Refrigerant-containing composition, use thereof, refrigerator having the same, and operation method of the refrigerator

Abstract

Provided is a composition capable of inhibiting disproportionation of a refrigerant containing HFO-1132. The composition is a composition containing a refrigerant containing trans-1,2-difluoroethylene (HFO-1132(E)), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and propane.

Description

Technical Field

[0001] This invention relates to compositions containing refrigerants, their use, refrigerators having the same, and methods of operating the refrigerators. Background Technology

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

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2012 / 157765 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] The technical problem to be solved by the present invention is to suppress the disproportionation of refrigerants containing HFO-1132.

[0008] Technical solutions for solving technical problems

[0009] Item 1. A composition containing a refrigerant, wherein,

[0010] The above refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), 2,3,3,3-tetrafluoro-1-propylene (R1234yf) and propane.

[0011] Item 2. The composition as described in Item 1, wherein,

[0012] In the aforementioned refrigerant, when the mass percentages of HFO-1132(E), R1234yf, and propane, based on their total mass, are set as x, y, and z respectively, in a three-component composition diagram where the total mass percentage of HFO-1132(E), R1234yf, and propane is 100%, the coordinates (x, y, z) are respectively connected to...

[0013] Point A (95.0, 0.0, 5.0),

[0014] Point B (60.0, 40.0, 0.0),

[0015] Point C(0.0, 100.0, 0.0) and

[0016] Point D(0.0,0.0,100.0)

[0017] The area enclosed by the lines AB, BC, CD, and DA of the four points, or on the line AB (excluding points A and B).

[0018] Item 3. The composition as described in Item 1, wherein,

[0019] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0020] Point A (95.0, 0.0, 5.0),

[0021] Point B (60.0, 40.0, 0.0),

[0022] Point C(0.0, 100.0, 0.0),

[0023] Point E1(0.0, 45.5, 54.5) and

[0024] Point F1(52.4,0.0,47.6)

[0025] The area enclosed by the lines AB, BC, CE1, E1F1, and F1A of the five points, or on the lines AB and E1F1 (excluding points A, B, E1, and F1).

[0026] Item 4. The composition as described in Item 1, wherein,

[0027] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0028] Point A (95.0, 0.0, 5.0),

[0029] Point B (60.0, 40.0, 0.0),

[0030] Point C(0.0, 100.0, 0.0),

[0031] Point E2(0.0, 59.4, 40.6) and

[0032] Point F2(68.5,0.0,31.5)

[0033] The area enclosed by the lines AB, BC, CE2, E2F2, and F2A of the five points, or on the lines AB and E2F2 (excluding points A, B, E2, and F2).

[0034] Item 5. The composition as described in Item 1, wherein,

[0035] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0036] Point A (95.0, 0.0, 5.0),

[0037] Point B (60.0, 40.0, 0.0),

[0038] Point C(0.0, 100.0, 0.0),

[0039] Point E3 (0.0, 73.4, 26.6) and

[0040] Point F3(84.6,0.0.15.4)

[0041] The area enclosed by the lines AB, BC, CE3, E3F3, and F3A of the five points, or on the lines AB and E3F3 (excluding points A, B, E3, and F3).

[0042] Item 6. The composition as described in Item 1, wherein,

[0043] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0044] Point A (95.0, 0.0, 5.0),

[0045] Point B (60.0, 40.0, 0.0),

[0046] Point C1(32.7, 67.3, 0.0) and

[0047] Point D1(15.4, 0.0, 84.6),

[0048] The area bounded by the lines AB, BC1, and D1A, and the connecting line C1D1, or the area on the aforementioned lines AB and C1D1 (excluding points A, B, C1, and D1), where the connecting line C1D1 is located at coordinates (0.0095y). 2 +0.615y + 15.4,y, -0.0095y 2 -0.615y+84.6) represents this.

[0049] Item 7. The composition as described in Item 1, wherein,

[0050] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0051] Point A (95.0, 0.0, 5.0),

[0052] Point B (60.0, 40.0, 0.0),

[0053] Point C2(41.7,58.3,0.0) and

[0054] Point D2(37.0, 0.0, 63.0),

[0055] The area enclosed by the lines AB, BC2, C2D2, and D2A connecting the four points, or on the lines AB and C2D2 (excluding points A, B, C2, and D2),

[0056] The line C2D2 is connected from the coordinates (0.0059y). 2 +0.7359y+37,y,-0.0059y 2 -0.7359y+63) means,

[0057] The lines AB, BC2, and D2A are all straight lines.

