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

Abstract

The objective of the present invention is to suppress disproportionation in a refrigerant containing HFO-1132(E) when the refrigerant pressure is 3.0 MPa. Another objective is to provide a new refrigerant containing HFO-1132(E). [Solution] A method for suppressing the disproportionation reaction of HFO-1132(E), comprising a step of operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains HFO-1132(E), R32, and R1234yf.

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] This disclosure suppresses disproportionation in refrigerants containing HFO-1132(E) when the refrigerant pressure is 3.0 MPa. In another aspect, the present disclosure provides a novel compound containing HFO-1132(E). The object is to provide a refrigerant. [Means for solving the problem]

[0005] Section 1. A composition comprising a refrigerant, The refrigerant is trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethanone (HFO-1132(E)), A method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using a composition containing fluorocarbon (R32) and 2,3,3,3-tetrafluoro-1-propene (R1234yf). So, The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point Q(54.0, 46.0, 0.0), Point R(44.0, 0.0, 56.0), Point P(0.0, 0.0, 100.0) and Point O(0.0, 100.0, 0.0) A method in which the point is within the area of ​​the figure enclosed by the lines QR, RP, PO, and OQ connecting the four points above, or on the line QR (excluding points Q and R). Section 2. A composition comprising a refrigerant, the refrigerant comprises HFO-1132(E), R32, and R1234yf; The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point M(19.8, 41.2, 39.0), Point K(19.8, 37.7, 42.5), Point L(12.2, 44.2, 43.6) and Point N(14.7, 44.2, 41.1) A composition that is within the area surrounded by the lines MK, KL, LN, and NM connecting the four points above, or that is on said lines MK, KL, LN, and NM. Section 3. A composition comprising a refrigerant, the refrigerant comprises HFO-1132(E), R32, and R1234yf; The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point I''(19.8, 23.3, 56.9), Point K''(19.8, 17.7, 62.5) and Point L'(12.1, 23.3, 64.6) Within the area of ​​the shape enclosed by the lines I''K'', K''L' and L'I'' connecting the three points respectively are on said straight lines I''K'', K''L' and L'I''. Section 4. A composition comprising a refrigerant, The refrigerant contains HFO-1132(E), R32 and R1234yf in a total amount of 99.5 mass% or more based on the total amount of the refrigerant. fruit, The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point C(28.7, 53.7, 17.6), Point D(9.0, 74.0, 17.0), Point A (26.0, 74.0, 0.0) and Point I (26.7, 73.3, 0.0) The point A is located within the area of ​​the figure enclosed by the line segments CD, DA, AI, and IC connecting the four points above, or on the line segments CD, DA, and IC (excluding points A and I), the line segments DA, AI, and IC are straight lines; and The coordinates (x, y, z) of the point on the line segment CD are (x, 0.0069x 2 -1.2909x+85.059, -0.0069x 2 +0.2909x+14.941), a composition. Section 5. A composition comprising a refrigerant, The refrigerant contains HFO-1132(E), R32 and R1234yf in a total amount of 99.5 mass% or more based on the total amount of the refrigerant. A composition comprising: The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point E(18.5, 53.1, 28.4), Point F(0.0, 72.8, 27.2), Point B (0.0, 73.9, 26.1) and Point K'(18.0, 74.0, 8.0) The point F and the point B are excluded from the figure enclosed by the line segments EF, FB, BK', and K'E connecting the four points above, or are on the line segments EF, BK', and K'E. The line segments FB, BK', and K'E are straight lines, and The coordinates (x, y, z) of the point on the line segment EF are (x, 0.0077x 2 -1.2066x+72.8, -0.0077x 2 +0.2066x+27.2), a composition. Section 6. A composition comprising a refrigerant, The refrigerant contains HFO-1132(E), R32 and R1234yf in a total amount of 99.5 mass% or more based on the total amount of the refrigerant. A composition comprising: The mass percentages of HFO-1132(E), R32, and R1234yf based on their total mass are x, y, and z, respectively. In this case, in a three-component composition diagram where the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are: Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point T(26.6, 23.3, 50.1) A composition that is within the area surrounded by the lines US, ST, and TU connecting the three points above, or that is on said lines US, ST, and TU. Section 7. A composition comprising a refrigerant, The refrigerant comprises: HFO-1132(E), R32 and R1234yf; and at least one additional refrigerant selected from the group consisting of 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; A composition comprising: Section 8. The refrigerant further comprises: at least one additional refrigerant selected from the group consisting of 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; Item 8. The composition according to any one of items 2 to 7, comprising: Section 9. Item 9. The composition according to any one of items 2 to 8, which is used as an alternative refrigerant to R32 and / or R410A. Section 10. Use of the composition according to any one of items 2 to 8 as an alternative refrigerant to R32 and / or R410A. Section 11. A refrigerator comprising the composition according to any one of items 2 to 8 as a working fluid. Section 12. A method for operating a refrigerator, comprising: Item 9. A method for producing a refrigerator comprising circulating the composition according to any one of items 2 to 8 as a working fluid in a refrigerator. method. [Effects of the Invention]

