38.0, 0.0, 62.0) Point L (22.6, 0.0, 77.4) Point M (14.0, 7.8, 78.2) Within the range of the figure enclosed by the straight lines D', D, DL, LM, and MD' connecting the four points of On 'D, DL, LM and MD' Item 3. The composition according to item 2. Section 11. 11. The composition according to any one of items 4 to 10, wherein the refrigerant further comprises HFO-1123. Section 12. Item 12. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of items 1 to 11. Section 13. 12. A refrigeration device comprising the composition according to any one of items 1 to 11 as a working fluid. Section 14. Item 9. The composition according to item 8, which is used to operate an automotive air conditioner. Section 15. Item 8. A refrigeration method comprising a step of operating a refrigeration device using the composition according to item 8, The refrigeration method, wherein the refrigeration device is an air conditioning device for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle. Section 16. A refrigeration device comprising the composition according to item 8 as a working fluid, The refrigeration apparatus is an air conditioning apparatus for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle. Section 17. 12. The composition according to any one of items 1 to 11, which is a replacement refrigerant for R410A, R134a, R1234yf, or R404A. 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0008] The present inventors have conducted intensive research to solve the above problems and have found that various mixed refrigerants described below have the above properties.
[0009] The present disclosure has been completed as a result of further research based on such findings. The present disclosure includes the following embodiments. <Terminology> In this specification, the term "refrigerant" includes at least compounds having a refrigerant number (ASHRAE number) beginning with R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and further In addition, even if a refrigerant number has not yet been assigned, it includes refrigerants that have the same refrigerant properties as those refrigerants. In terms of the chemical structure, refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons. Contains hydrofluorocarbons (HFCs).
[0010] In this specification, the term "composition containing a refrigerant" includes at least (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further contains other components and can be used to obtain a working fluid for a refrigerant by mixing with at least a refrigerating machine oil, and (3) a working fluid for a refrigerant containing a refrigerating machine oil. In this specification, of these three aspects, the composition (2) is referred to as a "refrigerant composition" to distinguish it from the refrigerant itself (including a mixture of refrigerants). Also, the working fluid for a refrigerant (3) is referred to as a "refrigerating machine oil-containing working fluid" to distinguish it from the "refrigerant composition".
[0011] In this specification, the term "substitution" when used in the context of "substituting" a first refrigerant with a second refrigerant means that, as a first type, equipment designed to operate using a first refrigerant can be operated under optimal conditions using a second refrigerant by only changing a few parts (at least one of refrigeration oil, gaskets, packing, expansion valves, dryers, and other parts) and adjusting the equipment as necessary. In other words, this type refers to operating the same equipment by "substituting" a refrigerant. The "substitution" of this type can be categorized into "drop-in substitution," "nearly drop-in substitution," and "retrofit," in order of the degree of change or adjustment required when replacing with the second refrigerant.
[0012] The second category, where equipment designed to operate with a second refrigerant is installed and used for the same application as an existing application of a first refrigerant, is also included in the term "substitution." This category refers to "substituting" a refrigerant to serve the same application.
[0013] In this specification, the term "refrigeration machine" refers to a device that removes heat from an object or space to lower its temperature below that of the surrounding air and maintains this low temperature. In other words, a refrigerator is a conversion device that obtains energy from the outside, performs work, and converts it into energy in order to transfer heat from a low temperature to a high temperature.
[0014] In this specification, the term "vehicle air conditioner" refers to a type of refrigeration device used in automobiles such as gasoline vehicles, hybrid vehicles, electric vehicles, hydrogen vehicles, etc. The term vehicle air conditioner refers to a refrigeration device consisting of a refrigeration cycle in which heat exchange is performed with a liquid refrigerant in an evaporator, the evaporated refrigerant gas is sucked into a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied in a condenser, and the refrigerant gas is further adiabatically expanded by passing through an expansion valve, and then supplied to the evaporator again as a liquid refrigerant.
[0015] In this specification, a refrigerant is classified as "toxicity category A" in accordance with the US ANSI / ASHRAE34-2019 standard. The permissible concentration of the mixed refrigerant (Occupational Exposure Limits (OEL)) is 400 ppm or more. In addition, "toxicity category B" means that the substance is mixed according to the US ANSI / ASHRAE34-2019 standard. This means that the permissible concentration of the combined refrigerant is less than 400 ppm.
