Composition containing refrigerant, use thereof, refrigerator having same, and method for operating refrigerator

Abstract

The technical problem to be solved by the invention is to provide a novel low-GWP mixed refrigerant. The solution of the present invention is to provide a composition containing a refrigerant, the refrigerant containing 22.6 to 57 mass% of trans-1, 2-difluoroethylene (HFO-1132 (E)) and 77.4 to 43 mass% of 1, 1-difluoroethane (R152a) with respect to the total of the trans-1, 2-difluoroethylene (HFO-1132 (E)) and the 1, 1-difluoroethane (R152a).

Description

Technical Field

[0001] The present invention relates to a composition containing a refrigerant, use thereof, a refrigerator having the composition, and a method for operating the refrigerator. Background Art

[0002] As a heat cycle working fluid that can replace R410A, a heat cycle working fluid containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2015 / 141678 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] The object of the present invention is to provide a new low GWP mixed refrigerant.

[0008] Technical solutions to problems

[0009] Item 1. A composition containing a refrigerant, wherein the refrigerant contains 22.6 to 57 mass% of trans-1,2-difluoroethylene (HFO-1132(E)) and 77.4 to 43 mass% of 1,1-difluoroethane (R152a) relative to the total of trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethane (R152a).

[0010] Item 2. The composition according to Item 1, comprising 22.9 to 57% by mass of HFO-1132(E)) and 77.1 to 43% by mass of R152a, based on the total amount of HFO-1132(E)) and R152a.

[0011] Item 3. The composition according to Item 1, comprising 28.3 to 57 mass% of HFO-1132(E)) and 71.7 to 43 mass% of R152a based on the total of HFO-1132(E)) and R152a.

[0012] Item 4. The composition according to any one of Items 1 to 3, comprising 99.5% by mass or more of HFO-1132(E) and R152a in total based on the total amount of the refrigerant.

[0013] Item 5. A composition containing a refrigerant, wherein:

[0014] The refrigerant contains 99.5% by mass or more of R152a, R32, and HFO-1132(E) relative to the total amount of the refrigerant, and

[0015] Assuming that the mass % of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R32, and R152a is 100 mass %, the coordinates (x, y, z) are located within the range of the figure enclosed by straight lines CD', D'E', E'F, FB, BA, and AC connecting the following six points, respectively, and on the line segments CD', D'E', E'F, and BA (excluding points A, C, B, and F).

[0016] Point C (60.0, 40.0, 0.0),

[0017] Point D'(57.4,5.0,37.6),

[0018] Point E'(17.5,5.0,77.5),

[0019] Point F(0.0,22.9,77.1),

[0020] Point B (0.0, 32.0, 68.0), and

[0021] Point A (55.7, 44.3, 0.0).

[0022] Item 6. The composition according to Item 5, wherein, in the refrigerant, the coordinates (x, y, z) are located within a range of a figure enclosed by straight lines C'D', D'J', J'K, and KC' connecting the following four points, respectively, and on the straight lines C'D', D'J', J'K, and KC'.

[0023] Point C'(58.3,17.7,24.0),

[0024] Point D'(57.4,5.0,37.6),

[0025] Point J'(22.9,5.0,72.1), and

[0026] Point K(19.3,9.0,71.7).

[0027] Item 7. The composition according to Item 5, wherein, in the refrigerant, the coordinates (x, y, z) are located within the range of a figure enclosed by straight lines C'D', 'D'L', L'M, and MC' connecting the following four points, and on the straight lines C'D', D'L', L'M, and MC'.

[0028] Point C'(58.3,17.7,24.0),

[0029] Point D'(57.4,5.0,37.6),

[0030] Point L'(17.1,5.0,77.9), and

[0031] Point M(14.0,7.8,78.2).

[0032] Item 8. The composition according to Item 2 or 5, which is a composition for replacing R410A.

[0033] Item 9. The composition according to Item 3 or 6, which is a composition for replacing R1234yf.

[0034] Item 10. The composition according to Item 9, which is a composition for replacing R1234yf and is a composition for refrigeration cycle operation of an air conditioner for electric vehicles.

[0035] Item 11. The composition according to Item 1 or 7, which is a composition for replacing R404A.

[0036] Item 12. A refrigeration device comprising:

[0037] a heat transfer cycle for circulating a refrigerant on the utilization side;

[0038] a heat source side heat transfer cycle that circulates a heat source side refrigerant; and

[0039] a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat-source-side refrigerant,

[0040] The heat source side refrigerant is the composition described in any one of items 1 to 7.

[0041] Item 13. A freezing method comprising the step of operating a freezing cycle using the composition according to any one of Items 1 to 7.

[0042] Item 14. A refrigeration device comprising the composition according to any one of Items 1 to 7 as a working fluid.

[0043] Effects of the Invention

[0044] The refrigerant of the present invention has a low GWP. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is a triangular diagram showing the composition of the refrigerant of the present invention.

[0046] Figure 2 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0047] Figure 3 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0048] Figure 4 It is a triangular diagram showing the composition of the refrigerant of the present invention. DETAILED DESCRIPTION

[0049] In order to solve the above-mentioned technical problems, the inventors of the present invention have conducted intensive studies and found that various mixed refrigerants described below have the above-mentioned characteristics.

