A method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using a composition containing a refrigerant.

Abstract

To provide a novel low-GWP mixed refrigerant.SOLUTION: As a solution, provided is a composition comprising a refrigerant, wherein the refrigerant includes 22.6-57 mass% of trans-1,2-difluoroethylene (HFO-1132(E)) and 43-77.4 mass% of 1,1-difluoroethane (R152a) based on the total amount thereof.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 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 comprising trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethane (R152a) in amounts of 22.6 to 57% by mass and 77.4 to 43% by mass, respectively, based on the total amount of the refrigerant. Section 2. Item 2. The composition according to item 1, comprising HFO-1132(E) and R152a in an amount of 22.9 to 57 mass% and 77.1 to 43 mass%, respectively, based on the total amount of these. Section 3. Item 2. The composition according to item 1, comprising HFO-1132(E) and R152a in amounts of 28.3 to 57 mass% and 71.7 to 43 mass%, respectively, based on the total amount of these. Section 4. The composition according to any one of items 1 to 3, comprising HFO-1132(E) and R152a in a total amount of 99.5 mass% or more based on the total amount of the refrigerant. Section 5. A composition comprising a refrigerant, The refrigerant contains R152a, R32 and HFO-1132(E) in a total amount of 99.5% by mass or more based on the total amount of the refrigerant. Includes and The mass percentages of HFO-1132(E), R32 and R152a based on the sum of these are x, y and z, respectively. In this case, 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) are as follows: Point C (60.0, 40.0, 0.0), Point D' (57.4, 5.0, 37.6), Point E' (17.5, 5.0, 77.5), Point F (0.0, 22.9, 77.1), Point B (0.0, 32.0, 68.0), and Point A (55.7, 44.3, 0.0) Within the area of ​​the figure enclosed by the straight lines CD', D'E', E'F, FB, BA and AC connecting the six points above, and on the line segments CD', D'E', E'F and BA above (excluding points A, C, B and F), Composition. Section 6. In the refrigerant, the coordinates (x, y, z) are: Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point J' (22.9, 5.0, 72.1), and Point K (19.3, 9.0, 71.7) Item 6. The composition according to item 5, which is within the area surrounded by the straight lines C'D', D'J', J'K, and KC' connecting the four points above, and which is on the straight lines C'D', D'J', J'K, and KC'. Section 7. In the refrigerant, the coordinates (x, y, z) are: Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point L' (17.1, 5.0, 77.9), and Point M (14.0, 7.8, 78.2) Item 6. The composition according to item 5, which is within the area surrounded by straight lines C'D', 'D'L', L'M and MC'' respectively connecting the four points above, and which is on said straight lines C'D', D'L', L'M and MC'. Section 8. Item 6. The composition according to item 2 or 5, which is an alternative to R410A. Section 9. Item 7. The composition according to item 3 or 6, which is an alternative to R1234yf. Section 10. It is a composition for replacing R1234yf and for use in the refrigeration cycle of air conditioners for electric vehicles. Item 10. The composition according to item 9. Section 11. Item 8. The composition according to item 1 or 7, which is an alternative to R404A. Section 12. 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 7. Section 13. Item 8. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of Items 1 to 7. Section 14. 8. A refrigeration device comprising the composition according to any one of items 1 to 7 as a working fluid. Effect of the Invention

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

[0007] [Figure 1] FIG. 1 is a ternary diagram showing the composition of the refrigerant 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] Pressures described in this specification are in units of absolute pressure unless otherwise specified.

[0016] 1. Refrigerant The refrigerants disclosed herein are trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethylene. Fluoroethane (R152a). The refrigerants of the present disclosure may further include difluoromethane (R32).

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

[0018] The refrigerant of the present disclosure may contain HFO-1132(E) and R152a in amounts of 22.6 to 57% by mass and 77.4 to 43% by mass, respectively, based on the total of these. This refrigerant has a refrigeration capacity ratio of 70% or more relative to R404A, and does not undergo disproportionation reactions at 5 MPa and 150°C. Therefore, this refrigerant can be used as an alternative refrigerant to R404A.