[0016] In the present invention, the permissible concentration (Occupational Exposure Limits (OEL)) of a mixed refrigerant refers to a value evaluated at the central composition unless otherwise specified. However, the OEL of each refrigerant is as follows: The calculation is as follows. R32: 1000ppm R152a: 1000ppm HFO-1132(E): 350 ppmppm
[0017] The OEL at the center composition of the mixed refrigerant is calculated using the following formula.
[0018]
number
[0019] Pressures described in this specification are in absolute pressure unless otherwise specified. do.
[0020] 1. Refrigerant The refrigerants disclosed herein contain 1,1-difluoroethane (R152a), difluoromethane (R32) and / or trans-1,2-difluoroethylene (HFO-1132(E)). Of the R152a, R32 and HFO-1132(E) contained in the refrigerants disclosed herein, those contained in an amount of 0.5 mass% or more based on the total amount of the refrigerant may be referred to as "essential refrigerants". As shown in the examples, the refrigerants disclosed herein may further contain HFO-1123, or trifluoroethylene (HFO-1123) may be used in place of HFO-1132(E). may also include
[0021] The refrigerants of the present disclosure are low GWP refrigerant mixtures.
[0022] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) meet the following requirements, the tolerable concentration is 400 ppm or more and the ASHRAE toxicity category is "A". <Requirements> Point Q (83.7, 16.3, 0.0), Point R (80.2, 0.0, 19.8) Point O (0.0, 0.0, 100.0) and Point P (0.0, 100.0, 0.0) It is within the area of the figure enclosed by straight lines QR, RO, OP, and PQ connecting these four points, or on said straight lines QR, RO, and OP (however, points Q, O, P, and straight line PQ are excluded).
[0023] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, This prevents disproportionation reactions and reduces the GWP to 400 or less. <Requirements> Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point O (0.0, 0.0, 100.0) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The area of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting these five points, or on said straight lines CD and BA (however, points C, O, and A are excluded).
[0024] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 400 or less, and the refrigeration capacity ratio compared to R410A is 50% or more. <Requirements> Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The line segments CD, DE, EE', E'F, FB, BA, and AC connecting the seven points above are within the area of the figure enclosed by these line segments, or are on the line segments CD, EE', E'F, and BA (excluding points C and A), and the line segments CD, DE, FB, BA, and AC are straight lines. The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6).
[0025] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 400 or less, and the refrigeration capacity ratio is 70% or more compared to R410A. <Requirements> Point C (54.0, 46.0, 0.0), Point G (38.0, 0.0, 62.0), Point G' (16.3, 0.0, 83.7) Point H' (8.2, 6.9, 84.9) Point H (0.0, 14.4, 85.6) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The points are located within the area of the figure enclosed by the line segments CG, GG', G'H', H'H, HB, BA, and AC connecting the seven points above, or on the line segments CG, GG', G'H', H'H, and BA (excluding points C and A), and the line segments CG, H'H, HB, BA, and AC are straight lines, The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249).
[0026] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 300 or less, and the refrigeration capacity ratio compared to R410A is 50% or more. <Requirements> Point C' (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) and Point B' (0.0, 32.0, 68.0) The points are located within the area enclosed by the line segments C'D, DE, EE', E'F, FB', and B'C' respectively connecting the six points above, or on the line segments C'D, EE', E'F, and B'C', and the line segments C'D, DE, FB', and B'C' are straight lines. The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6).
[0027] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 300 or less, and the refrigeration capacity ratio is 70% or more compared to R410A. <Requirements> Point C' (54.0, 46.0, 0.0), Point G (38.0, 0.0, 62.0), Point G' (16.3, 0.0, 83.7) Point H' (8.2, 6.9, 84.9) The line segments C'G, GG', G'H', and H'C' connect the four points respectively, and the line segments C'G and H'C' are straight lines. The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249).
[0028] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 150 or less, and the boiling point is -40°C or less. <Requirements> Point D' (43.0, 14.3, 42.7), Point D (38.0, 0.0, 62.0), Point J (28.3, 0.0, 71.7) Point K (19.3, 9.0, 71.7) Within the area enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points, or within the area enclosed by the straight line D On 'D, JK and KD'.