[0006] According to the present disclosure, when the refrigerant pressure is 3.0 MPa, the uneven Furthermore, in another aspect, the present disclosure provides a method for producing a pharmaceutical composition containing HFO-1132(E). This makes it possible to provide a new refrigerant that [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of an apparatus used in a flammability test. [Figure 2] FIG. 1 is a ternary diagram showing the composition of the composition of the present disclosure. [Figure 3] FIG. 1 is a ternary diagram showing the composition of the composition of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] HFO-1132(E) is chemically unstable due to its unsaturated bond, and there is a risk of disproportionation. As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, they found that in a refrigerant mixture containing HFO-1132(E), R32, and R1234yf in a specific mixing ratio, disproportionation of HFO-1132(E) is suppressed when the pressure of the refrigerant mixture is 3.0 MPa.

[0009] In another aspect, the present disclosure provides new refrigerants, including the new HFO-1132(E). It was served.

[0010] 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 designated by ISO817 (International Organization for Standardization) with a refrigerant number (ASHRAE number) beginning with R, which indicates the type of refrigerant. Furthermore, even if a refrigerant number has not yet been assigned, it also includes refrigerants that have equivalent refrigerant properties. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of chemical structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons. Contains hydrocarbons (HFCs).

[0011] 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."

[0012] 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.

[0013] 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.

[0014] 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.

[0015] In this specification, when a refrigerant has an RCL of x% or more, it refers to that refrigerant. This means that the refrigerant concentration limit (RCL) calculated in accordance with the US ANSI / ASHRAE34-2013 standard is x% or more. RCL is the concentration of refrigerant in the air taking into account a safety factor. The RCL is a concentration limit for a substance in an enclosed space where humans are present, and is an index aimed at reducing the risk of acute toxicity, suffocation, and flammability in such an enclosed space. The RCL is determined in accordance with the above standards. Specifically, acute toxicity exposure calculated according to 7.1.1, 7.1.2 and 7.1.3 of the above standard, respectively. The RCL is the lowest concentration among the Acute-Toxicity Exposure Limit (ATEL), Oxygen Deprivation Limit (ODL), and Flammable Concentration Limit (FCL).

[0016] In this specification, pressure refers to absolute pressure unless otherwise specified.

[0017] In this specification, a refrigerant is considered to be "WCF Mildly Flammable" in accordance with the US ANSI / ASHRAE34-2013 standard. The most flammable formulation (Worst case formulation for flammability; WCF) has the highest burning rate. This means that the speed is less than 10cm / s.

[0018] In this specification, the term "ASHRAE Mild Flammable (WCF & WCFF Mild Flammable)" refers to the refrigerant's combustion speed. Storage, transportation, and use based on ANSI / ASHRAE34-2013 using WCF, with a temperature of 10 cm / s or less. This means that the worst case fractionation for flammability (WCFF), identified by conducting a leakage test at the time of the test, has a burning velocity of 10 cm / s or less and is judged to be in the "2L class" flammability category according to the US ANSI / ASHRAE34-2013 standard.

[0019] 1. refrigerant 1.1 Refrigerant components The refrigerant of the present disclosure is a mixed refrigerant containing HFO-1132(E), R32, and R1234yf.

[0020] 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. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point Q(54.0, 46.0, 0.0), Point R(44.0, 0.0, 56.0), Point P(0.0, 0.0, 100.0) and Point O(0.0, 100.0, 0.0) The point is within the area of ​​the figure enclosed by the lines QR, RP, PO, and OQ connecting the four points above, or on the line QR (however, points Q and R are excluded).