[0019] The refrigerant of the present disclosure may contain 44.7 to 57 mass% of HFO-1132(E) and 55.3 to 43 mass% of R152a, based on the total of the two. This refrigerant has a refrigeration capacity ratio of 90% or more compared to R404A, and does not undergo disproportionation reaction at 5 MPa and 150°C. Therefore, this refrigerant can be used as an alternative refrigerant to R404A.

[0020] The refrigerant of the present disclosure may contain HFO-1132(E) and R152a in amounts of 22.9 to 57% by mass and 77.1 to 43% by mass, respectively, based on the total of these. This refrigerant has a refrigeration capacity ratio of 55% or more to R410A, and does not undergo disproportionation reactions at 5 MPa and 150°C. Therefore, this refrigerant can be used as an alternative refrigerant to R410A.

[0021] The refrigerant of the present disclosure may contain HFO-1132(E) and R152a in amounts of 41.4 to 57% by mass and 59.6 to 43% by mass, respectively, based on the total of these. This refrigerant has a refrigeration capacity ratio of 65% or more to R410A, and does not undergo disproportionation reactions at 5 MPa and 150°C. Therefore, this refrigerant can be used as an alternative refrigerant to R410A.

[0022] The refrigerant of the present disclosure may contain HFO-1132(E) and R152a in amounts of 28.3 to 57% by mass and 71.7 to 43% by mass, respectively, based on the total amount of the refrigerant. This refrigerant has a boiling point of -40°C or lower, and In addition, no disproportionation reaction occurs at 5 MPa and 150° C. This refrigerant can be used as an alternative to R1234yf.

[0023] The refrigerant of the present disclosure may contain HFO-1132(E) and R152a in amounts of 44.1 to 57 mass% and 55.9 to 43 mass%, respectively, based on the total of the refrigerants. This refrigerant has a refrigeration capacity ratio of 44.1 to 57 mass% relative to R1234yf. The refrigerant has a molecular weight of 165% or more and does not undergo disproportionation reaction at 5 MPa and 150° C. This refrigerant can be used as an alternative to R1234yf.

[0024] The refrigerants disclosed herein are HFO-1132(E) and R152a, in total: refrigerant containing 22.6% and 77.4% by mass, respectively; refrigerant containing 25.0% by mass and 75.0% by mass, respectively; refrigerant containing 28.3% and 71.7% by mass, respectively; Refrigerants containing 30.0% and 70.0% by mass, respectively; refrigerant containing 35.0% and 65.0% by mass, respectively; refrigerant containing 36.0% and 64.0% by mass, respectively; refrigerant containing 38.0% and 62.0% by mass, respectively; refrigerants containing 45.0% by mass and 55.0% by mass, respectively; and refrigerant containing 55.0% and 45.0% by mass, respectively; The refrigerant may exclude at least one refrigerant selected from the group consisting of:

[0025] In the above-mentioned embodiment, the refrigerant of the present disclosure may further contain an additional refrigerant in addition to HFO-1132(E) and R152a, within the range that does not impair the above-mentioned characteristics and effects. In this regard, in one embodiment, the refrigerant of the present disclosure contains HFO-1132(E) and R152a in total at 99% or less of the total amount of the refrigerant. It is preferable that the content is 0.5% by mass or more, more preferable that the content is 99.75% by mass or more, even more preferable that the content is 99.9% by mass or more, even more preferable that the content is 99.999% by mass or more, and even more preferable that the content is 99.9999% by mass or more. The refrigerant of the present disclosure may be substantially composed of HFO-1132(E) and R152a, in which case the refrigerant of the present disclosure may be composed of only HFO-1132(E), R152a and unavoidable impurities. Additionally, the refrigerant of the present disclosure may consist solely of HFO-1132(E) and R152a.

[0026] 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. Examples of the additional refrigerant include R32, acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0027] The refrigerant of the present disclosure further contains R32 in a content ratio different from that of the additional refrigerants described above, specifically The refrigerant may contain 5 mass % or more of R32 based on the entire refrigerant. Hereinafter, an embodiment in which the refrigerant contains 5 mass % or more of R32 based on the entire refrigerant will be described.