[0029] In the refrigerants disclosed in this disclosure, the quality of HFO-1132(E), R32 and R152a is based on the sum of these. When the mass percentages of HFO-1132(E), R32 and R152a are x, y and z, respectively, the total of HFO-1132(E), R32 and R152a is 100 mass%. In the three-component composition diagram, when the coordinates (x, y, z) satisfy the following requirements, As a result, no disproportionation reaction occurs, the GWP is 150 or less, and the refrigeration capacity ratio compared to R404A is 70% or more. <Requirements> Point D' (43.0, 14.3, 42.7) Point D (38.0, 0.0, 62.0) Point L (22.6, 0.0, 77.4) Point M (14.0, 7.8, 78.2) Within the range of the figure enclosed by the straight lines D', D, DL, LM, and MD' connecting the four points of On 'D, LM and MD'. The refrigerant disclosed in the present disclosure is a 3-component composition diagram in which the sum of HFO-1132(E), R32 and R152a is 100% by mass, and the point where HFO-1132(E) is 100% by mass is the apex, and the coordinates (x, y, z) are aligned along the line QR When it is above or below the line QR, the permissible concentration is 400 ppm or more. The ASHRAE toxicity category is "A."
[0030] The refrigerant disclosed in the present disclosure is a 3-component composition diagram in which the sum of HFO-1132(E), R32 and R152a is 100% by mass, and the point where HFO-1132(E) is 100% by mass is the apex, and the coordinates (x, y, z) are aligned along the line CD When the temperature is above the line CD or below the line CD, the disproportionation reaction occurs at 3 MPa and 150°C. In this case, even if the refrigerant pressure in the refrigeration cycle reaches 3 MPa and the refrigerant temperature reaches 150°C locally, the disproportionation reaction can be suppressed.
[0031] In addition, the refrigerant disclosed herein is effective in heating with a heat pump when its boiling point is −40.0° C. or lower. 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.
[0032] The refrigerant of the present disclosure may contain 10% by mass or more of HFO-1132(E) based on the entire refrigerant, It may contain 30% by mass or more, or 40% by mass or more. Preferably, it contains 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The refrigerant of the present disclosure may contain R32 at 10% by mass or more, or at 20% by mass or more, based on the entire refrigerant. It may contain 30% by mass or more, it may contain 40% by mass or more, it may contain 50% by mass or more The refrigerant of the present disclosure may contain R152a in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more relative to the entire refrigerant. It may contain 90% by mass or more.
[0033] The refrigerant of the present disclosure may contain additional refrigerants in addition to the essential refrigerants, as long as the above-mentioned characteristics and effects are not impaired. In this regard, in one embodiment, the refrigerant of the present disclosure preferably contains the total of the essential refrigerants in the total refrigerant at 99.5% by mass or more, and more preferably at 99.75% by mass or more. It is more preferable that the content is 99.9% by mass or more, and further preferably that the content is 99.999% by mass or more. It is even more preferable that the content of the cooling agent in the present disclosure is 99.9999% by mass or more, and it is most preferable that the content of the cooling agent in the present disclosure is 99.9999% by mass or more. The refrigerant may be substantially composed of only the essential refrigerant, in which case the refrigerant of the present disclosure may consist of only the essential refrigerant and unavoidable impurities. Additionally, the refrigerant of the present disclosure may consist of only essential refrigerants.
[0034] 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. Examples of the additional refrigerant include acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, and HFC-143a. , HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, 3 , 3,3-trifluoropropyne, etc.
[0035] 2. Refrigerant Composition The refrigerant composition of the present disclosure contains at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure. The refrigerant composition of the present disclosure can be further mixed with at least a refrigerating machine oil to obtain a working fluid for a refrigerating machine. The refrigerant composition of the present disclosure further contains at least one other component in addition to the refrigerant of the present disclosure. The refrigerant composition of the present disclosure may contain at least one of the following other components as necessary. As described above, when the refrigerant composition of the present disclosure is used as a working fluid in a refrigerator, it is usually mixed with at least a refrigerating machine oil. Therefore, the refrigerant composition of the present disclosure preferably does not substantially contain a refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure preferably contains 1 mass % or more of refrigerating machine oil relative to the entire refrigerant composition. It is preferably 0.1 mass % or less, and more preferably 0.1 mass % or less.
[0036] 2.1 water The refrigerant composition of the present disclosure may contain a small amount of water. The water content in the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant. This stabilizes the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant, and also makes the unsaturated fluorocarbon compound less susceptible to oxidation, thereby improving the stability of the refrigerant composition.
