Composition comprising refrigerant, use thereof, refrigerating machine having same, and method for operating said refrigerating machine

The present disclosure relates to a composition comprising a refrigerant, use of the composition, a refrigerating machine having the composition, and a method for operating the refrigerating machine.

R410A is currently used as an air conditioning refrigerant for home air conditioners etc. R410A is a two-component mixed refrigerant of difluoromethane (CH 2 F 2 :HFC-32 or R32) and pentafluoroethane (C 2 HF 5 :HFC-125 or R125), and is a pseudo-azeotropic composition.

However, the global warming potential (GWP) of R410A is 2088. Due to growing concerns about global warming, R32, which has a GWP of 675, has been increasingly used.

For this reason, various low-GWP mixed refrigerants that can replace R410A have been proposed (PTL 1).

Patent Literature

PTL 1: WO2015/141678

Technical Problem

The present inventors performed independent examination, and conceived of the idea that no prior art had developed refrigerant compositions having three types of performance, i.e., a refrigerating capacity (also referred to as “cooling capacity” or “capacity”) and a coefficient of performance (COP) that are equivalent to those of R410A, and a sufficiently low GWP. An object of the present disclosure is to solve this unique problem.

Solution to Problem

Item 1

A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene (R1234yf).

Item 2

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AA′, A′B, BD, DC′, C′C, CO, and OA that connect the following 7 points:

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0),

point C (32.9, 67.1, 0.0), and

point O (100.0, 0.0, 0.0),

or on the above line segments (excluding the points on the line segments BD, CO, and OA);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments BD, CO, and OA are straight lines.

Item 3

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments GI, IA, AA′, A′B, BD, DC′, C′C, and CG that connect the following 8 points:

point G (72.0, 28.0, 0.0),

point I (72.0, 0.0, 28.0),

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point C (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segments IA, BD, and CG);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments GI, IA, BD, and CG are straight lines.

Item 4

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments JP, PN, NK, KA′, A′B, BD, DC′, C′C, and CJ that connect the following 9 points:

point J (47.1, 52.9, 0.0),

point P (55.8, 42.0, 2.2),

point N (68.6, 16.3, 15.1),

point K (61.3, 5.4, 33.3),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point C (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segments BD and CJ);

the line segment PN is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment NK is represented by coordinates (x, 0.2421x 2 −29.955x+931.91, −0.2421x 2 +28.955x−831.91),

the line segment KA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments JP, BD, and CJ are straight lines.

Item 5

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments JP, PL, LM, A′B, BD, DC′, C′C, and CJ that connect the following 9 points:

point J (47.1, 52.9, 0.0),

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point C (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segments BD and CJ);

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43)

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments JP, LM, BD, and CJ are straight lines.

Item 6

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PL, LM, MA′, A′B, BF, FT, and TP that connect the following 7 points:

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point F (0.0, 61.8, 38.2), and

point T (35.8, 44.9, 19.3),

or on the above line segments (excluding the points on the line segment BF);

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment FT is represented by coordinates (x, 0.0078x 2 −0.7501x+61.8, −0.0078x 2 −0.2499x+38.2),

the line segment TP is represented by coordinates (x, 0.00672x 2 −0.7607x+63.525, −0.00672x 2 −0.2393x+36.475), and

the line segments LM and BF are straight lines.

Item 7

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PL, LQ, QR, and RP that connect the following 4 points:

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point Q (62.8, 29.6, 7.6), and

point R (49.8, 42.3, 7.9),

or on the above line segments;

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment RP is represented by coordinates (x, 0.00672x 2 −0.7607x+63.525, −0.00672x 2 −0.2393x+36.475), and

the line segments LQ and QR are straight lines.

Item 8

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments SM, MA′, A′B, BF, FT, and TS that connect the following 6 points:

point S (62.6, 28.3, 9.1),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point F (0.0, 61.8, 38.2), and

point T (35.8, 44.9, 19.3),

or on the above line segments,

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment FT is represented by coordinates (x, 0.0078x 2 −0.7501x+61.8, −0.0078x 2 −0.2499x+38.2),

the line segment TS is represented by coordinates (x, 0.0017x 2 −0.7869x+70.888, −0.0017x 2 −0.2131x+29.112), and

the line segments SM and BF are straight lines.