[0058] Item 8. The composition as described in Item 1, wherein,

[0059] In the aforementioned refrigerant, the coordinates (x, y, z) are respectively connected to...

[0060] Point A (95.0, 0.0, 5.0),

[0061] Point B (60.0, 40.0, 0.0),

[0062] Point C3(50.8,49.2,0.0) and

[0063] Point D3(53.0,0.0,47.0),

[0064] The area enclosed by the lines AB, BC3, C3D3, and D3A connecting the four points, or on the lines AB and C3D3 (excluding points A, B, C3, and D3),

[0065] The line C3D3 is connected from coordinates (0.0039y). 2 +0.763y+53,y,-0.0039y 2 -0.763y+47) means,

[0066] The lines AB, BC3, and D3A are all straight lines.

[0067] Item 9. The composition as described in any one of items 1 to 8, wherein,

[0068] z is 1 or more.

[0069] Item 10. The composition as described in any one of items 1 to 9, wherein,

[0070] It also contains refrigeration oil, and the above composition is used as a working fluid for refrigeration machines.

[0071] Item 11. The composition as described in any one of items 1 to 10, wherein,

[0072] Used as an alternative refrigerant to R410A.

[0073] Item 12. Use of any one of the compositions described in items 1 to 10 as an alternative refrigerant to R410A.

[0074] Item 13. A refrigeration unit, wherein,

[0075] The composition containing any one of items 1 to 10 is used as the working fluid.

[0076] Item 14. A method for operating a refrigeration unit, wherein,

[0077] The process includes circulating the composition described in any one of items 1 to 10 in a refrigeration unit as a working fluid.

[0078] Invention Effects

[0079] The refrigerant containing HFO-1132 of the present invention can suppress the disproportionation of HFO-1132. Detailed Implementation

[0080] HFO-1132 is chemically unstable due to the presence of unsaturated bonds, and may pose a risk of disproportionation. To address the aforementioned technical problems, the inventors of this invention conducted meticulous research and discovered that a mixed refrigerant containing HFO-1132(E), R1234yf, and propane in a specific mixing ratio possesses the aforementioned characteristics.

[0081] This invention is the result of further and repeated research based on the above insights. The invention includes the following embodiments.

[0082] <Definition of Terms>

[0083] In this specification, the term "refrigerant" includes at least compounds bearing the refrigerant number (ASHRAE number) designated by ISO 817 (International Organization for Standardization) that begins with the letter R to indicate the type of refrigerant, and also includes substances that, although not designated with a refrigerant number, possess equivalent refrigerant properties. From a structural perspective, refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0084] In this specification, the term "composition containing refrigerant" includes at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) a composition that also contains other components and is capable of being used to obtain a working fluid for refrigeration machines by mixing with at least refrigeration oil; and (3) a working fluid for refrigeration machines containing refrigeration oil. In this specification, in these three ways, the composition of (2) is distinguished from the refrigerant itself (including mixtures of refrigerants) and is described as a "refrigerant composition." Furthermore, the working fluid for refrigeration machines of (3) is distinguished from the "refrigerant composition" and is described as a "working fluid containing refrigeration oil."

[0085] In this specification, the term "replacement" is used in the context of "replacing" the first refrigerant with the second refrigerant. As a first type, it refers to a situation where, in equipment designed to operate using the first refrigerant, the second refrigerant can be used to operate under optimal conditions by making only minor changes to a few components (refrigeration oil, gaskets, packing, expansion valves, dryers, and at least one of other components) and equipment adjustments. That is, this type refers to "replacing" the refrigerant to operate the same equipment. As for this type of "replacement," depending on the degree of change or adjustment required when replacing with the second refrigerant, the methods can be, in ascending order of severity, "drop-in replacement," "near-drop-in replacement," and "retrofit."

[0086] As a second type, the use of a second refrigerant for the purpose of using equipment designed to operate with a second refrigerant for the same purpose as the existing use of the first refrigerant also falls under the term "substitution." This type refers to "substituting" a refrigerant to provide the same purpose.

[0087] In this specification, the term "refrigerator" refers to any device that extracts heat from an object or space, bringing it to a temperature lower than that of the surrounding external air, and maintains that low temperature. In other words, a refrigerator is a device that performs energy conversion by moving heat from a lower temperature to a higher temperature, obtaining energy from the outside, and performing work.

