Refrigerant-containing composition, its use, refrigerator having same and method of operating the refrigerator

Abstract

To suppress disproportionation in a refrigerant including HFO-1132(E).SOLUTION: The present invention discloses a method for suppressing the disproportionation reaction of trans-1,2-difluoroethylene (HFO-1132(E)), the method including a step for operating a refrigeration cycle by using a composition that includes a refrigerant, the refrigerant including HFO-1132(E) as well as trifluoroethylene (HFO-1123) and difluoromethane (R32).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] A working fluid containing 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 157765 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to suppress disproportionation in refrigerants containing HFO-1132(E). [Means for solving the problem]

[0005] Section 1. A composition comprising a refrigerant, The refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and difluoromethane (R32). A method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) A method in which the point is within the area of ​​the figure enclosed by the lines AB, BP, and PA connecting the three points above, or is on the line AB (excluding points A and B). Section 2. In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) The method according to item 1, wherein the point A is within the area surrounded by the lines AB, BD, DC, and CA connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C). Section 3. In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) The method according to item 1, wherein the point B is within the area of ​​the figure enclosed by the lines EB, BD', and D'E connecting the three points, or is on the lines EB and D'E (excluding points B and D'). Section 4. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) The method according to item 1, wherein the object is within the range of a figure enclosed by lines FG, GH, HD', D'I and IF connecting the five points above or on said lines (excluding point H, point D' and line HD'). Section 5. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) Item 3. The method according to Item 1, wherein the four points are within a range defined by lines FG, GJ, JI, and IF, respectively, connecting the four points, or are on the lines. Section 6. A composition comprising a refrigerant, Use of a composition comprising HFO-1132(E), HFO-1123 and R32 as a refrigerant for suppressing a disproportionation reaction of HFO-1132(E), When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) The point A is used within the area enclosed by the lines AB, BP, and PA connecting the three points above, or on the line AB (excluding points A and B). Section 7. In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) The use described in item 6, wherein the area is within the shape enclosed by the lines AB, BD, DC, and CA connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C). Section 8. In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) Item 7. The use according to item 6, wherein the area is within the shape enclosed by the lines EB, BD', and D'E connecting the three points above, or is on the lines EB and D'E (excluding points B and D'). Section 9. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) Item 7. The use according to Item 6, wherein the area is within a shape surrounded by lines FG, GH, HD', D'I, and IF connecting the five points above or is on said lines. Section 10. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) Item 7. The use according to Item 6, wherein the area is within a shape surrounded by lines FG, GJ, JI, and IF connecting the four points above or is on said lines. Section 11. of HFO-1123 and / or R32, Use of HFO-1132(E) to inhibit the disproportionation reaction, The suppression of the disproportionation reaction is When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) Use by mixing the materials so that they are within the area of ​​the figure enclosed by the lines AB, BP, and PA connecting the three points above, or on the line AB (excluding points A and B). Section 12. In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) The use according to item 11, wherein the area is within the shape enclosed by the lines AB, BD, DC, and CA connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C). Section 13. In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) Item 12. The use according to item 11, wherein the area is within the shape enclosed by the lines EB, BD', and D'E connecting the three points above, or is on the lines EB and D'E (excluding points B and D'). Section 14. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) Item 12. The use according to Item 11, wherein the area is within the shape enclosed by the lines FG, GH, HD', D'I, and IF connecting the five points above or on the lines (excluding points H, D', and line HD'). Section 15. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) Item 12. The use according to Item 11, wherein the area is within a shape surrounded by lines FG, GJ, JI, and IF connecting the four points above or is on said lines. Section 16. Contains HFO-1123 and / or R32 A composition for use in inhibiting the disproportionation reaction of HFO-1132(E), comprising: The suppression of the disproportionation reaction is When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) The composition is prepared by mixing the components so that the components are within the area defined by the lines AB, BP, and PA connecting the three points above or on the line AB (excluding points A and B). Section 17. In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) Item 17. The composition according to item 16, wherein the composition is within a range defined by lines AB, BD, DC, and CA respectively connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C). Section 18. In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) Item 17. The composition according to item 16, wherein the composition is within a range defined by lines EB, BD', and D'E connecting the three points above, or is on the lines EB and D'E (excluding points B and D'). Section 19. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) Item 17. The composition according to item 16, wherein the composition is within the area surrounded by lines FG, GH, HD', D'I, and IF connecting the five points above or on the lines (excluding points H, D', and line HD'). Section 20. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) Item 17. The composition according to Item 16, wherein the composition is within a range defined by lines FG, GJ, JI, and IF connecting the four points above or on the lines above. Section 21. A composition comprising a refrigerant, The refrigerant is HFO-1132(E), HFO-1123 and R32, HFO-1132(E), HFO-1123 and R32 are expressed as x, y, and z, respectively, as the mass% of these totals: HFO-1132(E), HFO-1123In the three-component composition diagram where the sum of R32 and R33 is 100 mass%, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) A composition located within the area surrounded by the lines FG, GH, HD', D'I and IF connecting the five points above or on said lines (excluding points H, D' and line HD'). Section 22. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) Item 22. The composition according to item 21, wherein the composition is within a range defined by lines FG, GJ, JI, and IF connecting the four points above or on the lines above. Section 23. Item 23. The composition according to any one of Items 20 to 22, further comprising a refrigerating machine oil and used as a working fluid for a refrigerating machine. Section 24. 24. The composition according to any one of items 20 to 23, which is used as an alternative refrigerant to R410A. Section 25. Use of the composition according to any one of items 4 to 6 as an alternative refrigerant to R410A. Section 26. 24. A refrigerator comprising the composition according to any one of items 20 to 23 as a working fluid. Section 27. A method for operating a refrigerator, comprising: 24. A method comprising circulating the composition according to any one of items 20 to 23 as a working fluid in a refrigerator. [Effects of the Invention]