[0050] The present invention has been completed through further research based on the above findings. The present invention includes the following embodiments.

[0051] Definition of terms

[0052] In this specification, the term "refrigerant" includes at least compounds labeled with an ASHRAE number beginning with "R," as defined by ISO 817 (International Organization for Standardization), and also includes substances that do not have an ASHRAE number but possess equivalent refrigerant properties. Based on the structure of the compounds, refrigerants are broadly categorized as "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0053] In this specification, the term "refrigerant-containing composition" includes at least: (1) the refrigerant itself (including a mixture of refrigerants); (2) a composition that further contains other components and can be used to obtain a refrigerator working fluid by mixing with at least refrigerator oil; and (3) a refrigerator working fluid containing refrigerator oil. In this specification, among these three methods, the composition in (2) is distinguished from the refrigerant itself (including a mixture of refrigerants) and expressed as a "refrigerant composition." Furthermore, the refrigerator working fluid in (3) is distinguished from the "refrigerant composition" and expressed as a "working fluid containing refrigerator oil."

[0054] In this specification, the term "replacement" is used in the context of "replacing" a first refrigerant with a second refrigerant. As a first type, it refers to a device designed to operate using a first refrigerant, which can be operated under optimal conditions using a second refrigerant by changing only a small number of components (refrigeration oil, gaskets, packings, expansion valves, dryers, at least one of other components) and adjusting the equipment as needed. In other words, this type refers to "replacing" the refrigerant to operate the same device. As a form of "replacement" of this type, there are "drop-in replacement", "nearly drop-in replacement" and "retrofit" in descending order, depending on the degree of change or adjustment required when replacing with the second refrigerant.

[0055] The second type, using a second refrigerant to adapt equipment designed to operate with it for the same purpose as the first refrigerant, also falls under the term "substitution." This type means the "substitution" refrigerant serves the same purpose.

[0056] In this specification, the term "refrigerator" refers to any device that removes heat from an object or space, bringing it to a lower temperature than the surrounding air, and maintaining that lower temperature. In other words, a refrigerator is a device that converts energy from an external source to produce work, moving heat from a lower temperature to a higher temperature.

[0057] In this specification, "vehicle air conditioning equipment" refers to a type of refrigeration system used in gasoline-powered vehicles, hybrid vehicles, electric vehicles, hydrogen-powered vehicles, and other vehicles. This refers to a refrigeration system that utilizes a refrigeration cycle. This refrigeration cycle uses an evaporator to exchange heat with a liquid refrigerant, a compressor to draw in the evaporated refrigerant gas, a condenser to cool and liquefy the adiabatically compressed refrigerant gas, and an expansion valve to adiabatically expand it before supplying it back to the evaporator as liquid refrigerant.

[0058] The pressure described in this specification is absolute pressure unless otherwise specified.

[0059] 1. refrigerant

[0060] The refrigerant of the present invention contains trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethane (R152a). The refrigerant of the present invention may further contain difluoromethane (R32).

[0061] The refrigerant of the present invention is a low GWP mixed refrigerant.

[0062] The refrigerant of the present invention can contain 22.6-57% by mass of HFO-1132(E) and 77.4-43% by mass of R152a, relative to the combined amount of HFO-1132(E) and R152a. This refrigerant has a refrigeration capacity ratio of 70% or greater relative to R404A and does not undergo a disproportionation reaction at 5 MPa and 150°C. Therefore, this refrigerant can be used as an R404A alternative.

[0063] The refrigerant of the present invention can contain 44.7-57% HFO-1132(E) and 55.3-43% R152a, relative to the combined mass of HFO-1132(E) and R152a. This refrigerant has a refrigeration capacity ratio of 90% or greater relative to R404A and does not undergo disproportionation at 5 MPa and 150°C. Therefore, it can be used as an R404A replacement.

[0064] The refrigerant of the present invention can contain 22.9-57% by mass of HFO-1132(E) and 77.1-43% by mass of R152a, relative to the combined amount of HFO-1132(E) and R152a. This refrigerant has a refrigeration capacity ratio of 55% or greater relative to R410A and does not undergo a disproportionation reaction at 5 MPa and 150°C. Therefore, this refrigerant can be used as an R410A alternative.

[0065] The refrigerant of the present invention can contain 41.4-57% by mass of HFO-1132(E) and 59.6-43% by mass of R152a, relative to the combined amount of HFO-1132(E) and R152a. This refrigerant has a refrigeration capacity ratio of 65% or greater relative to R410A and does not undergo disproportionation at 5 MPa and 150°C. Therefore, it can be used as an R410A alternative.

[0066] The refrigerant of the present invention can contain 28.3-57% by mass of HFO-1132(E) and 71.7-43% by mass of R152a, relative to the combined amount of HFO-1132(E) and R152a. This refrigerant has a boiling point of -40°C or lower and does not undergo disproportionation at 5 MPa and 150°C. It can be used as an R1234yf replacement refrigerant.