[0088] In this instruction manual, the term "slightly flammable" for refrigerant means that it is classified as "2L class" in the American ANSI / ASHRAE 34-2013 standard.

[0089] 1. refrigerant

[0090] 1.1 Refrigerant composition

[0091] The refrigerant of the present invention is a mixed refrigerant containing HFO-1132(E), R1234yf and propane.

[0092] The refrigerant of the present invention suppresses the disproportionation of HFO-1132(E) by satisfying the following requirements.

[0093] When the mass percentages of HFO-1132(E), R1234yf, and propane, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234yf, and propane is 100% by mass, the coordinates (x, y, z) are connected to the respective...

[0094] Point A (95.0, 0.0, 5.0),

[0095] Point B (60.0, 40.0, 0.0),

[0096] Point C(0.0, 100.0, 0.0) and

[0097] Point D(0.0,0.0,100.0)

[0098] The area enclosed by the lines AB, BC, CD, and DA of the four points, or on the line AB (excluding points A and B).

[0099] The refrigerant of this invention achieves a heat of combustion of 30 kJ / kg or less by satisfying the following requirement. Coordinates (x, y, z) are respectively connected...

[0100] Point A (95.0, 0.0, 5.0),

[0101] Point B (60.0, 40.0, 0.0),

[0102] Point C(0.0, 100.0, 0.0),

[0103] Point E1(0.0, 45.5, 54.5) and

[0104] Point F1(52.4,0.0,47.6)

[0105] The area enclosed by the lines AB, BC, CE1, E1F1, and F1A of the five points, or on the lines AB and E1F1 (excluding points A, B, E1, and F1).

[0106] The refrigerant of this invention achieves a heat of combustion of 25 kJ / kg or less by satisfying the following requirement. Coordinates (x, y, z) are respectively connected...

[0107] Point A (95.0, 0.0, 5.0),

[0108] Point B (60.0, 40.0, 0.0),

[0109] Point C(0.0, 100.0, 0.0),

[0110] Point E2(0.0, 59.4, 40.6) and

[0111] Point F2(68.5,0.0,31.5)

[0112] The area enclosed by the lines AB, BC, CE2, E2F2, and F2A of the five points, or on the lines E2F2 and F2B (excluding points B, E2, and F2).

[0113] The refrigerant of this invention achieves a heat of combustion of 20 kJ / kg or less by satisfying the following requirements. Coordinates (x, y, z) are respectively connected...

[0114] Point A (95.0, 0.0, 5.0),

[0115] Point B (60.0, 40.0, 0.0),

[0116] Point C(0.0, 100.0, 0.0),

[0117] Point E3 (0.0, 73.4, 26.6) and

[0118] Point F3(84.6,0.0.15.4)

[0119] The area enclosed by the lines AB, BC, CE3, E3F3, and F3A (points 5 and 6) or on the lines E3F3 and F3B (excluding points B, E3, and F3).

[0120] The refrigerant of the present invention has a refrigeration capacity of 60% or more relative to R410A by satisfying the following requirements.

[0121] The coordinates (x, y, z) are connected respectively.

[0122] Point A (95.0, 0.0, 5.0),

[0123] Point B (60.0, 40.0, 0.0),

[0124] Point C1(32.7, 67.3, 0.0) and

[0125] Point D1(15.4,0.0,84.6)

[0126] The area bounded by the lines AB, BC1, and D1A, and the connecting line C1D1, or the area on the aforementioned lines AB and C1D1 (excluding points A, B, C1, and D1), where the connecting line C1D1 is located at coordinates (0.0095y). 2 +0.615y + 15.4,y, -0.0095y 2 -0.615y+84.6) means,

[0127] The lines AB, BC1, and D1A are all straight lines.

[0128] The refrigerant of the present invention has a refrigeration capacity of 65% or more relative to R410A by satisfying the following requirements.

[0129] The coordinates (x, y, z) are connected respectively.

[0130] Point A (95.0, 0.0, 5.0),

[0131] Point B (60.0, 40.0, 0.0),

[0132] Point C2(41.7,58.3,0.0) and

[0133] Point D2(37.0, 0.0, 63.0),

[0134] The area enclosed by the lines AB, BC2, C2D2, and D2A connecting the four points, or on the lines AB and C2D2 (excluding points A, B, C2, and D2),

[0135] The line C2D2 is connected from the coordinates (0.0059y). 2 +0.7359y+37,y,-0.0059y 2 -0.7359y+63) means,

[0136] The lines AB, BC2, and D2A are all straight lines.