[0006] The present disclosure makes it possible to suppress disproportionation in refrigerants containing HFO-1132(E). [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 2 is a ternary diagram showing the composition ratios of refrigerant mixtures subjected to disproportionation suppression tests in Examples and the disproportionation limit lines derived from the results. [Figure 2] FIG. 1 is a ternary diagram showing the composition ratio of the composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] HFO-1132(E) is chemically unstable due to the presence of unsaturated bonds, and there is a possibility of a risk of disproportionation. As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that disproportionation of HFO-1132(E) is suppressed in a mixed refrigerant containing HFO-1132(E), HFO-1123, and R32 in a specific mixing ratio.

[0009] The present disclosure has been completed as a result of further research based on this finding. The present disclosure includes the following embodiments. <Terminology> In this specification, the term "refrigerant" includes at least compounds assigned a refrigerant number (ASHRAE number) beginning with the letter R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and also includes compounds that have equivalent refrigerant properties even if they have not yet been assigned a refrigerant number. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of their compound structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and 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). Furthermore, 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] As used herein, the term "substitution," when used in the context of "replacing" a first refrigerant with a second refrigerant, refers to a first type of equipment designed to operate using a first refrigerant, which can be operated under optimal conditions using a second refrigerant with only minor component changes (at least one of refrigeration oil, gaskets, packing, expansion valves, dryers, and other components) and equipment adjustments, as necessary. In other words, this type refers to operating the same equipment with a "substitution" of a refrigerant. This type of "substitution" can be categorized as "drop-in substitution," "nearly drop-in substitution," or "retrofit," in order of decreasing 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 purpose as an existing use of a first refrigerant, is also included in the term "substitution." This category refers to "substituting" a refrigerant to serve the same purpose.