[0067] The refrigerant of the present invention can contain 44.1-57% by mass of HFO-1132(E) and 55.9-43% by mass of R152a, relative to the combined amount of HFO-1132(E) and R152a. This refrigerant has a refrigeration capacity ratio of 165% or greater relative to R1234yf and does not undergo disproportionation at 5 MPa and 150°C. It can be used as an R1234yf alternative.

[0068] The refrigerant of the present invention may be a refrigerant excluding at least one refrigerant selected from the following refrigerants, that is, with respect to the total of HFO-1132(E) and R152a:

[0069] A refrigerant containing 22.6 mass% HFO-1132(E) and 77.4 mass% R152a;

[0070] A refrigerant containing 25.0 mass% HFO-1132(E) and 75.0 mass% R152a;

[0071] A refrigerant containing 28.3 mass% HFO-1132(E) and 71.7 mass% R152a;

[0072] A refrigerant containing 30.0 mass% HFO-1132(E) and 70.0 mass% R152a;

[0073] A refrigerant containing 35.0 mass% HFO-1132(E) and 65.0 mass% R152a;

[0074] A refrigerant containing 36.0 mass% HFO-1132(E) and 64.0 mass% R152a;

[0075] A refrigerant containing 38.0 mass% HFO-1132(E) and 62.0 mass% R152a;

[0076] A refrigerant containing 45.0 mass% of HFO-1132(E) and 55.0 mass% of R152a; and

[0077] A refrigerant containing 55.0% by mass of HFO-1132(E) and 45.0% by mass of R152a.

[0078] In the above-described embodiment, the refrigerant of the present invention may contain an additional refrigerant in addition to HFO-1132(E) and R152a, within a range that does not impair the above-described characteristics and effects. Regarding this point, in one embodiment, the refrigerant of the present invention preferably contains 99.5% by mass or more of HFO-1132(E) and R152a, more preferably 99.75% by mass or more, even more preferably 99.9% by mass or more, even more preferably 99.999% by mass or more, and most preferably 99.9999% by mass or more. The refrigerant of the present invention may also consist essentially only of HFO-1132(E) and R152a. In this case, the refrigerant of the present invention may consist only of HFO-1132(E), R152a, and unavoidable impurities. Alternatively, the refrigerant of the present invention may consist only of HFO-1132(E) and R152a.

[0079] The additional refrigerant is not particularly limited and can be selected from a wide range. A mixed refrigerant may contain one or more additional refrigerants. Examples of additional refrigerants include R32, acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0080] The refrigerant of the present invention may further contain R32 at a different content ratio from that of the additional refrigerant described above, specifically, 5% by mass or more relative to the total refrigerant. The following describes an embodiment in which the refrigerant contains 5% by mass or more of R32 relative to the total refrigerant.

[0081] In the refrigerant of the present invention, assuming that the mass percentages of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, when, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass%, the coordinates (x, y, z) satisfy the following conditions: no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity ratio relative to R410A is 55% or more.

[0082] <Conditions>

[0083] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD', D'E', E'F, FB, BA, and AC connecting the following six points, and on the above-mentioned line segments CD', D'E', E'F, and BA (excluding points A, C, B, and F).

[0084] Point D'(57.4,5.0,37.6),

[0085] Point E'(17.5,5.0,77.5),

[0086] Point F(0.0,22.9,77.1),

[0087] Point B (0.0, 32.0, 68.0), and

[0088] Point A (55.7, 44.3, 0.0).

[0089] In the refrigerant of the present invention, assuming that the mass percentages of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass%, when the coordinates (x, y, z) satisfy the following conditions: no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less.

[0090] <Conditions>

[0091] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines C'D', D'J', J'K, and KC' connecting the following four points, and on the straight lines C'D', D'J', J'K, and KC'.

[0092] Point C'(58.3,17.7,24.0),

[0093] Point D'(57.4,5.0,37.6),

[0094] Point J'(22.9,5.0,72.1), and

[0095] Point K(19.3,9.0,71.7).

[0096] In the refrigerant of the present invention, assuming that the mass percentages of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, when, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass%, the coordinates (x, y, z) satisfy the following conditions: no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity ratio relative to R404A is 70% or more.

[0097] <Conditions>

[0098] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines C'D', 'D'L', L'M, and MC' connecting the following four points, and on the straight lines C'D', D'L', L'M, and MC'.

[0099] Point C'(58.3,17.7,24.0),

[0100] Point D'(57.4,5.0,37.6),

[0101] Point L'(17.1,5.0,77.9), and

[0102] Point M(14.0,7.8,78.2).