[0037] 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.
[0038] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.
[0039] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.
[0040] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Polyfluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are particularly preferred.
[0041] 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-143a (1,1,1-trifluoroethane, CF3CH3) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-152a (1,1-difluoroethane, CHF2CH3) HFC-152 (1,2-difluoroethane, CH2FCH2F) HFC-161 (Fluoroethane, CH3CH2F) HFC-245fa (1,1,1,3,3-Pentafluoropropane, CF3CH2CHF2) HFC-236fa (1,1,1,3,3,3-Hexafluoropropane, CF3CH2CF3) HFC-236ea (1,1,1,2,3,3-Hexafluoropropane, CF3CHFCHF2) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3) HCFC-22 (Chlorodifluoromethane, CHClF2) HCFC-31 (Chlorofluoromethane, CH2ClF) CFC-1113 (Chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl methyl ether, CF3OCH3) HFE-227ea (Trifluoromethyl-Tetrafluoroethyl Ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)
[0042] The refrigerant compositions of the present disclosure may contain a total of about 10 parts per million (ppm) of tracer(s) based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 1000 ppm or less of tracer(s) based on the total refrigerant composition. The refrigerant compositions of the present disclosure may contain a total of about 30 ppm or more of tracer(s) based on the total refrigerant composition, more preferably about 50 ppm or more of tracer(s). The refrigerant compositions of the present disclosure may contain a total of about 500 ppm or less of tracer(s) based on the total refrigerant composition, and may contain a total of about 300 ppm or less of tracer(s).
[0043] 2.3 UV fluorescent dye The refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone or two types of ultraviolet fluorescent dyes. It may contain more than one.
[0044] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
[0045] 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.
[0046] 2.4 Stabilizer The refrigerant composition of the present disclosure may contain one type of stabilizer alone, or may contain two or more types of stabilizers.
[0047] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.
[0048] The stabilizers include, for example, nitro compounds, ethers, and amines.
[0049] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
[0050] An example of the ethers is 1,4-dioxane.
[0051] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.
[0052] Other examples include butylhydroxyxylene and benzotriazole.
[0053] 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% or less by mass.
[0054] 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.
[0055] The polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.
[0056] 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.
[0057] 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.
[0058] 3. Working fluid containing refrigeration oil The refrigerant oil-containing working fluid of the present disclosure comprises at least one of the refrigerant or refrigerant composition of the present disclosure and a refrigerant oil. The refrigerating machine oil-containing working fluid generally contains at least 10% by mass of 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 a refrigerating machine oil used in a compressor of a refrigerator with a refrigerant or a refrigerant composition. The refrigerating machine oil-containing working fluid generally contains at least 10% by mass of refrigerating machine oil. The refrigerating machine oil-containing working fluid generally contains at most 50% by mass of refrigerating machine oil.
[0059] 3.1 Refrigerating machine oil The composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oils.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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.
[0064] 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.
[0065] 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.
[0066] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.
[0067] 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.
[0068] 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.
[0069] Specifically, a method of operating a refrigerator of the present disclosure includes circulating a refrigerant of the present disclosure in the refrigerator.
[0070] Use in ASHRAE Toxicity Category A This disclosure includes methods of use with ASHRAE toxicity category A, whereas HFO-1132(E) is toxicity category B, but R15 By mixing it with 2a and / or R32, the mixed refrigerant can be treated as having an ASHRAE toxicity classification of A, just like the conventional R32 and R410A.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 6. Use for inhibiting disproportionation reactions The use of the present disclosure is for inhibiting the disproportionation reaction of R32 and / or R152a with HFO-1132(E). The use, wherein the inhibition of the disproportionation reaction is carried out by mixing HFO-1132(E) with R32 and / or R152a in the present This is done by mixing the refrigerants to obtain the disclosed mixing ratio.
[0075] 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.
[0076] 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
[0077] The present disclosure will be described in more detail below by way of examples, although the present disclosure is not limited to these examples.
[0078] The qualities of HFO-1132(E), R32 and R152a are shown in Table 1, based on their sum. A mixed refrigerant was prepared by mixing the above components in a ratio of % by volume.