[0137] The refrigerant of the present invention has a refrigeration capacity of 70% or more relative to R410A by satisfying the following requirements.

[0138] The coordinates (x, y, z) are connected respectively.

[0139] Point A (95.0, 0.0, 5.0),

[0140] Point B (60.0, 40.0, 0.0),

[0141] Point C3(50.8,49.2,0.0) and

[0142] Point D3(53.0,0.0,47.0),

[0143] The area enclosed by the lines AB, BC3, C3D3, and D3A connecting the four points, or on the lines AB and C3D3 (excluding points A, B, C3, and D3),

[0144] The line C3D3 is connected from coordinates (0.0039y). 2 +0.763y+53,y,-0.0039y 2 -0.763y+47) means,

[0145] The lines AB, BC3, and D3A are all straight lines.

[0146] The refrigerant of the present invention readily dissolves in high-boiling-point refrigeration oil when z is 1 or more. Examples of high-boiling-point refrigeration oils include, for instance, mineral oil used as refrigeration oil for R22. In this respect, z is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.

[0147] In the refrigerant of the present invention, the contents of HFO-1132(E), R1234yf and propane are preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less, respectively, relative to the total refrigerant.

[0148] In the refrigerant of the present invention, the contents of HFO-1132(E), R1234yf and propane are preferably 1% by mass or more, more preferably 2% by mass or more, and most preferably 3% by mass or more, relative to the total refrigerant.

[0149] In the refrigerant of the present invention, other additional refrigerants may be added besides HFO-1132(E), R1234yf, and propane, without impairing the aforementioned properties and effects. From this perspective, the refrigerant of the present invention preferably contains HFO-1132(E), R1234yf, and propane in a total content of 99.5% by mass or more relative to the total refrigerant, preferably 99.75% by mass or more, more preferably 99.9% by mass or more, further preferably 99.99% by mass or more, and most preferably 99.999% by mass or more. The refrigerant of the present invention may substantially consist only of HFO-1132(E), R1234yf, and propane. In the case where the refrigerant of the present invention is substantially composed only of HFO-1132(E), R1234yf and propane, it may also contain impurities that are inevitably mixed in during the manufacturing process of these components, in addition to HFO-1132(E), R1234yf and propane.

[0150] There are no particular limitations on the type of refrigerant that can be added; a wide range of options are available. As an additional refrigerant, the mixed refrigerant can contain only one type or two or more types.

[0151] 1.2 use

[0152] The refrigerant of the present invention can be preferably used as the working fluid in a refrigeration machine.

[0153] The compositions of the present invention are suitable for use as alternative refrigerants to R410A and R404A.

[0154] 2. Refrigerant Composition

[0155] 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. Furthermore, the refrigerant composition of the present invention can also be used to obtain a working fluid for refrigeration machines by mixing with at least refrigeration oil.

[0156] The refrigerant composition of the present invention contains at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may, as needed, contain at least one of the following other components. As described above, when the refrigerant composition of the present invention is used as the working fluid of a refrigeration machine, it is generally used in combination with at least refrigeration oil. Therefore, the refrigerant composition of the present invention preferably contains substantially no 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.

[0157] 2.1 water

[0158] The refrigerant composition of the present invention may contain trace amounts of water. The water content in the refrigerant composition is preferably 0.1% by mass or less relative to the total refrigerant. By containing trace amounts of water in the refrigerant composition, the intramolecular double bonds of the unsaturated fluorocarbon compounds that may be contained in the refrigerant can be stabilized, and the oxidation of the unsaturated fluorocarbon compounds is less likely to occur, thus improving the stability of the refrigerant composition.

[0159] 2.2 tracer

[0160] In order to track changes in the refrigerant composition of the present invention when it is diluted, contaminated, or otherwise altered, a tracer is added to the refrigerant composition of the present invention at a detectable concentration.

[0161] As a tracer, the refrigerant composition of the present invention may contain one or more tracers.

[0162] There are no particular limitations on the tracer used; it can be appropriately selected from commonly used tracers.

[0163] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorohydrocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorinated ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N₂O). Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorohydrocarbons, fluorocarbons, and fluorinated ethers are particularly preferred as tracers.

[0164] The following compounds are preferred as tracers.