[0021] The refrigerant disclosed herein satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) when the refrigerant pressure is 3.0 MPa, and not only does it have a GWP of 300 or less, but also has a refrigerant concentration limit of 100. RCL is 57g / m 3 As a result, the refrigeration capacity ratio to R410A becomes 90% or more, and the discharge temperature rise rate becomes 1.5% or less. In the refrigerant, the coordinates (x, y, z) are: Point M(19.8, 41.2, 39.0), Point K(19.8, 37.7, 42.5), Point L(12.2, 44.2, 43.6) and Point N(14.7, 44.2, 41.1) The four points are within the range of the figure enclosed by the lines MK, KL, LN, and NM respectively connecting these four points, or are on the lines MK, KL, LN, and NM.

[0022] The refrigerant disclosed herein satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) when the refrigerant pressure is 3.0 MPa, and not only does it have a GWP of 160 or less, but also has a refrigerant concentration limit of 160 or less. RCL is 57g / m 3 As a result, the refrigeration capacity ratio to R410A is 75% or more. In the refrigerant, the coordinates (x, y, z) are: Point I''(19.8, 23.3, 56.9), Point K''(19.8, 17.7, 62.5) and Point L'(12.1, 23.3, 64.6) Within the area of ​​the shape enclosed by the lines I''K'', K''L' and L'I'' connecting the three points respectively are on the straight lines I''K'', K''L' and L'I''.

[0023] The refrigerant disclosed herein satisfies the following requirements, thereby suppressing disproportionation of HFO-1132(E) when the refrigerant pressure is 3.0 MPa, and not only does it have a GWP of 160 or less, but also has a refrigerant concentration limit of 160 or less. RCL is 58g / m 3 As a result, the refrigeration capacity ratio to R410A is 75% or more. In the refrigerant, the coordinates (x, y, z) are: Point I'(18.2, 23.3, 58.5), Point K'(18.2, 18.8, 63.0) and Point L'(12.1, 23.3, 64.6) Within the range of the figure enclosed by the lines I'K', K'L' and L'I' connecting the three points above, or within the range of the lines It is on the lines I'K', K'L' and L'I'.

[0024] The refrigerant disclosed in this disclosure not only has a GWP of 500 or less by satisfying the following requirements, but also has a refrigeration capacity ratio of 95% or more compared to R32, is a WCF with low flammability, and prevents the disproportionation of HFO-1132(E). Therefore, it is possible to operate the refrigerator without taking measures to deal with disproportionation. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point C(28.7, 53.7, 17.6), Point D(9.0, 74.0, 17.0), Point A (26.0, 74.0, 0.0) and Point I (26.7, 73.3, 0.0) The point A is located within the area of ​​the figure enclosed by the line segments CD, DA, AI, and IC connecting the four points above, or on the line segments CD, DA, and IC (excluding points A and I), the line segments DA, AI, and IC are straight lines; and The coordinates (x, y, z) of the point on the line segment CD are (x, 0.0069x 2 -1.2909x+85.059, -0.0069x 2 +0.2909x+14.941).

[0025] By satisfying the following requirements, the refrigerant disclosed herein not only has a GWP of 500 or less, but also has a refrigeration capacity ratio of 95% or more compared to R32, is mildly flammable with WCFF, and can suppress disproportionation of HFO-1132(E). Therefore, it is possible to operate a chiller without taking measures to deal with disproportionation. In the refrigerant, the coordinates (x, y, z) are: Point C'(20.3, 61.7, 18.0), Point D (9.0, 74.0, 17.0) and Point J'(20.0, 74.0, 6.0) Within the area enclosed by the line segments C'D, DJ' and J'C' connecting the three points above, or within the area enclosed by the line segment C On 'D, DJ' and J'C' The line segments DJ' and J'C' are straight lines, and The coordinates (x, y, z) of the point on the line segment C'D are (x, 0.0069x 2 -1.2909x+85.059, -0.0069x 2 +0.2909x+14.941).