[0013] In this specification, the term "refrigerator" refers to a device that removes heat from an object or space, thereby lowering the temperature below that of the surrounding air, and maintaining that low temperature. In other words, a refrigerator is a conversion device that obtains energy from an external source, performs work, and converts it into energy in order to transfer heat from a low-temperature object to a high-temperature object.

[0014] Unless otherwise specified, pressures described in this specification are in units of absolute pressure (MPa).

[0015] In this specification, the term "RCL of x% or more" refers to a refrigerant whose RCL is x% or more, calculated in accordance with the ANSI / ASHRAE 34-2013 standard. The RCL is a concentration limit in the air that takes into account a safety factor and is an index intended to reduce the risk of acute toxicity, asphyxiation, and flammability in enclosed spaces where humans are present. The RCL is determined in accordance with the standard. Specifically, the RCL is the lowest concentration among the acute toxicity exposure limit (ATEL), oxygen deprivation limit (ODL), and flammable concentration limit (FCL), calculated in accordance with sections 7.1.1, 7.1.2, and 7.1.3 of the standard.

[0016] 1. refrigerant 1.1 Refrigerant components The refrigerant of the present disclosure is a mixed refrigerant containing HFO-1132(E), HFO-1123, and R32.

[0017] The refrigerant of the present disclosure satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) when the refrigerant pressure is 3.0 MPa. <Requirements> Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) The point is within the area enclosed by the lines AB, BP, and PA connecting the three points above, or is on the line AB (excluding points A and B).

[0018] The refrigerant of the present disclosure not only further suppresses disproportionation of HFO-1132(E) when the refrigerant pressure is 3.0 MPa, but also achieves a GWP of 400 or less by satisfying the following requirements: In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) The point A is within the area enclosed by the lines AB, BD, DC, and CA connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C).

[0019] The refrigerant of the present disclosure not only suppresses disproportionation of HFO-1132(E) but also has a GWP of 275 or less by satisfying the following requirements: <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) The point B is located within the area of ​​the figure enclosed by the lines EB, BD', and D'E connecting the three points above, or on the lines EB and D'E (excluding points B and D').

[0020] The refrigerant disclosed herein satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) and achieving a GWP of 275 or less when the refrigerant pressure is 3.0 MPa. Furthermore, the refrigerant concentration limit (RCL) is 60 g / m.3 This is the same as above, and the COP ratio to R410A is 96.5% or more. <Requirements> The refrigerant is HFO-1132(E), HFO-1123 and R32, HFO-1132(E), HFO-1123 and R32 are expressed as x, y, and z, respectively, as the mass% of these totals: HFO-1132(E), HFO-1123 In the three-component composition diagram where the sum of R32 and R33 is 100 mass%, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) The five points are within the area bounded by the lines FG, GH, HD', D'I and IF, or are on the lines.

[0021] The refrigerant disclosed herein not only suppresses disproportionation of HFO-1132(E) and has a GWP of 275 or less, but also has a refrigerant concentration limit (RCL) of 60 g / m by satisfying the following requirements: 3 As a result, the COP ratio to R410A becomes 96.5% or more, and the condensation temperature glide ratio to R410A becomes 2.0 or less. <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) The area is within the shape enclosed by the lines FG, GJ, JI, and IF connecting the four points above, or is on said lines.

[0022] The refrigerants of the present disclosure may contain, in addition to HFO-1132(E), HFO-1123, and R32, additional refrigerants, as long as the above-described properties and effects are not impaired. In this regard, the refrigerants of the present disclosure preferably contain 99.5 mass% or more of HFO-1132(E), HFO-1123, and R32 in total, based on the total refrigerant, more preferably 99.75 mass% or more, even more preferably 99.9 mass% or more, even more preferably 99.99 mass% or more, and most preferably 99.999 mass% or more. The refrigerants of the present disclosure may consist essentially of HFO-1132(E), HFO-1123, and R32, or may consist solely of HFO-1132(E), HFO-1123, and R32. When the refrigerant of the present disclosure consists essentially of only HFO-1132(E), HFO-1123, and R32, it may contain, in addition to HFO-1132(E), HFO-1123, and R32, impurities that are inevitably mixed in during the production process of these refrigerants.