[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 300 or less, and the refrigeration capacity ratio compared to R410A is 55% or more. <Requirements> Point D' (57.4, 5.0, 37.6), Point E' (17.5, 5.0, 77.5), Point F (0.0, 22.9, 77.1), Point B (0.0, 32.0, 68.0), and Point A (55.7, 44.3, 0.0) It is within the area of ​​the figure enclosed by the straight lines CD', D'E', E'F, FB, BA, and AC connecting the six points above, and on the line segments CD', D'E', E'F and BA (excluding points A, C, B, and F).

[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 boiling point is -40°C or less. <Requirements> Point C'(58.3, 17.7, 24.0), Point D'(57.4, 5.0, 37.6), Point J'(22.9, 5.0, 72.1), and Point K (19.3, 9.0, 71.7) It is within the area surrounded by straight lines C'D', D'J', J'K, and KC' connecting these four points, and is on said straight lines C'D', D'J', J'K, and KC'.

[0030] 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 C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point L' (17.1, 5.0, 77.9), and Point M (14.0, 7.8, 78.2) It lies within the area enclosed by straight lines C'D', 'D'L', L'M and MC' connecting these four points, and on said straight lines C'D', D'L', L'M and MC'.

[0031] The refrigerants disclosed herein are HFO-1132(E), R32 and R152a, with respect to the total: Refrigerant containing 5.0%, 25.0% and 70.0% by mass, respectively; refrigerant containing 12.2%, 34.7% and 53.1% by mass, respectively; refrigerant containing 14.0%, 7.8% and 78.2% by mass, respectively; refrigerant containing 15.0 mass%, 15.0 mass% and 70.0 mass%, respectively; refrigerant containing 15.0%, 25.0% and 60.0% by mass, respectively; refrigerant containing 15.0%, 35.0% and 50.0% by mass, respectively; refrigerant containing 19.3%, 9.0% and 71.7% by mass, respectively; refrigerant containing 25.0 mass%, 5.0 mass% and 70.0 mass%, respectively; refrigerant containing 25.0 mass%, 10.0 mass% and 65.0 mass%, respectively; refrigerant containing 25.0%, 15.0% and 60.0% by mass, respectively; refrigerant containing 25.0 mass%, 20.0 mass% and 55.0 mass%, respectively; refrigerant containing 25.0%, 30.0% and 45.0% by mass, respectively; refrigerant containing 26.5%, 20.7% and 52.8% by mass, respectively; Refrigerant containing 30.0 mass%, 10.0 mass% and 60.0 mass%, respectively; refrigerant containing 30.0%, 11.0% and 59.0% by mass, respectively; refrigerant containing 30.0%, 15.0% and 55.0% by mass, respectively; Refrigerants containing 35.0%, 5.0% and 60.0% by mass, respectively; refrigerant containing 35.0%, 10.0% and 55.0% by mass, respectively; refrigerant containing 35.0%, 15.0% and 50.0% by mass, respectively; Refrigerant containing 35.0%, 20.0% and 450.0% by mass, respectively; refrigerant containing 35.0%, 30.0% and 35.0% by mass, respectively; refrigerant containing 35.0%, 40.0% and 25.0% by mass, respectively; refrigerant containing 40.0 mass%, 10.0 mass% and 50.0 mass%, respectively; refrigerant containing 40.8%, 8.1% and 51.1% by mass, respectively; refrigerant containing 43.0%, 14.3% and 42.7% by mass, respectively; refrigerant containing 45.0 mass%, 10.0 mass% and 45.0 mass%, respectively; Refrigerants containing 45.0 mass%, 30.0 mass%, and 25.0 mass%, respectively refrigerant containing 45.0%, 40.0% and 15.0% by mass, respectively; refrigerant containing 55.0%, 10.0% and 35.0% by mass, respectively; refrigerant containing 55.0%, 20.0% and 25.0% by mass, respectively; Refrigerants containing 55.0%, 30.0% and 15.0% by mass, respectively; and refrigerant containing 55.0%, 40.0% and 5.0% by mass, respectively; The refrigerant may exclude at least one refrigerant selected from the group consisting of:

[0032] 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 below the line CD or lies below the line CD, disproportionation reaction occurs at 5 MPa and 150°C. In this case, even if the refrigerant pressure locally reaches 5 MPa and the refrigerant temperature locally reaches 150° C., the disproportionation reaction can be suppressed.