[0103] The refrigerant of the present invention may be a refrigerant excluding at least one refrigerant selected from the following refrigerants, that is, with respect to the total of HFO-1132(E), R32, and R152a:

[0104] A refrigerant containing 5.0 mass% HFO-1132(E), 25.0 mass% R32, and 70.0 mass% R152a;

[0105] A refrigerant containing 12.2 mass% HFO-1132(E), 34.7 mass% R32, and 53.1 mass% R152a;

[0106] A refrigerant containing 14.0 mass% of HFO-1132(E), 7.8 mass% of R32 and 78.2 mass% of R152a;

[0107] A refrigerant containing 15.0 mass% HFO-1132(E), 15.0 mass% R32, and 70.0 mass% R152a;

[0108] A refrigerant containing 15.0 mass% HFO-1132(E), 25.0 mass% R32, and 60.0 mass% R152a;

[0109] A refrigerant containing 15.0 mass% HFO-1132(E), 35.0 mass% R32, and 50.0 mass% R152a;

[0110] A refrigerant containing 19.3 mass% HFO-1132(E), 9.0 mass% R32, and 71.7 mass% R152a;

[0111] A refrigerant containing 25.0 mass% HFO-1132(E), 5.0 mass% R32, and 70.0 mass% R152a;

[0112] A refrigerant containing 25.0 mass% HFO-1132(E), 10.0 mass% R32, and 65.0 mass% R152a;

[0113] A refrigerant containing 25.0 mass% HFO-1132(E), 15.0 mass% R32, and 60.0 mass% R152a;

[0114] A refrigerant containing 25.0 mass% HFO-1132(E), 20.0 mass% R32, and 55.0 mass% R152a;

[0115] A refrigerant containing 25.0 mass% HFO-1132(E), 30.0 mass% R32, and 45.0 mass% R152a;

[0116] A refrigerant containing 26.5 mass% HFO-1132(E), 20.7 mass% R32, and 52.8 mass% R152a;

[0117] A refrigerant containing 30.0 mass% HFO-1132(E), 10.0 mass% R32, and 60.0 mass% R152a;

[0118] A refrigerant containing 30.0 mass% HFO-1132(E), 11.0 mass% R32, and 59.0 mass% R152a;

[0119] A refrigerant containing 30.0 mass% HFO-1132(E), 15.0 mass% R32, and 55.0 mass% R152a;

[0120] A refrigerant containing 35.0 mass% HFO-1132(E), 5.0 mass% R32, and 60.0 mass% R152a;

[0121] A refrigerant containing 35.0 mass% HFO-1132(E), 10.0 mass% R32, and 55.0 mass% R152a;

[0122] A refrigerant containing 35.0 mass% HFO-1132(E), 15.0 mass% R32, and 50.0 mass% R152a;

[0123] A refrigerant containing 35.0 mass% HFO-1132(E), 20.0 mass% R32, and 450. mass% R152a;

[0124] A refrigerant containing 35.0 mass% HFO-1132(E), 30.0 mass% R32, and 35.0 mass% R152a;

[0125] A refrigerant containing 35.0 mass% HFO-1132(E), 40.0 mass% R32, and 25.0 mass% R152a;

[0126] A refrigerant containing 40.0 mass% HFO-1132(E), 10.0 mass% R32, and 50.0 mass% R152a;

[0127] A refrigerant containing 40.8 mass% HFO-1132(E), 8.1 mass% R32, and 51.1 mass% R152a;

[0128] A refrigerant containing 43.0 mass% HFO-1132(E), 14.3 mass% R32, and 42.7 mass% R152a;

[0129] A refrigerant containing 45.0 mass% HFO-1132(E), 10.0 mass% R32, and 45.0 mass% R152a;

[0130] A refrigerant containing 45.0 mass% HFO-1132(E), 30.0 mass% R32, and 25.0 mass% R152a;

[0131] A refrigerant containing 45.0 mass% HFO-1132(E), 40.0 mass% R32, and 15.0 mass% R152a;

[0132] A refrigerant containing 55.0 mass% HFO-1132(E), 10.0 mass% R32, and 35.0 mass% R152a;

[0133] A refrigerant containing 55.0 mass% HFO-1132(E), 20.0 mass% R32, and 25.0 mass% R152a;

[0134] A refrigerant containing 55.0 mass% of HFO-1132(E), 30.0 mass% of R32, and 15.0 mass% of R152a; and

[0135] A refrigerant containing 55.0% by mass of HFO-1132(E), 40.0% by mass of R32, and 5.0% by mass of R152a.

[0136] Regarding the refrigerant of the present invention, in a three-component composition diagram in which the sum of HFO-1132(E), R32, and R152a is 100 mass%, and the point where HFO-1132(E) is 100 mass% is the upper vertex, when the coordinates (x, y, z) are on the above-mentioned straight line CD or below the straight line CD, no disproportionation reaction occurs at 5 MPa and 150°C. In this case, even if the refrigerant pressure in the refrigeration cycle is 5 MPa and the refrigerant temperature is 150°C, the disproportionation reaction can be suppressed.

[0137] Furthermore, the refrigerant of the present invention has the advantage of being easily used in heating systems using heat pumps due to its boiling point of -40.0°C or lower. For example, when used to operate the refrigeration cycle of a vehicle air conditioner, the refrigerant of the present invention has the advantage of being able to heat the vehicle using a heat pump that consumes less electricity than an electric heater. Examples of vehicle air conditioners include gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen vehicles.