Item 9

A composition comprising a refrigerant, the refrigerant comprising HFO-1132(E) and R1234yf, and optionally further comprising HFO-1123,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments Od, dg, gh, and hO that connect the following 4 points:

point d (87.6, 0.0, 12.4),

point g (18.2, 55.1, 26.7),

point h (56.7, 43.3, 0.0), and

point O (100.0, 0.0, 0.0),

or on the line segments Od, dg, and gh (excluding the points O and h);

the line segment dg is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, −0.0047y 2 +0.5177y+12.402),

the line segment gh is represented by coordinates (−0.0134z 2 −1.0825z+56.692, 0.0134z 2 +0.0825z+43.308, z), and the line segments HO and OD are straight lines.

Item 10

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments lg, gh, hi, and il that connect the following 4 points:

point l (72.5, 10.2, 17.3),

point g (18.2, 55.1, 26.7),

point h (56.7, 43.3, 0.0), and

point i (72.5, 27.5, 0.0) or

on the line segments lg, gh, and il (excluding the points h and i);

the line segment lg is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, 31 0.0047y 2 +0.5177y+12.402),

the line segment gh is represented by coordinates (−0.0134z 2 −1.0825z+56.692, 0.0134z 2 +0.0825z+43.308, z), and

the line segments hi and il are straight lines.

Item 11

The composition according to any one of Items 1 to 10, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.

Item 12

The composition according to any one of Items 1 to 11, for use as an alternative refrigerant for R410A.

Item 13

Use of the composition according to any one of Items 1 to 11 as an alternative refrigerant for R410A.

Item 14

A refrigerating machine comprising the composition according to any one of Items 1 to 11 as a working fluid.

Item 15

A method for operating a refrigerating machine, comprising the step of circulating the composition according to any one of Items 1 to 11 as a working fluid in a refrigerating machine.

Advantageous Effects of Invention

The refrigerant according to the present disclosure has three types of performance, i.e., a refrigerating capacity and a coefficient of performance that are equivalent to those of R410A, and a sufficiently low GWP.

FIG. 1 is a schematic view of an apparatus used in a flammability test.

FIG. 2 is a diagram showing points A to T and line segments that connect these points in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass %.

The present inventors conducted intensive study to solve the above problem, and consequently found that a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene (R1234yf) has the above properties.

The present disclosure has been completed as a result of further research based on this finding. The present disclosure includes the following embodiments.

Definition of Terms

In the present specification, the term “refrigerant” includes at least compounds that are specified in ISO 817 (International Organization for Standardization), and that are given a refrigerant number (ASHRAE number) representing the type of refrigerant with “R” at the beginning; and further includes refrigerants that have properties equivalent to those of such refrigerants, even though a refrigerant number is not yet given. Refrigerants are broadly divided into fluorocarbon compounds and non-fluorocarbon compounds in tams of the structure of the compounds. Fluorocarbon compounds include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), and the like.

In the present specification, the phrase “composition comprising a refrigerant” at least includes (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further comprises other components and that can be mixed with at least a refrigeration oil to obtain a working fluid for a refrigerating machine, and (3) a working fluid for a refrigerating machine containing a refrigeration oil. In the present specification, of these three embodiments, the composition (2) is referred to as a “refrigerant composition” so as to distinguish it from a refrigerant itself (including a mixture of refrigerants). Further, the working fluid for a refrigerating machine (3) is referred to as a “refrigeration oil-containing working fluid” so as to distinguish it from the “refrigerant composition.”

In the present specification, when the term “alternative” is used in a context in which the first refrigerant is replaced with the second refrigerant, the first type of “alternative” means that equipment designed for operation using the first refrigerant can be operated using the second refrigerant under optimum conditions, optionally with changes of only a few parts (at least one of the following: refrigeration oil, gasket, packing, expansion valve, dryer, and other parts) and equipment adjustment. In other words, this type of alternative means that the same equipment is operated with an alternative refrigerant. Embodiments of this type of “alternative” include “drop-in alternative,” “nearly drop-in alternative,” and “retrofit,” in the order in which the extent of changes and adjustment necessary for replacing the first refrigerant with the second refrigerant is smaller.

The term “alternative” also includes a second type of “alternative,” which means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use with the first refrigerant by using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.

In the present specification, the term “refrigerating machine” refers to machines in general that draw heat from an object or space to make its temperature lower than the temperature of ambient air, and maintain a low temperature. In other words, refrigerating machines refer to conversion machines that gain energy from the outside to do work, and that perform energy conversion, in order to transfer heat from where the temperature is lower to where the temperature is higher.