[0165] FC-14 (Tetrafluoromethane, CF4)

[0166] HCC-40 (chloromethane, CH3Cl)

[0167] HFC-23 (trifluoromethane, CHF3)

[0168] HFC-41 (fluoromethane, CH3Cl)

[0169] HFC-125 (pentafluoroethane, CF3CHF2)

[0170] HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)

[0171] HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)

[0172] HFC-143a (1,1,1-trifluoroethane, CF3CH3)

[0173] HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)

[0174] HFC-152a (1,1-difluoroethane, CHF2CH3)

[0175] HFC-152 (1,2-difluoroethane, CH2FCH2F)

[0176] HFC-161 (fluoroethane, CH3CH2F)

[0177] HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)

[0178] HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)

[0179] HFC-236ea(1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)

[0180] HFC-227ea(1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)

[0181] HCFC-22 (dichlorofluoromethane, CHClF2)

[0182] HCFC-31 (chlorofluoromethane, CH2ClF)

[0183] CFC-1113 (chlorotrifluoroethylene, CF2=CClF)

[0184] HFE-125 (trifluoromethyl difluoromethyl ether, CF3OCHF2)

[0185] HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)

[0186] HFE-143a (trifluoromethyl methyl ether, CF3OCH3)

[0187] HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)

[0188] HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0189] Relative to the overall refrigerant composition, the refrigerant composition of the present invention may contain tracers in a total preferably about 10 parts by weight (ppm) or more, and about 1000 ppm or less. Relative to the overall refrigerant composition, the total tracer content in the refrigerant composition of the present invention is preferably about 30 ppm or more, and more preferably about 50 ppm or more. Relative to the overall refrigerant composition, the total tracer content in the refrigerant composition of the present invention is preferably about 500 ppm or less, and more preferably about 300 ppm or less.

[0190] 2.3 Ultraviolet fluorescent dyes

[0191] As an ultraviolet fluorescent dye, the refrigerant composition of the present invention may contain a single type or two or more types.

[0192] As an ultraviolet fluorescent dye, there are no particular limitations, and it can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0193] Examples of ultraviolet fluorescent dyes include naphthalenediimide, coumarin, anthracene, phenanthrene, xanthracene, thioxanthene, benzoxanthracene, and fluorescein, as well as their derivatives. Naphthalenediimide and either or both of coumarin are particularly preferred as ultraviolet fluorescent dyes.

[0194] 2.4 stabilizer

[0195] As a stabilizer, the refrigerant composition of the present invention may contain one or more types of stabilizers.

[0196] As a stabilizer, there are no particular limitations; it can be appropriately selected from commonly used stabilizers.

[0197] Examples of stabilizers include nitro compounds, ethers, and amines.

[0198] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0199] Examples of ethers include 1,4-dioxane.

[0200] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0201] In addition, butylated hydroxyxylene, benzotriazole, etc. can also be listed.

[0202] The content of stabilizer is not particularly limited, but it is generally preferred to be 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant. The content of stabilizer is generally preferred to be 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant.

[0203] 2.5 Polymerization inhibitor

[0204] As a polymerization inhibitor, the refrigerant composition of the present invention may contain one or more inhibitors.

[0205] There are no particular limitations on the type of polymerization inhibitor used; it can be appropriately selected from commonly used polymerization inhibitors.

[0206] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0207] The proportion of the polymerization inhibitor is not particularly limited, but it is generally preferred to be 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total refrigerant. The proportion of the polymerization inhibitor relative to the total refrigerant is generally preferred to be 5% by mass or less, more preferably 5% by mass or less.

[0208] 3. Working fluid containing refrigeration oil

[0209] The working fluid containing refrigeration oil of the present invention contains at least the refrigerant or refrigerant composition of the present invention and refrigeration oil, and is used as a working fluid in a refrigeration unit. Specifically, the working fluid containing refrigeration oil of the present invention is obtained by mixing refrigeration oil used in the compressor of the refrigeration unit with the refrigerant or refrigerant composition. In the working fluid containing refrigeration oil, the refrigeration oil typically contains more than 10% by mass and less than 50% by mass.

[0210] 3.1 Refrigeration oil

[0211] As a refrigeration oil, the composition of the present invention may contain only one type or two or more types.

[0212] There are no particular limitations on the type of refrigeration oil used; any commonly used refrigeration oil can be selected. However, depending on the specific needs, a refrigeration oil that excels in improving the miscibility and stability of the aforementioned mixture can be chosen.