[0023] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one or more additional refrigerants. Examples of additional refrigerants include acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, HFC-152a, HFC-161, and 3,3,3-trifluoropropyne. The total amount of the additional refrigerant is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, even more preferably 0.1% by mass or less, and most preferably 0.01% by mass or less, based on the total amount of the refrigerant.

[0024] 1.2 Purpose The refrigerant of the present disclosure can be preferably used as a working fluid in a refrigerator.

[0025] The compositions of the present disclosure are suitable for use as replacement refrigerants for R410A.

[0026] 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. Furthermore, 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.

[0027] The refrigerant composition of the present disclosure 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 is preferably substantially free of refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure preferably contains refrigerating machine oil in an amount of 1 mass% or less, more preferably 0.1 mass% or less, relative to the total refrigerant composition.

[0028] 2.1 water The refrigerant composition of the present disclosure may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1 mass% or less based on the total refrigerant. When the refrigerant composition contains a trace amount of water, the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant are stabilized, and oxidation of the unsaturated fluorocarbon compounds is also made less likely, thereby improving the stability of the refrigerant composition.

[0029] 2.2 tracer The tracer is added to the refrigerant composition of the present disclosure at a detectable concentration so that if the refrigerant composition of the present disclosure is diluted, contaminated, or otherwise altered, the tracer can be traced.

[0030] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0031] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0032] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (NO), etc. Particularly preferred tracers are hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers.

[0033] The following compounds are preferred as tracers: FC-14 (tetrafluoromethane, CF4) HCC-40 (chloromethane, CH3Cl) HFC-23 (trifluoromethane, CHF3) HFC-41 (fluoromethane, CH3Cl) HFC-125 (pentafluoroethane, CF3CHF2) HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2) HFC-143a (1,1,1-trifluoroethane, CF3CH3) HFC-143 (1,1,2-trifluoroethane, CHF2CH2F) HFC-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)

[0034] The refrigerant compositions of the present disclosure may contain a total of about 10 parts per million (ppm) by weight or more of tracer(s) based on the total refrigerant composition, and may contain about 1000 ppm or less of tracer(s). The refrigerant compositions of the present disclosure preferably contain about 30 ppm or more of tracer(s) based on the total refrigerant composition, and more preferably contain about 50 ppm or more of tracer(s). The refrigerant compositions of the present disclosure preferably contain about 500 ppm or less of tracer(s) based on the total refrigerant composition, and more preferably contain about 300 ppm or less of tracer(s).

[0035] 2.3 UV fluorescent dye The refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone or two or more types.

[0036] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from among commonly used ultraviolet fluorescent dyes.

[0037] 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.

[0038] 2.4 stabilizers The refrigerant composition of the present disclosure may contain one type of stabilizer alone or two or more types.

[0039] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0040] Examples of stabilizers include nitro compounds, ethers, and amines.

[0041] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0042] An example of the ethers is 1,4-dioxane.

[0043] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0044] Other examples include butylhydroxyxylene and benzotriazole.

[0045] The stabilizer content is not particularly limited, but is usually preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the refrigerant. The stabilizer content is usually preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the refrigerant.

[0046] 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.

[0047] The polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.

[0048] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0049] The content of the polymerization inhibitor is not particularly limited, and is usually preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, based on the total mass of the refrigerant. The content of the polymerization inhibitor is usually preferably 5% by mass or less, and more preferably 5% by mass or less, based on the total mass of the refrigerant.

[0050] 3. Working fluid containing refrigeration oil The refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and a refrigerating machine oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerating machine oil-containing working fluid of the present disclosure is obtained by mixing the refrigerating machine oil used in the compressor of the refrigerator with the refrigerant or refrigerant composition. The refrigerating machine oil-containing working fluid generally contains 10 mass % or more and 50 mass % or less of the refrigerating machine oil.