In the present specification, a refrigerant having a “WCF lower flammability” means that the most flammable composition (worst case of formulation for flammability: WCF) has a burning velocity of 10 cm/s or less according to the US ANSI/ASHRAE Standard 34-2013. Further, in the present specification, a refrigerant having “ASHRAE lower flammability” means that the burning velocity of WCF is 10 cm/s or less, that the most flammable fraction composition (worst case of fractionation for flammability: WCFF), which is specified by performing a leakage test during storage, shipping, or use based on ANSI/ASHRAE 34-2013 using WCF, has a burning velocity of 10 cm/s or less, and that flammability classification according to the US ANSI/ASHRAE Standard 34-2013 is determined to classified as be “Class 2L.”

In the present specification, a refrigerant having an “RCL of x % or more” means that the refrigerant has a refrigerant concentration limit (RCL), calculated in accordance with the US ANSI/ASHRAE Standard 34-2013, of x % or more. RCL refers to a concentration limit in the air in consideration of safety factors. RCL is an index for reducing the risk of acute toxicity, suffocation, and flammability in a closed space where humans are present. RCL is determined in accordance with the ASHRAE Standard. More specifically, RCL is the lowest concentration among the acute toxicity exposure limit (ATEL), the oxygen deprivation limit (ODL), and the flammable concentration limit (FCL), which are respectively calculated in accordance with sections 7.1.1, 7.1.2, and 7.1.3 of the ASHRAE Standard.

In the present specification, temperature glide refers to an absolute value of the difference between the initial temperature and the end temperature in the phase change process of a composition containing the refrigerant of the present disclosure in the heat exchanger of a refrigerant system.

1. Refrigerant

1.1 Refrigerant Component

The refrigerant according to the present disclosure is a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene (R1234yf).

The refrigerant according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., a refrigerating capacity and a coefficient of performance that are equivalent to those of R410A, and a sufficiently low GWP.

The refrigerant according to the present disclosure is a composition comprising HFO-1132(E) and R1234yf, and optionally further comprising HFO-1123, and may further satisfy the following requirements. This refrigerant also has various properties desirable as an alternative refrigerant for R410A; i.e., it has a refrigerating capacity and a coefficient of performance that are equivalent to those of R410A, and a sufficiently low GWP.

Requirements

When the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AA′, A′B, BD, DC′, C′C, CO, and OA that connect the following 7 points:

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0),

point C (32.9, 67.1, 0.0), and

point O (100.0, 0.0, 0.0),

or on the above line segments (excluding the points on the line CO);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3,

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments BD, CO, and OA are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 92.5% or more relative to that of R410A.

When the mass % of HFO-1132(E), HFO-1123, and R1234yf, based on their sum in the refrigerant according to the present disclosure is respectively represented by x, y, and z, the refrigerant is preferably a refrigerant wherein coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within a figure surrounded by line segments GI, IA, AA′, A′B, BD, DC′, C′C, and CG that connect the following 8 points:

point G (72.0, 28.0, 0.0),

point I (72.0, 0.0, 28.0),

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point C (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segment CG);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments GI, IA, BD, and CG are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 92.5% or more relative to that of R410A; furthermore, the refrigerant has a WCF lower flammability according to the ASHRAE Standard (the WCF composition has a burning velocity of 10 cm/s or less).

When the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant according to the present disclosure is respectively represented by x, y, and z, the refrigerant is preferably a refrigerant wherein coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments JP, PN, NK, KA′, A′B, BD, DC′, C′C, and CJ that connect the following 9 points:

point J (47.1, 52.9, 0.0),

point P (55.8, 42.0, 2.2),

point N (68.6, 16.3, 15.1),

point K (61.3, 5.4, 33.3),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point C (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segment CJ);

the line segment PN is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment NK is represented by coordinates (x, 0.2421x 2 −29.955x+931.91, −0.2421x 2 +28.955x−831.91),

the line segment KA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments JP, BD, and CJ are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 92.5% or more relative to that of R410A; furthermore, the refrigerant exhibits a lower flammability (Class 2L) according to the ASHRAE Standard (the WCF composition and the WCFF composition have a burning velocity of 10 cm/s or less).