[0138] The refrigerant of the present invention may contain 20% or more of HFO-1132(E), 30% or more, 40% or more, or 50% or more of HFO-1132(E), relative to the total refrigerant. The refrigerant of the present invention may contain 5% or more of R32, 10% or more, 20% or more, 30% or more, or 40% or more of R32, relative to the total refrigerant. The refrigerant of the present invention may contain 10% or more of R152a, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more of R152a, relative to the total refrigerant.

[0139] The refrigerant of the present invention may contain additional refrigerants in addition to HFO-1132(E), R32, and R152a, within a range that does not impair the aforementioned properties and effects. In this regard, in one embodiment, the refrigerant of the present invention preferably contains a total of HFO-1132(E), R32, and R152a of 99.5% or more by mass, more preferably 99.75% or more by mass, even more preferably 99.9% or more by mass, and most preferably 99.9999% or more by mass, relative to the total refrigerant. The refrigerant of the present invention may also consist essentially solely of HFO-1132(E), R32, and R152a. In this case, the refrigerant of the present invention may consist solely of HFO-1132(E), R32, and R152a, along with unavoidable impurities. Alternatively, the refrigerant of the present invention may consist solely of HFO-1132(E), R32, and R152a.

[0140] The additional refrigerant is not particularly limited and can be selected from a wide range. A mixed refrigerant may contain one or more additional refrigerants. Examples of the additional refrigerant include acetylene, methylamine, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0141] 2. Refrigerant composition

[0142] The refrigerant composition of the present invention contains at least the refrigerant of the present invention and can be used for the same purposes as the refrigerant of the present invention. In addition, the refrigerant composition of the present invention can also be used to obtain a refrigerator working fluid by mixing with at least refrigerator oil.

[0143] The refrigerant composition of the present invention may contain at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may contain at least one of the following other components as needed. As described above, when the refrigerant composition of the present invention is used as a working fluid in a refrigerator, it is usually mixed with at least refrigeration oil. Therefore, the refrigerant composition of the present invention preferably does not substantially contain refrigeration oil. Specifically, with respect to the refrigerant composition of the present invention, the content of refrigeration oil relative to the total refrigerant composition is preferably 1% by mass or less, more preferably 0.1% by mass or less.

[0144] 2.1 Water

[0145] The refrigerant composition of the present invention may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1% by mass or less relative to the total refrigerant composition. The presence of a trace amount of water in the refrigerant composition stabilizes the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant and reduces oxidation of the unsaturated fluorocarbon compound, thereby improving the stability of the refrigerant composition.

[0146] 2.2 tracer

[0147] In order to track the changes in the refrigerant composition of the present invention when it undergoes dilution, contamination, or other changes, a tracer is added to the refrigerant composition of the present invention at a detectable concentration.

[0148] The refrigerant composition of the present invention may contain one type of tracer alone or two or more types of tracers.

[0149] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0150] Examples of the tracer include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorinated ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Particularly preferred tracers are hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluorinated ethers.

[0151] As the tracer, the following compounds are preferred.

[0152] FC-14 (tetrafluoromethane, CF4)

[0153] HCC-40 (Methyl Chloride, CH3Cl)

[0154] HFC-23 (trifluoromethane, CHF3)

[0155] HFC-41 (fluoromethane, CH3F)

[0156] HFC-125 (pentafluoroethane, CF3CHF2)

[0157] HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)

[0158] HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)

[0159] HFC-143a (1,1,1-trifluoroethane, CF3CH3)

[0160] HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)

[0161] HFC-152 (1,2-difluoroethane, CH2FCH2F)

[0162] HFC-161 (fluoroethane, CH3CH2F)

[0163] HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)

[0164] HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)

[0165] HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)

[0166] HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)

[0167] HCFC-22 (chlorodifluoromethane, CHClF2)

[0168] HCFC-31 (chlorofluoromethane, CH2ClF)

[0169] CFC-1113 (chlorotrifluoroethylene, CF2=CClF)

[0170] HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2)

[0171] HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)

[0172] HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)

[0173] HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)

[0174] HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0175] The refrigerant composition of the present invention may contain a total of about 10 parts per million (ppm) by weight or more of the tracer relative to the total refrigerant composition. Furthermore, the refrigerant composition of the present invention may contain a total of about 1000 ppm or less of the tracer relative to the total refrigerant composition. The refrigerant composition of the present invention may contain a total of preferably about 30 ppm or more, more preferably about 50 ppm or more of the tracer relative to the total refrigerant composition. The refrigerant composition of the present invention may contain a total of preferably about 500 ppm or less of the tracer relative to the total refrigerant composition, and may also contain a total of about 300 ppm or less of the tracer relative to the total refrigerant composition.

[0176] 2.3 UV fluorescent dye

[0177] The refrigerant composition of the present invention may contain a single type of ultraviolet fluorescent dye or two or more types of ultraviolet fluorescent dye.

[0178] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0179] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, benzoxanthene, fluorescein, and derivatives thereof. As ultraviolet fluorescent dyes, either or both of naphthalimide and coumarin are particularly preferred.

[0180] 2.4 stabilizer

[0181] The refrigerant composition of the present invention may contain one type of stabilizer alone or two or more types of stabilizers.