[0033] 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 consumes less power than an electric heater when used to operate the refrigeration cycle of an in-vehicle air conditioner. The advantage is that heating using a heat pump becomes possible. Examples of vehicle air conditioners include those for gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0034] The refrigerant of the present disclosure may contain 20% by mass or more of HFO-1132(E) based on the entire refrigerant, 30% by mass or more, 40% by mass or more, or 50% by mass or more of HFO-1132(E). The refrigerant of the present disclosure may contain 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more of R32 based on the entire refrigerant. The refrigerant of the present disclosure may contain 10% by mass or more of R152a based on the entire refrigerant. It may contain 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more. It may contain 70 mass % or more.

[0035] The refrigerant of the present disclosure may contain an additional refrigerant in addition to HFO-1132(E), R32, and R152a, as long as the above-mentioned properties and effects are not impaired. In this regard, in one embodiment, The refrigerant of the present disclosure preferably contains 99.5% by mass or more of HFO-1132(E), R32 and R152a in total, based on the total amount of the refrigerant, more preferably 99.75% by mass or more, and most preferably 99.9% by mass or more. It is more preferable that the content is 99.999% by mass, and it is even more preferable that the content is 99.9999% by mass or more. Most preferably, the refrigerant of the present disclosure is substantially composed of only HFO-1132(E), R32 and R152a. In this case, the refrigerants of the present disclosure may be HFO-1132(E), R32, and R152a. and unavoidable impurities. Additionally, the refrigerant of the present disclosure may consist solely of HFO-1132(E), R32 and R152a.

[0036] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one type of additional refrigerant alone or two or more types. Examples of the additional refrigerant include acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, 3,3 , 3-trifluoropropyne, etc.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0041] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0042] 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.

[0043] 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-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)

[0044] 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).

[0045] 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.

[0046] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0047] 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.

[0048] 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.

[0049] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0050] The stabilizers include, for example, nitro compounds, ethers, and amines.

[0051] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0052] An example of the ethers is 1,4-dioxane.

[0053] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine, diphenylamine, and the like.

[0054] Other examples include butylhydroxyxylene and benzotriazole.

[0055] 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.

[0056] 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.

[0057] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0069] 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.

[0070] 4. How to operate a refrigerator The method of operating a refrigerator according to the present disclosure is a method of operating a refrigerator using the refrigerant according to the present disclosure.

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

[0072] 5. Method for suppressing disproportionation reaction The method for suppressing a disproportionation reaction disclosed herein comprises the steps of: operating a refrigeration cycle using the refrigerant disclosed herein; The present invention relates to a method for inhibiting the disproportionation reaction of HFO-1132(E), comprising:

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

[0074] According to the method for suppressing a disproportionation reaction disclosed herein, it becomes possible to operate a refrigeration cycle while suppressing a disproportionation reaction even in a refrigerator that is not particularly provided with a means for suppressing a disproportionation reaction.

[0075] 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.

[0076] When used to inhibit a disproportionation reaction according to the present disclosure, the effect is particularly that the disproportionation reaction of HFO-1132(E) does not occur even when the refrigerant pressure is 5.0 MPa and the refrigerant temperature is 150°C.

[0077] 7. Refrigeration equipment The refrigeration device of the present disclosure comprises: a utilization side heat transport cycle for circulating a utilization side refrigerant; a heat source side heat transfer cycle for circulating a heat source side refrigerant; a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat source-side refrigerant, The heat source side refrigerant is the composition described in 1 above.

[0078] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

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

[0080] The quality of HFO-1132(E), R32 and R152a is shown in each table based on the sum of these. A mixed refrigerant was prepared by mixing the above components in a ratio of % by volume.