[0213] As a base oil for refrigeration oil, it is preferably selected from at least one of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0214] In addition to base oil, refrigeration oil may also contain additives. Additives may be at least one selected from antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoamers.

[0215] From a lubrication perspective, a kinematic viscosity of 5 cSt or higher at 40°C is preferred for refrigeration oil. From a lubrication perspective, a kinematic viscosity of 400 cSt or lower at 40°C is preferred for refrigeration oil.

[0216] The working fluid containing refrigeration oil of the present invention may also contain at least one additive as needed. Examples of additives include compatibilizers, etc.

[0217] 3.2 Compatibilizer

[0218] As a compatibilizer, the working fluid containing refrigeration oil of the present invention may contain only one type or two or more types.

[0219] There are no particular limitations on the compatibilizer; it can be appropriately selected from commonly used compatibilizers.

[0220] Examples of compatibilizers 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 compatibilizers.

[0221] 4. How to operate a refrigeration unit

[0222] The method of operating the refrigeration unit of the present invention is a method of operating the refrigeration unit using the refrigerant of the present invention.

[0223] Specifically, the method of operating the refrigeration machine of the present invention includes the step of circulating the refrigerant of the present invention within the refrigeration machine.

[0224] The implementation methods have been described above, but it should be understood that various changes in manner and details may be made without departing from the spirit and scope of the claimed protection.

[0225] Example

[0226] The following examples illustrate the invention in more detail. However, the invention is not limited to these examples.

[0227] HFO-1132(E), R1234yf, and propane were mixed at their total weights as shown in Tables 1 and 2, respectively, to prepare a mixed refrigerant.

[0228] For each of these refrigerant mixtures, calculate the COP ratio and refrigeration capacity ratio based on R410 or R404A. The calculation conditions are set as follows.

[0229] Evaporation temperature: 5℃

[0230] Condensation temperature: 45℃

[0231] Overheat level: 1K

[0232] Supercooling degree; 5K

[0233] E comp (Compression power): 0.7kWh

[0234] These values, along with the GWP of each refrigerant mixture, are shown in Tables 1 and 2.

[0235] The heat of combustion is calculated from the standard enthalpy of formation of HFO-1132(E), HFO-1234yf, propane, CO2, HF, COF2, and H2O to obtain the standard enthalpy of combustion.

[0236] The present invention has been described in more detail based on embodiments and comparative examples, but the invention is not limited thereto. Those skilled in the art will be able to make various changes, modifications, and alterations without departing from the scope of the invention.

[0237] (Experimental system for disproportionation reaction)

[0238] The recommended application of disproportionation is to implement and evaluate equipment that measures the combustion range of a mixture of gases containing halogens, as specified in the individual notices of the High Pressure Gas Safety Law, in accordance with Law A.

[0239] Specifically, the internal volume of 50 cm² can be controlled externally to a specified temperature. 3 Inside a spherical pressure vessel, the refrigerant components (described later) are sealed at a specified pressure, and then the platinum wire inside is melted, thereby applying approximately 30 J of energy. The presence of a disproportionation reaction is confirmed by measuring the temperature and pressure changes within the pressure vessel after the energy application. A pressure difference of 1 MPaG or more and a temperature difference of 10°C or more before and after ignition are considered indicative of a disproportionation reaction.

[0240] In the above experimental system, R1132(E), propane, and R1234yf were introduced from the gas cylinder into the pressure vessel. At this time, the internal pressure was 1.0 MPa, and the internal temperature was approximately 100°C. It should be noted that, in this invention, pressure refers to gauge pressure unless otherwise specified.

[0241] The results of the above tests showed that, in Comparative Examples 1-9, the internal pressure was confirmed to be above 10 MPa and the internal temperature to be above approximately 100°C. Afterwards, once the internal pressure and internal temperature had sufficiently decreased, the interior of the pressure vessel was examined, and a considerable amount of coal was found to have been produced. In Examples 1-58, the pressure was confirmed to be below 1 MPa and the temperature difference to be below 10°C.

[0242] [Table 1]

[0243]

[0244] [Table 2]

[0245]

[0246] These results show that the refrigerant of the present invention can suppress the disproportionation of HFO-1132(E) by satisfying the following requirements.

[0247] When the mass percentages of HFO-1132(E), R1234yf, and propane, based on their sum, are set as x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234yf, and propane is 100% by mass, the coordinates (x, y, z) are connected to the respective...