[0026] By satisfying the following requirements, the refrigerant disclosed in this disclosure not only has a GWP of 500 or less, but also has a refrigeration capacity ratio of 90% or more compared to R32, and by reducing the concentration of the highly flammable E-HFO-1132E by 2%, it becomes a mildly flammable WCFF with a high safety factor, and can also suppress the disproportionation of HFO-1132(E). Therefore, the refrigerator can be operated without taking measures to deal with disproportionation. In the refrigerant, the coordinates (x, y, z) are: Point E(18.5, 53.1, 28.4), Point F(0.0, 72.8, 27.2), Point B (0.0, 73.9, 26.1) and Point K'(18.0, 74.0, 8.0) The point F and the point B are excluded from the figure enclosed by the line segments EF, FB, BK', and K'E connecting the four points above, or are on the line segments EF, BK', and K'E. The line segments FB, BK', and K'E are straight lines, and The coordinates (x, y, z) of the point on the line segment EF are (x, 0.0077x 2 -1.2066x+72.8, -0.0077x 2 +0.2066x+27.2).

[0027] The refrigerant disclosed herein has a refrigerant concentration limit (RCL) of 50 g / m by satisfying the following requirements: 3 End The refrigeration capacity ratio to R32 is 76% or more, and the GWP is 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point T(26.6, 23.3, 50.1) It is within the area of ​​the figure enclosed by the lines US, ST, and TU connecting these three points, or is on said lines US, ST, and TU.

[0028] The refrigerant disclosed in this disclosure satisfies the following requirements, eliminating the need for disproportionation measures and providing a The freezing capacity ratio is 76% or more and the GWP is 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point W(30.0, 23.4, 46.6), Point S'(30.0, 20.9, 49.1) and Point T(26.6, 23.3, 50.1) The point is within the area of ​​the figure enclosed by the lines WS', S'T and TW respectively connecting the three points, or is on the lines WS', S'T and TW.

[0029] The refrigerant disclosed herein has an RCL of 50 g / m by satisfying the following requirements: 3 This is the result of the condensation graph. The ID will be 4.2K or less and the GWP will be 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point Z(27.7, 23.4, 48.9) The area is within the shape enclosed by the lines US, SZ, and ZU connecting the three points above, or is on the lines US, SZ, and ZU.

[0030] The refrigerant of the present disclosure satisfies the following requirements, thereby eliminating the need for disproportionation countermeasures, achieving a condensation glide of 4.2 K or less, and a GWP of 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point W(30.0, 23.4, 46.6), Point Z'(30.0, 21.5, 48.5) and Point Z(27.7, 23.4, 48.9) The area is within the shape enclosed by the lines WZ', Z'Z and ZW respectively connecting these three points, or is on the lines WZ', Z'Z and ZW.

[0031] The refrigerant disclosed herein has an RCL of 50 g / m by satisfying the following requirements:3 This is the result of the condensation graph. The ID will be 4.2K or less and the GWP will be 150 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point X(32.8, 21.9, 45.3), Point S(32.8, 19.1, 48.1) and Point Y (29.5, 21.9, 48.6) The area is within the shape enclosed by the lines XS, SY, and YX connecting the three points above, or is on the lines XS, SY, and YX.

[0032] The refrigerant disclosed in this disclosure satisfies the following requirements, eliminating the need for disproportionation countermeasures and achieving an RCL of 50 g / m 3 This means that the condensation glide is 4.2K or less and the GWP is 150 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point Y'(30.0, 21.9, 48.1), Point Z'(30.0,21.5,48.5) and Point Y (29.5, 21.9, 48.6) Within the range of the figure enclosed by the lines Y'Z', Z'Y and YY' connecting the three points above, or within the range of the line Y On 'Z', Z'Y and YY'.

[0033] The refrigerant of the present disclosure preferably contains 54 mass% or less of HFO-1132(E) based on the total refrigerant. It is more preferable that the content is 44% by mass or less, further preferably 32.8% by mass or less, and most preferably 30% by mass or less, since no disproportionation countermeasures are required.

[0034] The refrigerant of the present disclosure preferably contains 5% by mass or more of HFO-1132(E) based on the total refrigerant, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more. It is most preferable that the content be 100% by mass or more.