[0081] Each of these mixed refrigerants was examined for the presence or absence of a disproportionation reaction using the following test method and conditions. Test Method The refrigerant composition to be tested was transferred and filled into the test vessel, heated to 150°C, and then the Pt wire in the vessel was By applying a voltage to melt the refrigerant composition, 30 J of energy was given to the refrigerant composition. The presence or absence of this was judged by a sudden increase in pressure and temperature inside the device. Test conditions Test container: 38cc SUS container Test temperature: 150℃ Pressure: 5 MPa Judgment criteria "Non-explosive": The temperature or pressure after Pt filament melting is less than twice as high, and a rapid disproportionation reaction does not occur. not present. "Explosion": The temperature or pressure after Pt filament melting reached more than double the normal level, causing a sudden disproportionation reaction. . [Table 1]

[0082] The results in Table 1 show that the refrigerant of the present disclosure does not undergo disproportionation within the region shown in the ternary diagram in FIG.

[0083] Furthermore, for each of the above mixed refrigerants, the GWP, COP ratio and refrigeration capacity ratio against the refrigerants listed in the table were evaluated as follows. The GWP of HFO-1132(E) was set to 1, and the GWPs of R32 and R152a were calculated based on the values ​​in the Fourth Assessment Report of the IPCC (Intergovernmental Panel on Climate Change). The GWP of the refrigerants was evaluated. The COP, refrigeration capacity, and boiling point of the mixed refrigerants were also evaluated by the National Institute of The theoretical calculation of the refrigeration cycle of the mixed refrigerant was performed 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 was obtained by actual measurement and 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%

[0084] In the following table, "COP ratio" and "refrigeration capacity ratio" indicate the ratio (%) to R410A, R1234yf, or R404A. In the table, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant becomes atmospheric pressure (101.33 kPa).

[0085] The coefficient of performance (COP) was calculated using the following formula. COP = (refrigeration capacity or heating capacity) / power consumption

[0086] 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.

[0087] In the table below, "Driving distance (available)" refers to a vehicle equipped with a secondary battery of a certain capacity. In an electric vehicle, the distance that can be driven without heating (power consumption of heating is 0) is taken as 100%, and the distance that can be driven with heating is expressed as a relative percentage (%). This is what was done.

[0088] 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.

[0089] 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

[0090] 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).

[0091] The driving distance was calculated using the following formula. Driving distance = (battery capacity) / (power consumption + power consumption for heating)

[0092] The evaluation results are shown in the table below.

[0093] [Table 2]

[0094] From the results in Table 1, it can be seen that a mixed refrigerant consisting only of HFO-1132(E)) and R152a has a refrigeration capacity ratio of 55% or more to R410A and does not undergo disproportionation reaction at 5 MPa and 150°C when the mixed refrigerant contains 57% or less of HFO-1132(E)) and 43% or more of R152a by mass, respectively. It is clear that

[0095] [Table 3]

[0096] The results in Table 3 show that a refrigerant mixture consisting only of HFO-1132(E)) and R152a has a boiling point of -40°C or lower and does not undergo disproportionation at 5 MPa and 150°C when the contents of HFO-1132(E)) and R152a are 57% by mass or less and 32% by mass or more, respectively, of the entire refrigerant mixture.

[0097] [Table 4]

[0098] From the results in Table 4, it can be seen that a refrigerant mixture consisting only of HFO-1132(E)) and R152a has a refrigeration capacity ratio of 70% or more relative to R404A and does not undergo disproportionation reactions at 5 MPa and 150°C when it contains 57% or less by mass of HFO-1132(E)) and 43% or more by mass of R152a, respectively, relative to the entire refrigerant mixture. It is clear that

[0099] [Table 5]

[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 total is 100 mass%, when the coordinates (x, y, z) satisfy the following requirements, the disproportionation reaction does not occur at 5 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity ratio compared to R410A is 55% or more (Figure 2). <Requirements> Point D' (57.4, 5.0, 37.6), Point E' (17.5, 5.0, 77.5), Point F (0.0, 22.9, 77.1), Point B (0.0, 32.0, 68.0), and Point A (55.7, 44.3, 0.0) It is within the area of ​​the figure enclosed by the straight lines CD', D'E', E'F, FB, BA, and AC connecting the six points above, and on the line segments CD', D'E', E'F and BA (excluding points A, C, B, and F).