When the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant according to the present disclosure is respectively represented by x, y, and z, the refrigerant is preferably a refrigerant wherein coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments JP, PL, LM, MA′, A′B, BD, DC′, C′C, and CJ that connect the following 9 points:

point J (47.1, 52.9, 0.0),

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0), and

point (32.9, 67.1, 0.0),

or on the above line segments (excluding the points on the line segment CJ);

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.008 2 x2−0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments JP, LM, BD, and CJ are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 92.5% or more relative to that of R410A; furthermore, the refrigerant has an RCL of 40 g/m 3 or more.

When the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant according to the present disclosure is respectively represented by x, y, and z, the refrigerant is preferably a refrigerant wherein coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PL, LM, MA′, A′B, BF, FT, and TP that connect the following 7 points:

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point F (0.0, 61.8, 38.2), and

point T (35.8, 44.9, 19.3),

or on the above line segments (excluding the points on the line segment BF);

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment FT is represented by coordinates (x, 0.0078x 2 −0.7501x+61.8, −0.0078x 2 −0.2499x+38.2),

the line segment TP is represented by coordinates (x, 0.00672x 2 −0.7607x+63.525, −0.00672x 2 −0.2393x+36.475), and

the line segments LM and BF are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 95% or more relative to that of R410A; furthermore, the refrigerant has an RCL of 40 g/m 3 or more.

The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments PL, LQ, QR, and RP that connect the following 4 points:

point P (55.8, 42.0, 2.2),

point L (63.1, 31.9, 5.0),

point Q (62.8, 29.6, 7.6), and

point R (49.8, 42.3, 7.9),

or on the above line segments;

the line segment PL is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

the line segment RP is represented by coordinates (x, 0.00672x 2 −0.7607x+63.525, −0.00672x 2 −0.2393x+36.475), and

the line segments LQ and QR are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a COP of 95% or more relative to that of R410A, and an RCL of 40 g/m 3 or more; furthermore, the refrigerant has a condensation temperature glide of 1° C. or less.

The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments SM, MA′, A′B, BF, FT, and TS that connect the following 6 points:

point S (62.6, 28.3, 9.1),

point M (60.3, 6.2, 33.5),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point F (0.0, 61.8, 38.2), and

point T (35.8, 44.9, 19.3),

or on the above line segments,

the line segment MA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment FT is represented by coordinates (x, 0.0078x 2 −0.7501x+61.8, −0.0078x 2 −0.2499x+38.2),

the line segment TS is represented by coordinates (x, 0.0017x 2 −0.7869x+70.888, −0.0017x 2 −0.2131x+29.112), and

the line segments SM and BF are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, a COP of 95% or more relative to that of R410A, and an RCL of 40 g/m 3 or more; furthermore, the refrigerant has a discharge pressure of 105% or more relative to that of R410A.

The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments Od, dg, gh, and hO that connect the following 4 points:

point d (87.6, 0.0, 12.4),

point g (18.2, 55.1, 26.7),

point h (56.7, 43.3, 0.0), and

point o (100.0, 0.0, 0.0),

or on the line segments Od, dg, gh, and hO (excluding the points O and h);

the line segment dg is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, −0.0047y 2 +0.5177y+12.402),

the line segment gh is represented by coordinates (−0.0134z 2 −1.0825z+56.692, 0.0134z 2 +0.0825z+43.308, z), and

the line segments hO and Od are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A.

The refrigerant according to the present disclosure is preferably a refrigerant wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf, based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments lg, gh, hi, and il that connect the following 4 points:

point l (72.5, 10.2, 17.3),

point g (18.2, 55.1, 26.7),

point h (56.7, 43.3, 0.0), and

point i (72.5, 27.5, 0.0) or

on the line segments lg, gh, and il (excluding the points h and i);

the line segment lg is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, −0.0047y 2 +0.5177y+12.402),

the line gh is represented by coordinates (−0.0134z 2 −1.0825z+56.692, 0.0134z 2 +0.0825z+43.308, z), and

the line segments hi and il are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 92.5% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A; furthermore, the refrigerant has a lower flammability (Class 2L) according to the ASHRAE Standard.

The refrigerant according to the present disclosure is preferably a refrigerant wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments Od, de, ef, and fO that connect the following 4 points:

point d (87.6, 0.0, 12.4),

point e (31.1, 42.9, 26.0),

point f (65.5, 34.5, 0.0), and

point O (100.0, 0.0, 0.0),

or on the line segments Od, de, and ef (excluding the points O and f);

the line segment de is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, −0.0047y 2 +0.5177y+12.402),

the line segment ef is represented by coordinates (−0.0064z 2 −1.1565z+65.501, 0.0064z 2 +0.1565z+34.499, z), and

the line segments fO and Od are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 93.5% or more relative to that of R410A, and a COP ratio of 93.5% or more relative to that of R410A.