[0079] The permissible concentrations (OEL values) of each of these mixed refrigerants were investigated. [Table 1] From the results in Table 1, it can be seen that the refrigerant of the present disclosure has an allowable concentration of 400 ppm or more within the region shown in the triangular diagram in FIG. 1, and is classified as "A" in the ASHRAE toxicity category.
[0080] HFO-1132(E), R32 and R152a are shown in Table 21 based on their sum. A mixed refrigerant was prepared by mixing the above components at a ratio of % by mass.
[0081] Each of these mixed refrigerants was examined for the presence or absence of a disproportionation reaction using the following test method and conditions. Test Method The refrigerant composition to be tested was transferred and filled into the test vessel, heated to 150°C, and then the Pt wire in the vessel was By applying a voltage to melt the refrigerant composition, 30 J of energy was given to the refrigerant composition. The presence or absence of this was judged by a sudden increase in pressure and temperature inside the device. Test conditions Test container: 38cc SUS container Test temperature: 150℃ Pressure: 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. .
[0082] [Table 2]
[0083] The results in Table 2 show that the refrigerant of the present disclosure does not undergo disproportionation within the region shown in the triangular diagram in FIG.
[0084] The GWP of HFO-1132(E) is set to 1, and the GWPs of R32 and R152a are set to 100% by the Intergovernmental Panel on Climate Change (IPCC). The GWP of the mixed refrigerant was evaluated based on the values in the Fourth Assessment Report of the International Conference on Climate Change (ICC) 2011. The COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were calculated by performing theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0). The physical property data of HFO-1132(E) used in the theoretical calculation of the refrigeration cycle was obtained from actual measurements. This was added to Refprop.10.0. <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%
[0085] In the table below, "COP ratio" and "refrigeration capacity ratio" are the ratios to R410A, R404A, or R1234yf. In the table, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa).
[0086] The coefficient of performance (COP) was calculated using the following formula. COP = (refrigeration capacity or heating capacity) / power consumption
[0087] In the table below, "Power consumption (%)" refers to the amount of power consumed by an electric vehicle to run. This indicates electrical energy, and is expressed as a ratio to the amount of electricity consumed when the refrigerant is HFO-1234yf. In the table, "Electric energy consumed for heating (%)" indicates the electrical energy used to operate the heating function of an electric vehicle, and is expressed as a ratio to the amount of electricity consumed when the refrigerant is HFO-1234yf.
[0088] In the table below, "Driving distance (with)" refers to the relative percentage (%) of the driving distance when driving with heating on, when the driving distance (without) without heating (heating power consumption is 0) is taken as 100%, for an electric vehicle equipped with a secondary battery of a certain electric capacity. This is what was done.
[0089] The heating method used was an electric heater system for heating refrigerants with a boiling point above -40°C, and a heat pump system for heating refrigerants with a boiling point below -40°C.
[0090] The amount of power consumed during heating was calculated using the following formula. Note that heating COP means "heating efficiency." Taste. Power consumption when heating = Heating capacity / Heating COP
[0091] Regarding heating efficiency, in the case of an electric heater, the heating COP is 1, and the same amount of electricity is consumed for heating as for power. In other words, the power consumption for heating is E=E / (1+COP).
[0092] The driving distance was calculated using the following formula. Driving distance = (battery capacity) / (power consumption + power consumption for heating)
[0093] These values are shown in the table below along with the GWP for each refrigerant mixture.
[0094] [Table 3]
[0095] The coordinates on the line segments E-E'-F and G-G'-H' were determined based on the least squares method as follows.
[0096] [Table 4]
[0097] [Table 5]
[0098] [Table 6]
[0099] [Table 7]
[0100] From these results, it can be seen that the refrigerants disclosed herein, HFO-1132(E), R32 and R152a, When the mass percentages based on the sum are x, y, and z, respectively, the mass percentages of HFO-1132(E), R32, and R152a are In a three-component composition diagram where the sum is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C and the GWP is 400 or less (Figure 2 1). <Requirements> Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point O (0.0, 0.0, 100.0) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) It is within the area of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting these five points, or is on said straight lines CD and BA.