[0035] The refrigerant of the present disclosure may contain, in addition to HFO-1132(E), R32, and R1234yf, other additional refrigerants, as long as the above-mentioned properties and effects are not impaired. However, the total amount of HFO-1132(E), R32 and R1234yf is preferably 99.5 mass% or more, more preferably 99.75 mass% or more, and even more preferably 99.9 mass% or more, based on the total amount of the refrigerant. It is preferable that the content is 99.99% by mass or more, even more preferable that the content is 99.999% by mass or more, and most preferable that the content is 99.999% by mass or more. The refrigerant of the present disclosure is preferably one consisting essentially of HFO-1132(E), R32, and R1234yf. It may be composed of only HFO-1132(E), R32 and R1234yf. When the refrigerants shown in the table are composed essentially of HFO-1132(E), R32, and R1234yf, they may contain, in addition to HFO-1132(E), R32, and R1234yf, impurities that are inevitably mixed in during the production process.

[0036] 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 refrigerants is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, based on the total amount of the refrigerant. It is more preferably 0.1% by mass or less, and most preferably 0.01% by mass or less. stomach.

[0037] 1.2 Purpose The refrigerant of the present disclosure can be preferably used as a working fluid in a refrigerator.

[0038] The compositions of the present disclosure are suitable for use as replacement refrigerants for R32 and / or R410A.

[0039] 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. 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 also 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.

[0040] 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 relative to the total refrigerant. This stabilizes the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant, and also makes the unsaturated fluorocarbon compounds less susceptible to oxidation, thereby improving the stability of the refrigerant composition.

[0041] 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.

[0042] The refrigerant composition of the present disclosure may contain one type of tracer alone or two or more types of tracers.

[0043] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0044] 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 (NO). Polyfluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are particularly preferred.

[0045] 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-difluoromethyl ether, CF3OCHF2) Fluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl-methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0046] 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).

[0047] 2.3 UV fluorescent dye The refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone, or may contain two or more types.

[0048] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from among commonly used ultraviolet fluorescent dyes.

[0049] 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.

[0050] 2.4 stabilizers The refrigerant composition of the present disclosure may contain one type of stabilizer alone or two or more types.

[0051] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0052] Examples of stabilizers include nitro compounds, ethers, and amines.

[0053] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0054] An example of the ethers is 1,4-dioxane.

[0055] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0056] Other examples include butylhydroxyxylene and benzotriazole.

[0057] 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.

[0058] 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.

[0059] The polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.

[0060] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, and hydroquinone. Examples of suitable phenols include methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0061] 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 amount 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 amount of the refrigerant. It is more preferable that

[0062] 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.

[0063] 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.

[0064] The refrigerating machine oil is not particularly limited and can be appropriately selected from among commonly used refrigerating machine oils. In this case, the refrigerating machine oil may be selected, if necessary, taking into consideration the miscibility and compatibility with the mixture. A refrigerator oil that is superior in terms of improving the stability of the mixture can be appropriately selected.

[0065] Examples of base oils for refrigerating machine oils include polyalkylene glycol (PAG), polyol ether (PAE), and At least one selected from the group consisting of polyvinyl ether (POE) and polyvinyl ether (PVE) is preferred.

[0066] 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.

[0067] 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. .

[0068] 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.

[0069] 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.

[0070] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0071] 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.

[0072] 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.

[0073] Specifically, a method of operating a refrigerator according to the present disclosure includes circulating a refrigerant according to the present disclosure in the refrigerator.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 6. Use for inhibiting disproportionation reactions The use of the present disclosure is intended to suppress the disproportionation reaction of R32 and / or R1234yf with HFO-1132(E). The suppression of the disproportionation reaction is achieved by using HFO-1132(E), R32 and R1234yf in the process of the present disclosure. This is done by mixing the refrigerants to achieve the desired mixing ratio.

[0078] 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.

[0079] 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]

[0080] The present disclosure will be described in more detail below with reference to examples, but is not limited to these examples.

[0081] HFO-1132(E), R32 and R1234yf are shown in Tables 1 to 3, respectively, based on their sum. A mixed refrigerant was prepared by mixing the components in the above-mentioned mass percentages.

[0082] 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. 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 applied. The presence or absence of this was judged by a sudden increase in pressure and temperature inside the device. Test conditions Test container: 38cc SUS container Test temperature: 150℃ Pressure: 3.0 MPa (absolute pressure) Judgment criteria "No explosion": The temperature or pressure after Pt fusing is less than twice the normal value, and a rapid disproportionation reaction does not occur. not present. "Explosion": The temperature or pressure after Pt wire melting reached more than double the normal value, causing a sudden disproportionation reaction. .