[0182] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0183] Examples of the stabilizer include nitro compounds, ethers, and amines.

[0184] Examples of the nitro compound include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0185] Examples of the ethers include 1,4-dioxane and the like.

[0186] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0187] Other examples include butylated hydroxyxylene and benzotriazole.

[0188] The content of the stabilizer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total refrigerant, and preferably 5% by mass or less, more preferably 2% by mass or less.

[0189] 2.5 polymerization inhibitors

[0190] The refrigerant composition of the present invention may contain one type of polymerization inhibitor alone or two or more types thereof.

[0191] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0192] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0193] The content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total refrigerant, and preferably 5% by mass or less, more preferably 2% by mass or less.

[0194] 3. Working fluid containing refrigeration oil

[0195] The working fluid containing refrigerator oil of the present invention contains at least the refrigerant or refrigerant composition of the present invention and refrigerator oil, and is used as the working fluid in refrigerator. Specifically, the working fluid containing refrigerator oil of the present invention is obtained by mixing the refrigerator oil used in the compressor of refrigerator with the refrigerant or refrigerant composition. In the working fluid containing refrigerator oil, the refrigerator oil of more than 10 mass % is usually contained. In the working fluid containing refrigerator oil, the refrigerator oil of less than 50 mass % is usually contained.

[0196] 3.1 Refrigeration oil

[0197] The composition of the present invention may contain one type of refrigeration oil alone or two or more types of refrigeration oil.

[0198] The refrigeration oil is not particularly limited and can be appropriately selected from commonly used refrigeration oils. In this case, a refrigeration oil that is more excellent in improving the compatibility with the mixture and the stability of the mixture can be appropriately selected as needed.

[0199] As the base oil of the refrigeration oil, for example, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferable.

[0200] In addition to the base oil, the refrigeration oil may contain additives. The additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoaming agents.

[0201] From the perspective of lubrication, the refrigeration oil preferably has a kinematic viscosity of 5 cSt or more at 40° C. From the perspective of lubrication, the refrigeration oil preferably has a kinematic viscosity of 400 cSt or less at 40° C.

[0202] The working fluid containing refrigeration oil of the present invention may further contain at least one additive as needed. Examples of the additive include the following solubilizers.

[0203] 3.2 solubilizer

[0204] The refrigeration oil-containing working fluid of the present invention may contain one type of solubilizing agent alone or two or more types of solubilizing agents.

[0205] The solubilizing agent is not particularly limited and can be appropriately selected from commonly used solubilizing agents.

[0206] Examples of the solubilizing agent include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluorinated ethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as the solubilizing agent.

[0207] 4. How to operate a freezer

[0208] The method for operating a refrigerator of the present invention is a method for operating a refrigerator using the refrigerant of the present invention.

[0209] Specifically, the method for operating a refrigerator of the present invention includes the step of circulating the refrigerant of the present invention in the refrigerator.

[0210] 5. Methods for inhibiting disproportionation reactions

[0211] The method for suppressing the disproportionation reaction of the present invention is a method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using the refrigerant of the present invention.

[0212] The method for suppressing the disproportionation reaction of the present invention can achieve the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring, particularly when the refrigerant pressure is 5.0 MPa and the refrigerant temperature reaches 150°C.

[0213] According to the method for suppressing the disproportionation reaction of the present invention, it is possible to operate the refrigeration cycle while suppressing the disproportionation reaction, particularly in a refrigerator not provided with a disproportionation reaction suppressing unit.

[0214] 6. Use for inhibiting disproportionation reaction

[0215] The present invention relates to the use of R32 and / or R152a for inhibiting the disproportionation reaction of HFO-1132(E). The disproportionation reaction is inhibited by mixing HFO-1132(E) with R32 and / or R152a at the mixing ratio of the refrigerant of the present invention.

[0216] In the application of the present invention for suppressing the disproportionation reaction, the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring can be achieved, particularly when the refrigerant pressure is 5.0 MPa and the refrigerant temperature reaches 150°C.

[0217] 7. Refrigeration equipment

[0218] The refrigeration device of the present invention has:

[0219] a heat transfer cycle for circulating a refrigerant on the utilization side;

[0220] a heat source side heat transfer cycle that circulates a heat source side refrigerant; and

[0221] a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat-source-side refrigerant,

[0222] The heat source side refrigerant is the composition described in 1. above.

[0223] Although the embodiments have been described above, it should be understood that various changes in form and details may be made without departing from the spirit and scope of the scope of the claims.

[0224] Example

[0225] The following examples are given to further explain the present invention in detail, but the present invention is not limited to these examples.

[0226] HFO-1132(E), R32, and R152a were mixed at the mass % shown in each table based on the total amount thereof to prepare a mixed refrigerant.

[0227] For each of these mixed refrigerants, the presence or absence of disproportionation reaction was examined using the following test method and test conditions.

[0228] Test methods

[0229] The refrigerant composition to be tested was transferred and filled into a test container. After heating to 150°C, a voltage was applied to the Pt wire inside the container to cause it to fuse, thereby supplying 30 J of energy to the refrigerant composition. The occurrence of a disproportionation reaction was determined by the rapid increase in pressure and temperature within the apparatus.