[0051] 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.

[0052] The refrigerating machine oil is not particularly limited and can be appropriately selected from commonly used refrigerating machine oils. In this case, if necessary, a refrigerating machine oil that is superior in terms of miscibility with the mixture and the effect of improving the stability of the mixture can be appropriately selected.

[0053] The base oil of the refrigerating machine oil is preferably at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0054] The refrigerating machine oil may further contain, in addition to the base oil, an additive such as 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.

[0055] From the viewpoint of lubrication, a refrigerating machine oil having a kinematic viscosity of 5 cSt or more at 40° C. is preferred. From the viewpoint of lubrication, a refrigerating machine oil having a kinematic viscosity of 400 cSt or less at 40° C. is preferred.

[0056] 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.

[0057] 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.

[0058] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0059] Examples of the compatibilizer include polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether, and 1,1,1-trifluoroalkane, etc. Polyoxyalkylene glycol ether is particularly preferred as the compatibilizer.

[0060] 4. How to operate a refrigerator The method for operating a refrigerator according to the present disclosure is a method for operating a refrigerator using the refrigerant according to the present disclosure.

[0061] Specifically, a method of operating a refrigerator according to the present disclosure includes circulating a refrigerant according to the present disclosure in the refrigerator.

[0062] 5. Method for suppressing disproportionation reaction The method for suppressing the disproportionation reaction of the present disclosure is a method for suppressing the disproportionation reaction of HFO-1132(E), which includes a step of operating a refrigeration cycle using the refrigerant of the present disclosure.

[0063] The method for inhibiting the disproportionation reaction of the present disclosure has the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring, particularly when the refrigerant pressure is 3.0 MPa.

[0064] The method for suppressing a disproportionation reaction disclosed herein makes it possible to operate a refrigeration cycle even in a refrigerator that is not particularly provided with a means for suppressing a disproportionation reaction.

[0065] 6. Use for inhibiting disproportionation reactions The use of the present disclosure is the use of HFO-1123 and / or R32 to suppress the disproportionation reaction of HFO-1132(E), and the suppression of the disproportionation reaction is achieved by mixing HFO-1132(E), HFO-1123, and R32 in a mixing ratio of the refrigerant of the present disclosure.

[0066] When used to inhibit disproportionation reactions according to the present disclosure, the effect of preventing disproportionation reactions of HFO-1132(E) from occurring is particularly pronounced when the refrigerant pressure is 3.0 MPa.

[0067] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0068] The present disclosure will be described in more detail below with reference to examples, but is not limited to these examples.

[0069] Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1123, and R32 in the mass percentages shown in Tables 1 to 3, based on the total mass of these.

[0070] Each of these mixed refrigerants was examined for the presence or absence of disproportionation reactions using the following test method and conditions. The results are shown in Table 1 and Figure 1. Test Method The refrigerant composition to be tested was transferred and filled into a test vessel and heated to 150°C. A voltage was then applied to a Pt wire inside the vessel, causing it to melt and break, thereby giving the refrigerant composition 30 J of energy. The presence or absence of a disproportionation reaction was determined 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 "No explosion": The temperature or pressure after Pt fusing is less than doubled, and no sudden disproportionation reaction occurs. "Explosion": The temperature or pressure after Pt wire melting reached more than double the normal value, causing a sudden disproportionation reaction.

[0071] [Table 1]

[0072] Furthermore, the COP ratio and refrigeration capacity ratio of each of these mixed refrigerants were calculated based on R410. The calculation conditions were as follows: Evaporation temperature: 5℃ Condensation temperature: 45℃ Superheat degree: 5K Supercooling degree; 5K Compressor efficiency: 70%

[0073] These values, along with the GWP for each mixed refrigerant, are shown in Tables 2 to 4. Table 4 also shows the results of investigating whether or not a disproportionation reaction occurred.