[0083] [Table 1]

[0084] In addition, for each of these mixed refrigerants, the COP ratio and refrigeration capacity are compared based on R410A or R32. The power ratios of R410A, R32 and mixtures of HFO-1132(E), R1234yf, and R32 were calculated. The cycle performance of the composition was determined by theoretical calculations of the refrigeration cycle of the refrigerant mixture under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). Note that the physical property data for HFO-1132(E) was determined from actual measurements. Evaporation temperature: 5℃ Condensation temperature: 45℃ Superheat degree: 5K Supercooling degree; 5K Compressor efficiency: 70%

[0085] These values ​​are shown in Tables 2 to 8 along with the GWP for each refrigerant mixture.

[0086] [Table 2]

[0087] [Table 3]

[0088] [Table 4]

[0089] [Table 5]

[0090] [Table 6]

[0091] [Table 7]

[0092] [Table 8]

[0093] The burning rate test was carried out using the apparatus shown in Figure 1 as follows. First, the mixed refrigerant used was 99.5% or more pure and was degassed by repeating cycles of freezing, pumping, and thawing until no trace of air was visible on the vacuum gauge. The burning rate was measured using the closed-circuit method. The initial temperature was ambient temperature. Ignition was performed by generating an electric spark between electrodes at the center of the sample cell. The discharge duration was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The flame propagation state was observed using the Schlieren method. Visualization was performed in a cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two acrylic windows that allowed light to pass through. ) was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of the flame were recorded with a high-speed digital video camera at a framing rate of 600 fps and saved on a PC. The burning rate (Su (cm / s)) is expressed as the volume of unburned gas consumed by a unit area of ​​flame surface per unit time, and is calculated using the following formula: Su=Sb*ρu / ρb Sb: Flame propagation speed (cm / s) ρu: Adiabatic flame temperature (unburned) ρb: Adiabatic flame temperature (burned) where: Sb was obtained from the Schlieren video image, ρu was the measured temperature, and ρb was calculated from the heat of combustion and the specific heat at constant pressure of the combustion gas. The results are shown in Table 9.

[0094] [Table 9]

[0095] The approximate curve connecting the three points was calculated using the least squares method, as shown in the table below.

[0096] [Table 10]

[0097] From these results, it can be seen that the mixed refrigerant of HFO-1132(E), R32 and R1234yf satisfies the following requirements: This indicates that the disproportionation of HFO-1132(E) is suppressed. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point Q(54.0, 46.0, 0.0), Point R(44.0, 0.0, 56.0), Point P(0.0, 0.0, 100.0) and Point O(0.0, 100.0, 0.0) The point is within the area of ​​the figure enclosed by the lines QR, RP, PO, and OQ connecting the four points above, or on the line QR (however, points Q and R are excluded).

[0098] From these results, it can be seen that the mixed refrigerant of HFO-1132(E), R32 and R1234yf satisfies the following requirements: This not only suppresses the disproportionation of HFO-1132(E) and keeps its GWP at 300 or less, but also Furthermore, the refrigerant concentration limit (RCL) is 57 g / m 3 As a result, it can be seen that the refrigeration capacity ratio to R410A is 90% or more, and the discharge temperature rise rate is 1.5% or less. In the refrigerant, the coordinates (x, y, z) are: Point M(19.8, 41.2, 39.0), Point K(19.8, 37.7, 42.5), Point L(12.2, 44.2, 43.6) and Point N(14.7, 44.2, 41.1) The four points are within the range of the figure enclosed by the lines MK, KL, LN, and NM respectively connecting these four points, or are on the lines MK, KL, LN, and NM.

[0099] From these results, it can be seen that the mixed refrigerant of HFO-1132(E), R32 and R1234yf satisfies the following requirements: This not only suppresses the disproportionation of HFO-1132(E), but also keeps the GWP below 160. The refrigerant concentration limit (RCL) is 57g / m 3 As a result, it is clear that the refrigeration capacity ratio to R410A is 75% or more. In the refrigerant, the coordinates (x, y, z) are: Point I''(19.8, 23.3, 56.9), Point K''(19.8, 17.7, 62.5) and Point L'(12.1, 23.3, 64.6) Within the area of ​​the shape enclosed by the lines I''K'', K''L' and L'I'' connecting the three points respectively are on the straight lines I''K'', K''L' and L'I''.