[0230] Test conditions

[0231] Test container: 38cc SUS container;

[0232] Test temperature: 150℃;

[0233] Pressure: 5MPa.

[0234] Judgment Criteria

[0235] “No explosion”: The temperature or pressure after the Pt wire melts is less than 2 times, and no rapid disproportionation reaction occurs.

[0236] "Explosion": After the Pt wire melts, the temperature or pressure reaches more than 2 times, and a rapid disproportionation reaction occurs.

[0237] [Table 1]

[0238]

[0239] According to the results in Table 1, it can be seen that the refrigerant of the present invention is Figure 1 No disproportionation occurs within the region shown in the triangle plot shown.

[0240] In addition, for each of the above-mentioned mixed refrigerants, the GWP, and the COP ratio and refrigeration capacity ratio relative to the refrigerants recorded in the table were evaluated as follows. The GWP of HFO-1132 (E) was set to 1, and the GWP of R32 and R152a were evaluated based on the values of the Fourth Report of the IPCC (Intergovernmental Panel on Climate Change). In addition, the COP, refrigeration capacity and boiling point of the mixed refrigerant were obtained by using the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) of the National Institute of Science and Technology (NIST) and performing theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions. Among them, the physical property data of HFO-1132 (E) used for the theoretical calculation of the refrigeration cycle were obtained by actual measurement and added to Refprop.10.0.

[0241] <Comparison to R410A>

[0242]

[0243] <Ratio to R1234yf>

[0244]

[0245] <Ratio to R404A>

[0246]

[0247] In the following tables, "COP ratio" and "refrigeration capacity ratio" indicate the ratio (%) to R410A, R1234yf, or R404A. In the tables, "boiling point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant reaches atmospheric pressure (101.33 kPa).

[0248] The coefficient of performance (COP) is calculated using the following formula.

[0249] COP = (refrigeration capacity or heating capacity) / power consumption

[0250] In the following table, "Power Consumption (%)" indicates the electrical energy used for driving an electric vehicle, expressed as a ratio to the electrical energy consumption when R1234yf is used as the refrigerant. "Heating Power Consumption (%)" indicates the electrical energy used for heating an electric vehicle, expressed as a ratio to the electrical energy consumption when R1234yf is used as the refrigerant.

[0251] In the table below, "Drivable distance (with)" refers to the distance that can be traveled when heating is used and driving, expressed as a relative proportion (%), when the drivable distance (without) when traveling without heating (the power consumption for heating is 0) is set to 100% in an electric vehicle equipped with a secondary battery with a certain charge.

[0252] Regarding the heating method, an electric heater method is used for heating of refrigerants with a boiling point exceeding -40°C, while a heat pump method is used for heating of refrigerants with a boiling point below -40°C.

[0253] The power consumption when using heating is calculated using the following formula: Heating COP stands for "heating efficiency."

[0254] Electricity consumption when heating = Heating capacity / Heating COP

[0255] Regarding heating efficiency, in the case of an electric heater, heating COP = 1, and the same amount of electricity as power is consumed during heating. In other words, the power consumption for heating is E = E / (1 + COP).

[0256] The drivable distance is calculated using the following formula.

[0257] Driving distance = (battery capacity) / (power consumption for propulsion + power consumption for heating)

[0258] The evaluation results are shown in the following table.

[0259] [Table 2]

[0260]

[0261] The results in Table 1 show that a mixed refrigerant consisting solely of HFO-1132(E) and R152a, when containing 57% by mass or less of HFO-1132(E) and 43% by mass or more of R152a relative to the total mass of the mixed refrigerant, has a refrigeration capacity ratio of 55% or more relative to that of R410A, and does not undergo a disproportionation reaction at 5 MPa and 150°C.

[0262] [Table 3]

[0263]

[0264] The results in Table 3 show that a mixed refrigerant consisting solely of HFO-1132(E) and R152a has a boiling point of -40°C or lower, and does not undergo a disproportionation reaction at 5 MPa and 150°C, when containing 57% by mass or less of HFO-1132(E) and 32% by mass or more of R152a relative to the total mixed refrigerant.

[0265] [Table 4]

[0266]

[0267] The results in Table 4 show that a mixed refrigerant consisting solely of HFO-1132(E) and R152a, when containing 57% by mass or less of HFO-1132(E) and 43% by mass or more of R152a relative to the total mixed refrigerant, has a refrigeration capacity ratio of 70% or more relative to that of R404A, and does not undergo a disproportionation reaction at 5 MPa and 150°C.

[0268] [Table 5]

[0269]

[0270]

[0271] From these results, it can be seen that in the refrigerant of the present invention, when the mass percentages of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass%, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity ratio relative to R410A is 55% or more ( Figure 2 ).

[0272] <Conditions>

[0273] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD', D'E', E'F, FB, BA, and AC connecting the following six points, and on the above-mentioned line segments CD', D'E', E'F, and BA (excluding points A, C, B, and F).