[0248] Point A (95.0, 0.0, 5.0),

[0249] Point B (60.0, 40.0, 0.0),

[0250] Point C(0.0, 100.0, 0.0) and

[0251] Point D(0.0,0.0,100.0)

[0252] The area enclosed by the lines AB, BC, CD, and DA of the four points, or on the line AB (excluding points A and B).

[0253] These results show that the refrigerant of the present invention achieves a heat of combustion of 30 kJ / kg or less by satisfying the following requirements.

[0254] The coordinates (x, y, z) are connected respectively.

[0255] Point A (95.0, 0.0, 5.0),

[0256] Point B (60.0, 40.0, 0.0),

[0257] Point C(0.0, 100.0, 0.0),

[0258] Point E1(0.0, 45.5, 54.5) and

[0259] Point F1(52.4,0.0,47.6)

[0260] The area enclosed by the lines AB, BC, CE1, E1F1, and F1A of the five points, or on the lines AB and E1F1 (excluding points A, B, E1, and F1).

[0261] These results show that the refrigerant of the present invention achieves a heat of combustion of 25 kJ / kg or less by satisfying the following requirements.

[0262] The coordinates (x, y, z) are connected respectively.

[0263] Point A (95.0, 0.0, 5.0),

[0264] Point B (60.0, 40.0, 0.0),

[0265] Point C(0.0, 100.0, 0.0),

[0266] Point E2(0.0, 59.4, 40.6) and

[0267] Point F2(68.5,0.0,31.5)

[0268] The area enclosed by the lines AB, BC, CE2, E2F2, and F2A of the five points, or on the lines E2F2 and F2B (excluding points B, E2, and F2).

[0269] These results show that the refrigerant of the present invention achieves a heat of combustion of less than 20 kJ / kg by satisfying the following requirements.

[0270] The coordinates (x, y, z) are connected respectively.

[0271] Point A (95.0, 0.0, 5.0),

[0272] Point B (60.0, 40.0, 0.0),

[0273] Point C(0.0, 100.0, 0.0),

[0274] Point E3 (0.0, 73.4, 26.6) and

[0275] Point F3(84.6,0.0.15.4)

[0276] Within the area bounded by the lines AB, BC, CE3, E3F3, and F3A (points 5 and 6), or on the lines E3F3 and F3B (excluding points B, E2, and F3).

[0277] These results show that the refrigerant of the present invention achieves a refrigeration capacity of more than 60% relative to R410A by satisfying the following requirements.

[0278] The coordinates (x, y, z) are connected respectively.

[0279] Point A (95.0, 0.0, 5.0),

[0280] Point B (60.0, 40.0, 0.0),

[0281] Point C1(32.7, 67.3, 0.0) and

[0282] Point D1(15.4,0.0,84.6)

[0283] The area bounded by the lines AB, BC1, and D1A, and the connecting line C1D1, or the area on the aforementioned lines AB and C1D1 (excluding points A, B, C1, and D1), where the connecting line C1D1 is located at coordinates (0.0095y). 2 +0.615y + 15.4,y, -0.0095y 2 -0.615y+84.6) means,

[0284] The lines AB, BC1, and D1A are all straight lines.

[0285] These results show that the refrigerant of the present invention achieves a refrigeration capacity of more than 65% relative to R410A by satisfying the following requirements.

[0286] The coordinates (x, y, z) are connected respectively.

[0287] Point A (95.0, 0.0, 5.0),

[0288] Point B (60.0, 40.0, 0.0),

[0289] Point C2(41.7,58.3,0.0) and

[0290] Point D2(37.0,0.0,63.0)

[0291] The area enclosed by the lines AB, BC2, C2D2, and D2A connecting the four points, or on the lines AB and C2D2 (excluding points A, B, C2, and D2),

[0292] The line C2D2 is connected from the coordinates (0.0059y). 2 +0.7359y+37,y,-0.0059y 2 -0.7359y+63) means,

[0293] The lines AB, BC2, and D2A are all straight lines.

[0294] These results show that the refrigerant of the present invention achieves a refrigeration capacity of more than 70% relative to R410A by satisfying the following requirements.

[0295] The coordinates (x, y, z) are connected respectively.

[0296] Point A (95.0, 0.0, 5.0),

[0297] Point B (60.0, 40.0, 0.0),

[0298] Point C3(50.8,49.2,0.0) and

[0299] Point D3(53.0,0.0,47.0)

[0300] The area enclosed by the lines AB, BC3, C3D3, and D3A connecting the four points, or on the lines AB and C3D3 (excluding points A, B, C3, and D3),

[0301] The line C3D3 is connected from coordinates (0.0039y). 2 +0.763y+53,y,-0.0039y 2 -0.763y+47) means,

[0302] The lines AB, BC3, and D3A are all straight lines.