[0074] [Table 2]

[0075] [Table 3]

[0076] [Table 4]

[0077] These results show that a refrigerant mixture of HFO-1132(E), HFO-1123 and R32 satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) at a refrigerant pressure of 3.0 MPa. <Requirements> Point A(54.0, 0.0, 46.0), Point B (0.0, 68.0, 32.0) and Point P(0.0, 0.0, 100.0) The point is within the area enclosed by the lines AB, BP, and PA connecting the three points above, or is on the line AB (excluding points A and B).

[0078] These results show that a refrigerant mixture of HFO-1132(E), HFO-1123 and R32 that satisfies the following requirements not only further suppresses disproportionation of HFO-1132(E) at a refrigerant pressure of 3.0 MPa, but also achieves a GWP of 400 or less. <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point A(54.0, 0.0, 46.0), Point B(0.0, 68.0, 32.0), Point D(0.0, 40.8, 59.2) and Point C(40.8, 0.0, 59.2) The point A is within the area enclosed by the lines AB, BD, DC, and CA connecting the four points above, or is on the lines AB and DC (excluding points A, B, D, and C).

[0079] These results show that a refrigerant mixture of HFO-1132(E), HFO-1123 and R32 not only suppresses disproportionation of HFO-1132(E), but also keeps the GWP at 275 or less by satisfying the following requirements: <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) The point B is located within the area of ​​the figure enclosed by the lines EB, BD', and D'E connecting the three points above, or on the lines EB and D'E (excluding points B and D').

[0080] These results show that the mixed refrigerant of HFO-1132(E), HFO-1123 and R32 satisfies the following requirements, thereby suppressing the disproportionation of HFO-1132(E) and achieving a GWP of 275 or less. In addition, the refrigerant concentration limit (RCL) is 60g / m 3 It can be seen that the COP ratio to R410A is 96.5% or more. <Requirements> The refrigerant is HFO-1132(E), HFO-1123 and R32, HFO-1132(E), HFO-1123 and R32 are expressed as x, y, and z, respectively, as the mass% of these totals: HFO-1132(E), HFO-1123 In the three-component composition diagram where the sum of R32 and R33 is 100 mass%, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) The five points are within the area bounded by the lines FG, GH, HD', D'I and IF, or are on the lines.

[0081] These results show that the mixed refrigerant of HFO-1132(E), HFO-1123 and R32 satisfies the following requirements, thereby suppressing the disproportionation of HFO-1132(E) and achieving a GWP of 275 or less. In addition, the refrigerant concentration limit (RCL) is 60g / m 3 As a result, it can be seen that the COP ratio to R410A is 96.5% or more, and the condensation temperature glide ratio to R410A is 2.0 or less. <Requirements> In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) The area is within the shape enclosed by the lines FG, GJ, JI, and IF connecting the four points above, or is on said lines.

Claims

1. A method for inhibiting the disproportionation reaction of HFO-1132(E), comprising: operating a refrigeration cycle using a composition containing a refrigerant, The refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and difluoromethane (R32) in a total amount of 99.5% by mass or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) A method in which the point B is within the area of ​​the figure enclosed by the lines EB, BD', and D'E connecting the three points above, or is on the lines EB and D'E (excluding points B and D').

2. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) 2. The method according to claim 1, wherein the object is located within a range of a figure enclosed by straight lines FG, GH, HD', D'I and IF respectively connecting the five points above or on said straight lines (excluding point H, point D' and line HD').

3. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) 2. The method according to claim 1, wherein the distance is within a range of a figure enclosed by lines FG, GJ, JI, and IF respectively connecting the four points above or on said lines.

4. Use of a composition containing a refrigerant for inhibiting the disproportionation reaction of HFO-1132(E), comprising: The refrigerant contains HFO-1132(E), HFO-1123, and R32 in a total amount of 99.5% by mass or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) Use within the area of ​​the shape enclosed by the lines EB, BD', and D'E connecting the three points above, or on the lines EB and D'E (excluding points B and D').

5. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) The use according to claim 4, wherein the area is within a shape surrounded by lines FG, GH, HD', D'I and IF respectively connecting the five points above or on said lines.

6. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) The use according to claim 4, wherein the area is within a shape surrounded by lines FG, GJ, JI and IF respectively connecting the four points above or on said lines.

7. of HFO-1123 and / or R32, Use of HFO-1132(E) to inhibit the disproportionation reaction, The suppression of the disproportionation reaction is In a refrigerant containing a total of 99.5 mass% or more of HFO-1132(E), HFO-1123, and R32, when the mass% of HFO-1132(E), HFO-1123, and R32 based on their total sum is x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) The use is carried out by mixing HFO-1132(E), HFO-1123 and R32 so that the mixture is within the area enclosed by the straight lines EB, BD' and D'E connecting the three points above or on the straight lines EB and D'E (excluding points B and D').

8. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) The use according to claim 7, wherein the area is within the shape enclosed by the straight lines FG, GH, HD', D'I and IF connecting the five points above or on said straight lines (excluding point H, point D' and line HD').

9. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) The use according to claim 7, wherein the area is within a shape surrounded by lines FG, GJ, JI and IF respectively connecting the four points above or on said lines.

10. containing HFO-1123 and / or R32, A composition for use in inhibiting the disproportionation reaction of HFO-1132(E), comprising: The suppression of the disproportionation reaction is In a refrigerant containing a total of 99.5 mass% or more of HFO-1132(E), HFO-1123, and R32, when the mass% of HFO-1132(E), HFO-1123, and R32 based on their total sum is x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point E(33.6, 25.7, 40.7), Point B (0.0, 68.0, 32.0) and Point D'(0.0, 59.3, 40.7) The composition is prepared by mixing HFO-1132(E), HFO-1123 and R32 so that the area is within the shape enclosed by the straight lines EB, BD' and D'E connecting the three points above or on the straight lines EB and D'E (excluding points B and D').

11. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) 11. The composition according to claim 10, wherein the composition is within a range surrounded by lines FG, GH, HD', D'I, and IF respectively connecting the five points above or on said lines (excluding point H, point D', and line HD').

12. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) 11. The composition according to claim 10, which is located within a range surrounded by lines FG, GJ, JI, and IF connecting the four points above or on said lines.

13. A composition comprising a refrigerant, The refrigerant contains HFO-1132(E), HFO-1123, and R32 in a total amount of 99.5% by mass or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), HFO-1123, and R32 based on their sum are x, y, and z, respectively, in a three-component composition diagram where the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass%, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point H(0.0, 59.8, 40.2), Point D'(0.0, 59.3, 40.7) and Point I (19.2, 40.1, 40.7) A composition located within the area surrounded by the lines FG, GH, HD', D'I and IF connecting the five points above or on said lines (excluding points H, D' and line HD').

14. In the refrigerant, the coordinates (x, y, z) are: Point F(19.5, 43.4, 37.1), Point G(10.0, 50.8, 39.2), Point J (13.9, 45.4, 40.7) and Point I (19.2, 40.1, 40.7) 14. The composition according to claim 13, which is located within a range surrounded by lines FG, GJ, JI, and IF connecting the four points above or on said lines.

15. The composition according to claim 13 or 14, further comprising a refrigerating machine oil and used as a working fluid for a refrigerating machine.

16. The composition according to claim 13 or 14, which is used as an alternative refrigerant to R410A.

17. Use of the composition according to claim 13 or 14 as an alternative refrigerant to R410A.

18. A refrigerator comprising the composition of claim 13 or 14 as a working fluid.

19. 15. A method for operating a refrigerator, comprising circulating the composition of claim 13 or 14 as a working fluid in the refrigerator.

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