[0101] From these results, it can be seen that the refrigerants disclosed herein, HFO-1132(E), R32 and R152a, When the mass percentages based on the sum are x, y, and z, respectively, the mass percentages of HFO-1132(E), R32, and R152a are In a three-component composition diagram where the sum total is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C, the GWP is 400 or less, and the refrigeration capacity ratio compared to R410A is 50% or more (Figure 2). <Requirements> Point C (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The seven points are respectively connected by the line segments CD, DE, EE', E'F, FB, BA, and AC, and are within the area of the figure enclosed by these line segments CD, DE, EE', E'F, FB, BA, and AC, or on said line segments CD, EE', E'F, and BA, and the line segments CD, DE, FB, BA, and AC are straight lines. The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6).
[0102] From these results, it can be seen that the refrigerants disclosed herein, HFO-1132(E), R32 and R152a, When the mass percentages based on the sum are x, y, and z, respectively, the mass percentages of HFO-1132(E), R32, and R152a are In a three-component composition diagram where the sum total is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C, the GWP is 400 or less, and the refrigeration capacity ratio compared to R410A is 70% or more (Figure 2). <Requirements> Point C (54.0, 46.0, 0.0), Point G (38.0, 0.0, 62.0), Point G' (16.3, 0.0, 83.7) Point H' (8.2, 6.9, 84.9) Point H (0.0, 14.4, 85.6) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The seven points are respectively connected within the area of the figure enclosed by the line segments CG, GG', G'H', H'H, HB, BA, and AC, or on said line segments CG, GG', G'H', H'H, and BA, and the line segments CG, H'H, HB, BA, and AC are straight lines, The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249).
[0103] From these results, it can be seen that the refrigerants disclosed herein, HFO-1132(E), R32 and R152a, When the mass percentages based on the sum are x, y, and z, respectively, the mass percentages of HFO-1132(E), R32, and R152a are In a three-component composition diagram where the sum total is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity ratio compared to R410A is 50% or more (Figure 2). <Requirements> Point C' (54.0, 46.0, 0.0), Point D (38.0, 0.0, 62.0), Point E (14.0, 0.0, 86.0) Point E' (7.0, 7.0, 86.0) Point F (0.0, 14.4, 85.6) and Point B' (0.0, 32.0, 68.0) The points are located within the area enclosed by the line segments C'D, DE, EE', E'F, FB', and B'C' respectively connecting the six points above, or on the line segments C'D, EE', E'F, and B'C', and the line segments C'D, DE, FB', and B'C' are straight lines. The coordinates (x, y, z) of points on the line segments EE' and E'F are expressed as (x, 0.0041x2-1.0857x+14.4, -0.0041x2+0.0857x+85.6).
[0104] From these results, it can be seen that the refrigerants disclosed herein, HFO-1132(E), R32 and R152a, When the mass percentages based on the sum are x, y, and z, respectively, the mass percentages of HFO-1132(E), R32, and R152a are In a three-component composition diagram where the sum total is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 3 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity ratio compared to R410A is 70% or more (Figure 2). <Requirements> Point C' (54.0, 46.0, 0.0), Point G (38.0, 0.0, 62.0), Point G' (16.3, 0.0, 83.7) Point H' (8.2, 6.9, 84.9) The coordinates (x, y, z) of points on line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249).
[0105] [Table 8]
[0106] [Table 9]
[0107] In addition, from the results of Tables 8 and 9, the refrigerants disclosed herein, HFO-1132(E), R32 and R152a In a three-component composition diagram in which the sum of HFO-1132(E), R32 and R152a is 100% by mass, the coordinates (x, y, z) satisfy the following requirements: When added, no disproportionation reaction occurs at 3 MPa and 150°C, the GWP is 150 or less, and the boiling point It can be seen that the temperature drops below -40°C (Figure 3). <Requirements> Point D' (43.0, 14.3, 42.7), Point D (38.0, 0.0, 62.0), Point J (28.3, 0.0, 71.7) Point K (19.3, 9.0, 71.7) Within the area enclosed by the straight lines D'D, DJ, JK, and KD' connecting the four points, or within the area enclosed by the straight line D On 'D, JK and KD'.