Claims

1. A composition containing a refrigerant, characterized in that: The refrigerant contains, in total, more than 99.5% by mass of trans-1,2-difluoroethylene (HFO-1132(E)), 2,3,3,3-tetrafluoro-1-propylene (R1234yf), and propane relative to the total refrigerant. In the refrigerant, when the mass percentages of HFO-1132(E), R1234yf, and propane, based on their total mass, are set as x, y, and z respectively, in a three-component composition diagram where the total mass percentage of HFO-1132(E), R1234yf, and propane is 100%, the coordinates (x, y, z) are respectively connected to... Point A'(80.0,0.0,20.0), Point B (60.0, 40.0, 0.0), Point C(0.0, 100.0, 0.0) and The area enclosed by the lines A'B, BC, CD, and DA' of point D(0.0,0.0,100.0) or on line A'B, excluding points on lines BC, CD, and DA'.

2. The composition according to claim 1, characterized in that: It contains refrigerant. The refrigerant contains HFO-1132(E), R1234yf, and propane in a total of 99.5% by mass relative to the total refrigerant. In the refrigerant, when the mass percentages of HFO-1132(E), R1234yf, and propane, based on their total mass, are set as x, y, and z respectively, in a three-component composition diagram where the total mass percentage of HFO-1132(E), R1234yf, and propane is 100%, the coordinates (x, y, z) are respectively connected to... Point A'(80.0,0.0,20.0), Point B (60.0, 40.0, 0.0), Point C(0.0, 100.0, 0.0), Point E1(0.0, 45.5, 54.5) and The area enclosed by the lines A'B, BC, CE1, E1F1, and F1A' of point F1(52.4,0.0,47.6) or on the lines A'B and E1F1, excluding points on the lines BC, CE1, and F1A'.

3. The composition according to claim 1, characterized in that: It contains refrigerant. The refrigerant contains HFO-1132(E), R1234yf, and propane in a total of 99.5% by mass relative to the total refrigerant. In the refrigerant, when the mass percentages of HFO-1132(E), R1234yf, and propane, based on their total mass, are set as x, y, and z respectively, in a three-component composition diagram where the total mass percentage of HFO-1132(E), R1234yf, and propane is 100%, the coordinates (x, y, z) are respectively connected to... Point A'(80.0,0.0,20.0), Point B (60.0, 40.0, 0.0), Point C(0.0, 100.0, 0.0), Point E2(0.0, 59.4, 40.6) and The area enclosed by the lines A'B, BC, CE2, E2F2, and F2A' of point F2 (68.5, 0.0, 31.5) or on the lines A'B and E2F2, excluding points on the lines BC, CE2, and F2A'.

4. The composition according to claim 1, characterized in that: It contains refrigerant. The refrigerant contains HFO-1132(E), R1234yf, and propane in a total of 99.5% by mass relative to the total refrigerant. In the refrigerant, when the mass percentages of HFO-1132(E), R1234yf, and propane, based on their total mass, are set as x, y, and z respectively, in a three-component composition diagram where the total mass percentage of HFO-1132(E), R1234yf, and propane is 100%, the coordinates (x, y, z) are respectively connected to... Point A'(80.0,0.0,20.0), Point B (60.0, 40.0, 0.0), Point C(0.0, 100.0, 0.0) and The area enclosed by the lines A'B, BC, CE3, and E3A' of point E3 (0.0, 73.4, 26.6) or on the lines A'B and E3A', excluding points on the lines BC and CE3.

5. The composition according to any one of claims 1 to 4, characterized in that: z is 1 or more.

6. The composition according to any one of claims 1 to 4, characterized in that: It also contains refrigeration oil, and the composition is used as a working fluid for refrigeration machines.

7. The composition according to any one of claims 1 to 4, characterized in that: Used as an alternative refrigerant to R410A.

8. Use of the composition according to any one of claims 1 to 6 as an alternative refrigerant to R410A.

9. A refrigeration unit, characterized in that: The composition comprising any one of claims 1 to 6 is used as the working fluid.

10. A method for operating a refrigeration unit, characterized in that: The process includes circulating the composition of any one of claims 1 to 6 in a refrigeration unit as a working fluid.

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