The refrigerant according to the present disclosure is preferably a refrigerant wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is respectively represented by x, y, and z,

coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments le, ef, fi, and il that connect the following 4 points:

point l (72.5, 10.2, 17.3),

point e (31.1, 42.9, 26.0),

point f (65.5, 34.5, 0.0), and

point i (72.5, 27.5, 0.0),

or on the line segments le, ef, and il (excluding the points f and i);

the line segment le is represented by coordinates (0.0047y 2 −1.5177y+87.598, y, −0.0047y 2 +0.5177y+12.402),

the line segment ef is represented by coordinates (−0.0134z 2 −1.0825z+56.692, 0.0134z 2 +0.0825z+43.308, z), and

the line segments fi and il are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 93.5% or more relative to that of R410A, and a COP ratio of 93.5% or more relative to that of R410A; furthermore, the refrigerant has a lower flammability (Class 2L) according to the ASHRAE Standard.

The refrigerant according to the present disclosure is preferably a refrigerant wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is respectively represented by x, y, and z,

coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments Oa, ab, bc, and cO that connect the following 4 points:

point a (93.4, 0.0, 6.6),

point b (55.6, 26.6, 17.8),

point c (77.6, 22.4, 0.0), and

point O (100.0, 0.0, 0.0),

or on the line segments Oa, ab, and bc (excluding the points O and c);

the line segment ab is represented by coordinates (0.0052y 2 −1.5588y+93.385, y, −0.0052y 2 +0.5588y+6.615),

the line segment be is represented by coordinates (−0.0032z 2 −1.1791z+77.593, 0.0032z 2 +0.1791z+22.407, z), and

the line segments cO and Oa are straight lines.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to that of R410A, and a COP ratio of 95% or more relative to that of R410A.

The refrigerant according to the present disclosure is preferably a refrigerant wherein

when the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is respectively represented by x, y, and z,

coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments kb, bj, and jk that connect the following 3 points:

point k (72.5, 14.1, 13.4),

point b (55.6, 26.6, 17.8), and

point j (72.5, 23.2, 4.3),

or on the line segments kb, bj, and jk;

the line segment kb is represented by coordinates (0.0052y 2 −1.5588y+93.385, y, and −0.0052y 2 +0.5588y+6.615),

the line segment bj is represented by coordinates (−0.0032z 2 −1.1791z+77.593, 0.0032z 2 +0.1791z+22.407, z), and

the line segment jk is a straight line.

When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to that of R410A, and a COP ratio of 95% or more relative to that of R410A; furthermore, the refrigerant has a lower flammability (Class 2L) according to the ASHRAE Standard.

The refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), HFO-1123, and R1234yf, as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure preferably comprises HFO-1132(E), HFO-1123, and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more, based on the entire refrigerant.

The refrigerant according to the present disclosure may comprise HFO-1132(E), HFO-1123, and R1234yf in a total amount of 99.5 mass % or more, 99.75 mass % or more, or 99.9 mass % or more, based on the entire refrigerant.

Additional refrigerants are not particularly limited and can be widely selected. The mixed refrigerant may contain one additional refrigerant, or two or more additional refrigerants.

1.2. Use

The refrigerant according to the present disclosure can be preferably used as a working fluid in a refrigerating machine.

The composition according to the present disclosure is suitable for use as an alternative refrigerant for R410A.

2. Refrigerant Composition

The refrigerant composition according to the present disclosure comprises at least the refrigerant according to the present disclosure, and can be used for the same use as the refrigerant according to the present disclosure. Moreover, the refrigerant composition according to the present disclosure can be further mixed with at least a refrigeration oil to thereby obtain a working fluid for a refrigerating machine.

The refrigerant composition according to the present disclosure further comprises at least one other component in addition to the refrigerant according to the present disclosure. The refrigerant composition according to the present disclosure may comprise at least one of the following other components, if necessary. As described above, when the refrigerant composition according to the present disclosure is used as a working fluid in a refrigerating machine, it is generally used as a mixture with at least a refrigeration oil. Therefore, it is preferable that the refrigerant composition according to the present disclosure does not substantially comprise a refrigeration oil.