[0274] Point D'(57.4,5.0,37.6),

[0275] Point E'(17.5,5.0,77.5),

[0276] Point F(0.0,22.9,77.1),

[0277] Point B (0.0, 32.0, 68.0), and

[0278] Point A (55.7, 44.3, 0.0).

[0279] [Table 6]

[0280]

[0281]

[0282] Furthermore, from the results in Table 6, it can be seen that in the refrigerant of the present invention, when the mass % of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass %, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less ( Figure 3 ).

[0283] <Conditions>

[0284] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines C'D', D'J', J'K, and KC' connecting the following four points, and on the straight lines C'D', D'J', J'K, and KC'.

[0285] Point C'(58.3,17.7,24.0),

[0286] Point D'(57.4,5.0,37.6),

[0287] Point J'(22.9,5.0,72.1),

[0288] Point K(19.3,9.0,71.7).

[0289] [Table 7]

[0290]

[0291]

[0292] Furthermore, from the results in Table 7, it can be seen that in the refrigerant of the present invention, when the mass % of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram where the total of HFO-1132(E), R32, and R152a is 100 mass %, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity ratio relative to R404A is 70% or more ( Figure 4 ).

[0293] <Conditions>

[0294] The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines C'D', 'D'L', L'M, and MC' connecting the following four points, and on the straight lines C'D', D'L', L'M, and MC'.

[0295] Point C'(58.3,17.7,24.0), point D'(57.4,5.0,37.6), point L'(17.1,5.0,77.9), and point M(14.0,7.8,78.2).

Claims

1. A composition containing a refrigerant, characterized in that: The refrigerant contains 22.6 to 57% by mass of trans-1,2-difluoroethylene (HFO-1132(E)) and 77.4 to 43% by mass of 1,1-difluoroethane (R152a) relative to the total of trans-1,2-difluoroethylene (HFO-1132(E)) and 1,1-difluoroethane (R152a).

2. The composition according to claim 1, wherein: The content of HFO-1132(E)) and R152a is 22.9 to 57% by mass and 77.1 to 43% by mass, respectively, based on the total of HFO-1132(E)) and R152a.

3. The composition according to claim 1, wherein: The content of HFO-1132(E)) and R152a is 28.3 to 57% by mass and 71.7 to 43% by mass, respectively, based on the total of HFO-1132(E)) and R152a.

4. The composition according to any one of claims 1 to 3, wherein: The total amount of HFO-1132(E) and R152a contained is 99.5% by mass or more based on the entire refrigerant.

5. A composition containing a refrigerant, characterized in that: The refrigerant contains 99.5% by mass or more of R152a, R32, and HFO-1132(E) in total relative to the total refrigerant, and Assuming that the mass % of HFO-1132(E), R32, and R152a based on their total are x, y, and z, respectively, in a three-component composition diagram in which the total of HFO-1132(E), R32, and R152a is 100 mass %, the coordinates (x, y, z) are located within the range of the figure enclosed by straight lines CD', D'E', E'F, FB, BA, and AC connecting the following six points, respectively, and on the line segments CD', D'E', E'F, and BA, excluding points A, C, B, and F. Point C (60.0, 40.0, 0.0), Point D'(57.4,5.0,37.6), Point E'(17.5,5.0,77.5), Point F(0.0,22.9,77.1), Point B (0.0, 32.0, 68.0), and Point A (55.7, 44.3, 0.0).

6. The composition according to claim 5, wherein: In the refrigerant, the coordinates (x, y, z) are located within the range of a figure enclosed by straight lines C'D', D'J', J'K, and KC' connecting the following four points, and on the straight lines C'D', D'J', J'K, and KC'. Point C'(58.3,17.7,24.0), Point D'(57.4,5.0,37.6), Point J'(22.9,5.0,72.1), and Point K(19.3,9.0,71.7).

7. The composition according to claim 5, characterized in that: In the refrigerant, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines C'D', 'D'L', L'M, and MC' connecting the following four points, and on the straight lines C'D', D'L', L'M, and MC'. Point C'(58.3,17.7,24.0), Point D'(57.4,5.0,37.6), Point L'(17.1,5.0,77.9), and Point M(14.0,7.8,78.2).

8. The composition according to claim 2 or 5, wherein: It is a composition for replacing R410A.

9. The composition according to claim 3 or 6, wherein: It is a composition for replacing R1234yf.

10. The composition according to claim 9, wherein: This is a composition for replacing R1234yf and for use in refrigeration cycle operation of air conditioners for electric vehicles.

11. The composition according to claim 1 or 7, wherein: It is a composition for replacing R404A.

12. A refrigeration device, characterized in that: have: a heat transfer cycle for circulating a refrigerant on the utilization side; a heat source side heat transfer cycle that circulates a heat source side refrigerant; and a cascade heat exchanger for exchanging heat between the utilization-side refrigerant and the heat-source-side refrigerant, The heat source side refrigerant is the composition according to any one of claims 1 to 7.

13. A freezing method, characterized in that: The method comprises the step of operating a refrigeration cycle using the composition according to any one of claims 1 to 7.

14. A refrigeration device, characterized in that: The working fluid comprises the composition according to any one of claims 1 to 7.

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