[0100] From these results, it can be seen that the mixed refrigerant of HFO-1132(E), R32 and R1234yf satisfies the following requirements: This not only suppresses the disproportionation of HFO-1132(E), but also keeps the GWP below 160. The refrigerant concentration limit (RCL) is 58g / m 3 As a result, it is clear that the refrigeration capacity ratio to R410A is 75% or more. In the refrigerant, the coordinates (x, y, z) are: Point I'(18.2, 23.3, 58.5), Point K'(18.2, 18.8, 63.0) and Point L'(12.1, 23.3, 64.6) Within the range of the figure enclosed by the lines I'K', K'L' and L'I' connecting the three points above, or within the range of the lines It is on the lines I'K', K'L' and L'I'.

[0101] The refrigerant disclosed in this disclosure not only has a GWP of 500 or less by satisfying the following requirements, but also has a refrigeration capacity ratio of 95% or more compared to R32, is a WCF with low flammability, and prevents the disproportionation of HFO-1132(E). Therefore, it is possible to operate the refrigerator without taking measures to deal with disproportionation. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point C(28.7, 53.7, 17.6), Point D(9.0, 74.0, 17.0), Point A (26.0, 74.0, 0.0) and Point I (26.7, 73.3, 0.0) The point A is located within the area of ​​the figure enclosed by the line segments CD, DA, AI, and IC connecting the four points above, or on the line segments CD, DA, and IC (excluding points A and I), the line segments DA, AI, and IC are straight lines; and The coordinates (x, y, z) of the point on the line segment CD are (x, 0.0069x 2 -1.2909x+85.059, -0.0069x 2 +0.2909x+14.941).

[0102] By satisfying the following requirements, the refrigerant disclosed herein not only has a GWP of 500 or less, but also has a refrigeration capacity ratio of 95% or more compared to R32, is mildly flammable with WCFF, and can suppress disproportionation of HFO-1132(E). Therefore, it is possible to operate a chiller without taking measures to deal with disproportionation. In the refrigerant, the coordinates (x, y, z) are: Point C'(20.3, 61.7, 18.0), Point D (9.0, 74.0, 17.0) and Point J'(20.0, 74.0, 6.0) Within the area enclosed by the line segments C'D, DJ' and J'C' connecting the three points above, or within the area enclosed by the line segment C On 'D, DJ' and J'C' The line segments DJ' and J'C' are straight lines, and The coordinates (x, y, z) of the point on the line segment C'D are (x, 0.0069x 2 -1.2909x+85.059, -0.0069x 2 +0.2909x+14.941).

[0103] The refrigerant disclosed in the present disclosure not only has a GWP of 500 or less by satisfying the following requirements, but also The refrigeration capacity ratio to R32 is 90% or more, and by reducing the concentration of the highly flammable E-HFO-1132E by 2%, it becomes a WCFF with a high safety factor and can suppress the disproportionation of HFO-1132(E). Therefore, the refrigerator can be operated without taking measures to deal with disproportionation. In the refrigerant, the coordinates (x, y, z) are: Point E(18.5, 53.1, 28.4), Point F(0.0, 72.8, 27.2), Point B (0.0, 73.9, 26.1) and Point K'(18.0, 74.0, 8.0) The point F and the point B are excluded from the figure enclosed by the line segments EF, FB, BK', and K'E connecting the four points above, or are on the line segments EF, BK', and K'E. The line segments FB, BK', and K'E are straight lines, and The coordinates (x, y, z) of the point on the line segment EF are (x, 0.0077x 2 -1.2066x+72.8, -0.0077x 2 +0.2066x+27.2).

[0104] From these results, the refrigerant disclosed herein can achieve a refrigerant concentration limit (RCL) of 50 g / m by satisfying the following requirements: 3As a result, it can be seen that the refrigeration capacity ratio to R32 is 76% or more and the GWP is 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point T(26.6, 23.3, 50.1) It is within the area of ​​the figure enclosed by the lines US, ST, and TU connecting these three points, or is on said lines US, ST, and TU.

[0105] These results show that the refrigerant of the present disclosure does not require disproportionation countermeasures, has a refrigeration capacity ratio of 76% or more compared to R32, and has a GWP of 160 or less by satisfying the following requirements: When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point W(30.0, 23.4, 46.6), Point S'(30.0, 20.9, 49.1) and Point T(26.6, 23.3, 50.1) The point is within the area of ​​the figure enclosed by the lines WS', S'T and TW respectively connecting the three points, or is on the lines WS', S'T and TW.