Specifically, in the refrigerant composition according to the present disclosure, the content of the refrigeration oil based on the entire refrigerant composition is preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %.

2.1. Water

The refrigerant composition according to the present disclosure may contain a small amount of water. The water content of the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant. A small amount of water contained in the refrigerant composition stabilizes double bonds in the molecules of unsaturated fluorocarbon compounds that can be present in the refrigerant, and makes it less likely that the unsaturated fluorocarbon compounds will be oxidized, thus increasing the stability of the refrigerant composition.

2.2. Tracer

A tracer is added to the refrigerant composition according to the present disclosure at a detectable concentration such that when the refrigerant composition has been diluted, contaminated, or undergone other changes, the tracer can trace the changes.

The refrigerant composition according to the present disclosure may comprise a single tracer, or two or more tracers.

The tracer is not limited, and can be suitably selected from commonly used tracers.

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 (N 2 O). The tracer is particularly preferably a hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon, a hydrochlorocarbon, a fluorocarbon, or a fluoroether.

The following compounds are preferable as the tracer.

FC-14 (tetrafluoromethane, CF 4 ) HCC-40 (chloromethane, CH 3 Cl) HFC-23 (trifluoromethane, CHF 3 ) HFC-41 (fluoromethane, CH 3 Cl) HFC-125 (pentafluoroethane, CF 3 CHF 2 ) HFC-134a (1,1,1,2-tetrafluoroethane, CF 3 CH 2 F) HFC-134 (1,1,2,2-tetrafluoroethane, CHF 2 CHF 2 ) HFC-143a (1,1,1-trifluoroethane, CF 3 CH 3 ) HFC-143 (1,1,2-trifluoroethane, CHF 2 CH 2 F) HFC-152a (1,1-difluoroethane, CHF 2 CH 3 ) HFC-152 (1,2-difluoroethane, CH 2 FCH 2 F) HFC-161 (fluoroethane, CH 3 CH 2 F) HFC-245fa (1,1,1,3,3-pentafluoropropane, CF 3 CH 2 CHF 2 ) HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF 3 CH 2 CF 3 ) HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF 3 CHFCHF 2 ) HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF 3 CHFCF 3 ) HCFC-22 (chlorodifluoromethane, CHClF 2 ) HCFC-31 (chlorofluoromethane, CH 2 ClF) CFC-1113 (chlorotrifluoroethylene, CF 2 ═CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF 3 OCHF 2 ) HFE-134a (trifluoromethyl-fluoromethyl ether, CF 3 OCH 2 F) HFE-143a (trifluoromethyl-methyl ether, CF 3 OCH 3 ) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF 3 OCHFCF 3 ) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF 3 OCH 2 CF 3 )

The refrigerant composition according to the present disclosure may contain one or more tracers at a total concentration of about 10 parts per million by weight (ppm) to about 1000 ppm based on the entire refrigerant composition. The refrigerant composition according to the present disclosure may preferably contain one or more tracers at a total concentration of about 30 ppm to about 500 ppm, and more preferably about 50 ppm to about 300 ppm, based on the entire refrigerant composition.

2.3. Ultraviolet Fluorescent Dye

The refrigerant composition according to the present disclosure may comprise a single ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.

The ultraviolet fluorescent dye is not limited, and can be suitably selected from commonly used ultraviolet fluorescent dyes.

Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. The ultraviolet fluorescent dye is particularly preferably either naphthalimide or coumarin, or both.

2.4. Stabilizer

The refrigerant composition according to the present disclosure may comprise a single stabilizer, or two or more stabilizers.

The stabilizer is not limited, and can be suitably selected from commonly used stabilizers.

Examples of stabilizers include nitro compounds, ethers, and amines.

Examples of nitro compounds include aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitro benzene and nitro styrene.

Examples of ethers include 1,4-dioxane.

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

Examples of stabilizers also include butylhydroxyxylene and benzotriazole.

The content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.

2.5. Polymerization Inhibitor

The refrigerant composition according to the present disclosure may comprise a single polymerization inhibitor, or two or more polymerization inhibitors.

The polymerization inhibitor is not limited, and can be suitably selected from commonly used polymerization inhibitors.

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

The content of the polymerization inhibitor is not limited. Generally, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.