[0108] [Table 10]
[0109] [Table 11]
[0110] Furthermore, from the results of Tables 10 and 11, in the refrigerant of the present disclosure, when the mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R152a is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3 MPa and 150°C, the GWP is 150 or less, and It can be seen that the refrigeration capacity ratio compared to R404A is over 70% (Figure 3). <Requirements> Point D' (43.0, 14.3, 42.7) Point D (38.0, 0.0, 62.0) Point L (22.6, 0.0, 77.4) Point M (14.0, 7.8, 78.2) Within the range of the figure enclosed by the straight lines D', D, DL, LM, and MD' connecting the four points of On 'D, LM and MD'. Furthermore, from the results of Tables 7, 9, and 11, in the refrigerant of the present disclosure, 1,1-difluoroethane (R152a), difluoromethane (R32), and X account for 99.5 mass % in total of the entire refrigerant. % or more, X is trans-1,2-difluoroethylene (HFO-1132(E)) and / or It is understood that trifluoroethylene (HFO-1123) may also be used.
Claims
1. A composition containing a refrigerant, wherein the refrigerant contains 1,1-difluoroethane (R152a), trans-1,2-difluoroethylene (HFO-1132(E)), and difluoromethane (R32) in a total amount of 99.5 mass% or more based on the total amount of the refrigerant; When the mass percentages of HFO-1132(E), R32, and R152a based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and R152a is 100 mass%, the coordinates (x, y, z) are: Point C (54.0, 46.0, 0.0), Point G (40.8, 8.1, 51.1), Point G' (26.5, 20.7, 52.8) Point H' (12.2, 34.7, 53.1) Point H (0.0, 47.6, 52.4) Point B (0.0, 50.0, 50.0) and Point A (40.8, 59.2, 0.0) The points are within the area of the shape enclosed by the line segments CG, GG', G'H', H'H, HB, BA, and AC connecting the seven points above, or are on the line segments CG, GG', G'H', H'H, and BA (excluding points C, B, and A), and the line segments CG, H'H, HB, BA, and AC are straight lines, The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249). composition.
2. When the mass percentages of HFO-1132(E), R32 and R152a based on their sum are x, y and z, respectively, in a ternary composition diagram in which the sum of HFO-1132(E), R32 and R152a is 100 mass%, the coordinates (x, y, z) are: Point C' (53.4, 43.8, 2.8) Point G (40.8, 8.1, 51.1), Point G' (26.5, 20.7, 52.8) Point H' (12.2, 34.7, 53.1) The line segments C'G, GG', G'H', and H'C' connect the four points respectively, and the line segments C'G, GG', G'H', and H'C' are straight lines. The coordinates (x, y, z) of points on the line segments GG' and G'H' are expressed as (x, 0.0034x2-1.1115x+47.751, -0.0034x2+0.1115x+52.249). The composition of claim 1.
3. A composition containing a refrigerant, wherein the refrigerant contains R152a, HFO-1132(E), and R32 in a total amount of 99.5 mass% or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), R32, and R152a based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and R152a is 100 mass%, the coordinates (x, y, z) are: Point D' (43.0, 14.3, 42.7), Point D (38.0, 0.0, 62.0), Point J (28.3, 0.0, 71.7) Point K (19.3, 9.0, 71.7) The four points are respectively connected by straight lines D'D, DJ, JK, and KD', and are within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD', or are on the straight lines D'D, DJ, JK, and KD'. composition.
4. A composition containing a refrigerant, wherein the refrigerant contains R152a, HFO-1132(E), and R32 in a total amount of 99.5 mass% or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), R32, and R152a based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and R152a is 100 mass%, the coordinates (x, y, z) are: Point D' (43.0, 14.3, 42.7) Point D (38.0, 0.0, 62.0) Point L (22.6, 0.0, 77.4) Point M (14.0, 7.8, 78.2) The four points are respectively connected by straight lines D'D, DL, LM, and MD', and are within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD'. composition.
5. 5. The composition of claim 1, wherein the refrigerant further comprises HFO-1123.
6. A refrigeration method comprising the step of operating a refrigeration cycle using the composition according to any one of claims 1 to 4.
7. A refrigeration device comprising the composition of any one of claims 1 to 4 as a working fluid.
8. 10. The composition of claim 2 used to operate an automotive air conditioning system.
9. 10. A method of refrigeration comprising operating a refrigeration system with the composition of claim 2, The refrigeration method, wherein the refrigeration device is an air conditioning device for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle.
10. 10. A refrigeration system comprising the composition of claim 2 as a working fluid, The refrigeration device is an air conditioning device for a gasoline vehicle, a hybrid vehicle, an electric vehicle, or a hydrogen vehicle.
11. The composition according to any one of claims 1 to 4, which is a replacement refrigerant for R410A, R134a, R1234yf or R404A.