[0106] From these results, it can be seen that the refrigerant disclosed herein has an RCL of 50 g / m by satisfying the following requirements: 3 Below It can be seen that the condensation glide is 4.2K or less and the GWP is 160 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point Z(27.7, 23.4, 48.9) The area is within the shape enclosed by the lines US, SZ, and ZU connecting the three points above, or is on the lines US, SZ, and ZU.

[0107] These results show that the refrigerant of the present disclosure does not require disproportionation countermeasures, has a condensation glide of 4.2 K or less, and has a GWP of 160 or less by satisfying the following requirements: When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point W(30.0, 23.4, 46.6), Point Z'(30.0, 21.5, 48.5) and Point Z(27.7, 23.4, 48.9) The area is within the shape enclosed by the lines WZ', Z'Z and ZW respectively connecting these three points, or is on the lines WZ', Z'Z and ZW.

[0108] From these results, it can be seen that the refrigerant disclosed herein has an RCL of 50 g / m by satisfying the following requirements: 3 Below It can be seen that the condensation glide is 4.2K or less and the GWP is 150 or less. When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point X(32.8, 21.9, 45.3), Point S(32.8, 19.1, 48.1) and Point Y (29.5, 21.9, 48.6) The area is within the shape enclosed by the lines XS, SY, and YX connecting the three points above, or is on the lines XS, SY, and YX.

[0109] From these results, the refrigerant disclosed herein does not require disproportionation measures and has an RCL of 50 g / m by satisfying the following requirements: 3 or more, the condensed glide is 4.2K or less, and the GWP is 150 or less It turns out that: When the mass percentages of HFO-1132(E), R32, and R1234yf based on their sum are x, y, and z, respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is 100 mass%, The coordinates (x, y, z) are Point Y'(30.0, 21.9, 48.1), Point Z'(30.0,21.5,48.5) and Point Y (29.5, 21.9, 48.6) Within the range of the figure enclosed by the lines Y'Z', Z'Y and YY' connecting the three points above, or within the range of the line Y On 'Z', Z'Y and YY'. [Explanation of symbols]

[0110] 1: Sample cell 2: High-speed camera 3: Xenon lamp 4: Collimating lens 5: Collimating lens 6: Ring filter

Claims

1. A composition comprising a refrigerant, A method for suppressing a disproportionation reaction of HFO-1132(E) at 150°C and 3.0 MPa (absolute pressure), comprising the step of operating a refrigeration cycle using a composition in which the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32) and 2,3,3,3-tetrafluoro-1-propene (R1234yf) in total at 99.5 mass% or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), R32 and R1234yf based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point Q(54.0, 46.0, 0.0), Point R(44.0, 0.0, 56.0), Point P(0.0, 0.0, 100.0) and Point O(0.0, 100.0, 0.0) A method in which the point is within the area surrounded by the straight lines QR, RP, PO, and OQ connecting the four points above, or is on said straight line QR (excluding points Q and R).

2. A composition comprising a refrigerant, The refrigerant is a composition containing HFO-1132(E), R32 and R1234yf in a total amount of 99.5 mass% or more based on the total amount of the refrigerant, When the mass percentages of HFO-1132(E), R32 and R1234yf based on their sum are x, y and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32 and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point U(32.8, 23.4, 43.8), Point S(32.8, 19.1, 48.1) and Point T(26.6, 23.3, 50.1) A composition that is within the area surrounded by straight lines US, ST and TU respectively connecting the three points above, or that is on said straight lines US, ST and TU.

3. The refrigerant further comprises: at least one additional refrigerant selected from the group consisting of 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 composition of claim 2 comprising:

4. The composition according to claim 2 or 3, which is used as an alternative refrigerant to R32 and / or R410A.

5. Use of the composition according to claim 2 or 3 as an alternative refrigerant to R32 and / or R410A.

6. A refrigerator comprising the composition according to claim 2 or 3 as a working fluid.

7. A method for operating a refrigerator, comprising the steps of:

4. The method of claim 3, further comprising the step of circulating the composition according to claim 2 or 3 as a working fluid in a refrigerator. method.

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