[0101] [Table 6]

[0102] In addition, the results in Table 6 show that, among the refrigerants disclosed in this disclosure, HFO-1132(E), R32 and R152a When the mass percentages based on the sum of these 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) satisfy the following requirements: At 5 MPa and 150°C, no disproportionation reaction occurs, the GWP is 150 or less, and the boiling point is -40 It can be seen that the temperature is below ℃ (Figure 3). <Requirements> Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point J' (22.9, 5.0, 72.1), Point K (19.3, 9.0, 71.7) It is within the area surrounded by straight lines C'D', D'J', J'K, and KC' connecting these four points, and is on said straight lines C'D', D'J', J'K, and KC'.

[0103] [Table 7]

[0104] Furthermore, from the results in Table 7, it can be seen that, among the refrigerants disclosed herein, HFO-1132(E), R32 and R152a When the mass percentages 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%, the coordinates (x, y, z) satisfy the following requirements: It can be seen that, at 5 MPa and 150°C, no disproportionation reaction occurs, the GWP is 150 or less, and the refrigeration capacity ratio compared to R404A is 70% or more (Figure 4). <Requirements> Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point L' (17.1, 5.0, 77.9), and Point M (14.0, 7.8, 78.2) It lies within the area enclosed by straight lines C'D', 'D'L', L'M and MC' connecting these four points, and on said straight lines C'D', D'L', L'M and MC'.

Claims

1. A method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethane (R152a) in amounts of 22.6 to 57% by mass and 77.4 to 43% by mass, respectively, relative to the total amount thereof.

2. The method according to claim 1, comprising HFO-1132(E) and R152a in amounts of 44.7 to 57% by mass and 55.3 to 43% by mass, respectively, relative to their total.

3. The method according to claim 1, comprising HFO-1132(E) and R152a in amounts of 22.9 to 57% by mass and 77.1 to 43% by mass, respectively, relative to their total.

4. The method according to claim 1, comprising HFO-1132(E) and R152a in amounts of 41.4 to 57% by mass and 58.6 to 43% by mass, respectively, relative to their total.

5. The method according to claim 1, comprising HFO-1132(E) and R152a in amounts of 28.3 to 57% by mass and 71.7 to 43% by mass, respectively, relative to their total.

6. The method according to claim 1, comprising HFO-1132(E) and R152a in amounts of 44.1 to 57% by mass and 55.9 to 43% by mass, respectively, relative to their total.

7. The method according to any one of claims 1 to 6, wherein HFO-1132(E) and R152a are included in a total of 99.5% by mass or more relative to the total amount of refrigerant.

8. A composition containing a refrigerant, A method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using a composition in which the refrigerant contains 99.5% by mass or more of R152a, R32, and HFO-1132(E) in total relative to the total refrigerant, When x, y, and z are the mass percentages based on the sum of HFO-1132(E), R32, and R152a, respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and R152a is 100% by mass, The coordinates (x, y, z) are Point C (60.0, 40.0, 0.0), Point D' (57.4, 5.0, 37.6), Point E' (17.5, 5.0, 77.5), Point F (0.0, 22.9, 77.1), Point B (0.0, 32.0, 68.0), and Point A (55.7, 44.3, 0.0) A method that includes the area within the figure enclosed by the lines CD', D'E', E'F, FB, BA, and AC connecting the six points, and the line segments CD', D'E', E'F and BA (excluding points A, C, B, and F).

9. In the aforementioned refrigerant, the coordinates (x, y, z) are: Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point J' (22.9, 5.0, 72.1), and Point K (19.3, 9.0, 71.7) The method according to claim 8, wherein the figure is located within the area enclosed by the lines C'D', D'J', J'K, and KC' connecting the four points, and is on the lines C'D', D'J', J'K, and KC'.

10. In the aforementioned refrigerant, the coordinates (x, y, z) are: Point C' (58.3, 17.7, 24.0), Point D' (57.4, 5.0, 37.6), Point L' (17.1, 5.0, 77.9), and Point M (14.0, 7.8, 78.2) The method according to claim 8, wherein the figure is located within the area enclosed by the lines C'D', D'L', L'M, and MC' connecting the four points, and is on the lines C'D', D'L', L'M, and MC'.

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