3. Refrigeration Oil-Containing Working Fluid

The refrigeration oil-containing working fluid according to the present disclosure comprises at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, for use as a working fluid in a refrigerating machine. Specifically, the refrigeration oil-containing working fluid according to the present disclosure is obtained by mixing a refrigeration oil used in a compressor of a refrigerating machine with the refrigerant or the refrigerant composition. The refrigeration oil-containing working fluid generally comprises 10 to 50 mass % of refrigeration oil.

3.1. Refrigeration Oil

The composition according to the present disclosure may comprise a single refrigeration oil, or two or more refrigeration oils.

The refrigeration oil is not limited, and can be suitably selected from commonly used refrigeration oils. In this case, refrigeration oils that are superior in the action of increasing the miscibility with the mixture and the stability of the mixture, for example, are suitably selected as necessary.

The base oil of the refrigeration oil is preferably, for example, at least one member selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).

The refrigeration oil may further contain additives in addition to the base oil. The additive may be at least one member selected from the group consisting of antioxidants, extreme-pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oil agents, and antifoaming agents.

A refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40° C. is preferable from the standpoint of lubrication.

The refrigeration oil-containing working fluid according to the present disclosure may further optionally contain at least one additive. Examples of additives include compatibilizing agents described below.

3.2. Compatibilizing Agent

The refrigeration oil-containing working fluid according to the present disclosure may comprise a single compatibilizing agent, or two or more compatibilizing agents.

The compatibilizing agent is not limited, and can be suitably selected from commonly used compatibilizing agents.

Examples of compatibilizing agents include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. The compatibilizing agent is particularly preferably a polyoxyalkylene glycol ether.

4. Method for Operating Refrigerating Machine

The method for operating a refrigerating machine according to the present disclosure is a method for operating a refrigerating machine using the refrigerant according to the present disclosure.

Specifically, the method for operating a refrigerating machine according to the present disclosure comprises the step of circulating the refrigerant according to the present disclosure in a refrigerating machine.

The embodiments are described above; however, it will be understood that various changes in forms and details can be made without departing from the spirit and scope of the claims.

The present disclosure is described in more detail below with reference to Examples. However, the present disclosure is not limited to the Examples.

The GWP of R1234yf and a composition consisting of a mixed refrigerant R410A (R32=50%/R125=50%) was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth report. The GWP of HFO-1132(E), which was not stated therein, was assumed to be 1 from HFO-1132a (GWP=1 or less) and HFO-1123 (GWP=0.3, described in PTL 1). The refrigerating capacity of R410A and compositions each comprising a mixture of HFO-1132(E), HFO-1123, and R1234yf was determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.

Further, the RCL of the mixture was calculated with the LFL of HFO-1132(E) being 4.7 vol. %, the LFL of HFO-1123 being 10 vol. %, and the LFL of R1234yf being 6.2 vol. %, in accordance with the ASHRAE Standard 34-2013.

Evaporating temperature: 5° C.

Condensation temperature: 45° C.

Degree of superheating: 5 K

Degree of subcooling: 5 K

Compressor efficiency: 70%

Tables 1 to 34 show these values together with the GWP of each mixed refrigerant.

These results indicate that under the condition that the mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AA′, A′B, BD, DC′, C′C, CO, and OA that connect the following 7 points:

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point D (0.0, 80.4, 19.6),

point C′ (19.5, 70.5, 10.0),

point C (32.9, 67.1, 0.0), and

point O (100.0, 0.0, 0.0),

or on the above line segments (excluding the points on the line segment CO);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3,

the line segment DC′ is represented by coordinates (x, 0.0082x 2 −0.6671x+80.4, −0.0082x 2 −0.3329x+19.6),

the line segment C′C is represented by coordinates (x, 0.0067x 2 −0.6034x+79.729, −0.0067x 2 −0.3966x+20.271), and

the line segments BD, CO, and OA are straight lines,

the refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 92.5% or more relative to that of R410A.

The point on the line segment AA′ was determined by obtaining an approximate curve connecting point A, Example 1, and point A′ by the least square method.

The point on the line segment A′B was determined by obtaining an approximate curve connecting point A′, Example 3, and point B by the least square method.

The point on the line segment DC′ was determined by obtaining an approximate curve connecting point D, Example 6, and point C′ by the least square method.

The point on the line segment C′C was determined by obtaining an approximate curve connecting point C′, Example 4, and point C by the least square method.

Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure surrounded by line segments AA′, A′B, BF, FT, TE, EO, and OA that connect the following 7 points:

point A (68.6, 0.0, 31.4),

point A′ (30.6, 30.0, 39.4),

point B (0.0, 58.7, 41.3),

point F (0.0, 61.8, 38.2),

point T (35.8, 44.9, 19.3),

point E (58.0, 42.0, 0.0) and

point O (100.0, 0.0, 0.0),

or on the above line segments (excluding the points on the line EO);

the line segment AA′ is represented by coordinates (x, 0.0016x 2 −0.9473x+57.497, −0.0016x 2 −0.0527x+42.503),

the line segment A′B is represented by coordinates (x, 0.0029x 2 −1.0268x+58.7, −0.0029x 2 +0.0268x+41.3),

the line segment FT is represented by coordinates (x, 0.0078x 2 −0.7501x+61.8, −0.0078x 2 −0.2499x+38.2), and

the line segment TE is represented by coordinates (x, 0.0098x 2 −0.0398x+42.0, −0.0098x 2 −0.9602x+58.0), and

the line segments BF, FO, and OA are straight lines,

the refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP of 95% or more relative to that of R410A.

The point on the line segment FT was determined by obtaining an approximate curve connecting three points, i.e., points T, E′, and F, by the least square method.

The point on the line segment TE was determined by obtaining an approximate curve connecting three points, i.e., points E, R, and T, by the least square method.

The results in Tables 1 to 34 clearly indicate that in a ternary composition diagram of the mixed refrigerant of HFO-1132(E), HFO-1123, and R1234yf in which the sum of these components is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, the point (0.0, 100.0, 0.0) is on the left side, and the point (0.0, 0.0, 100.0) is on the right side, when coordinates (x,y,z) are on or below the line segment LM connecting point L (63.1, 31.9, 5.0) and point M (60.3, 6.2, 33.5), the refrigerant has an RCL of 40 g/m 3 or more.

The results in Tables 1 to 34 clearly indicate that in a ternary composition diagram of the mixed refrigerant of HFO-1132(E), HFO-1123 and R1234yf in which their sum is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, the point (0.0, 100.0, 0.0) is on the left side, and the point (0.0, 0.0, 100.0) is on the right side, when coordinates (x,y,z) are on the line segment QR connecting point Q (62.8, 29.6, 7.6) and point R (49.8, 42.3, 7.9) or on the left side of the line segment, the refrigerant has a temperature glide of 1° C. or less.

The results in Tables 1 to 34 clearly indicate that in a ternary composition diagram of the mixed refrigerant of HFO-1132(E), HFO-1123, and R1234yf in which their sum is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, the point (0.0, 100.0, 0.0) is on the left side, and the point (0.0, 0.0, 100.0) is on the right side, when coordinates (x,y,z) are on the line segment ST connecting point S (62.6, 28.3, 9.1) and point T (35.8, 44.9, 19.3) or on the right side of the line segment, the refrigerant has a discharge pressure of 105% or less relative to that of 410A.

In these compositions, R1234yf contributes to reducing flammability, and suppressing deterioration of polymerization etc. Therefore, the composition preferably contains R1234yf.

Further, the burning velocity of these mixed refrigerants whose mixed formulations were adjusted to WCF concentrations was measured according to the ANSI/ASHRAE Standard 34-2013. Compositions having a burning velocity of 10 cm/s or less were determined to be classified as “Class 2L (lower flammability).”

A burning velocity test was performed using the apparatus shown in FIG. 1 in the following manner. First, the mixed refrigerants used had a purity of 99.5% or more, and were degassed by repeating a cycle of freezing, pumping, and thawing until no traces of air were observed on the vacuum gauge. The burning velocity was measured by the closed method. The initial temperature was ambient temperature. Ignition was performed by generating an electric spark between the electrodes in the center of a sample cell. The duration of the discharge was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The spread of the flame was visualized using schlieren photographs. A cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two light transmission acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of the flame were recorded by a high-speed digital video camera at a frame rate of 600 fps and stored on a PC.

Each WCFF concentration was obtained by using the WCF concentration as the initial concentration and performing a leak simulation using NIST Standard Reference Database REFLEAK Version 4.0.

Tables 35 and 36 show the results.

The results in Table 35 clearly indicate that when a mixed refrigerant of HFO-1132(E), HFO-1123, and R1234yf contains HFO-1132(E) in a proportion of 72.0 mass % or less based on their sum, the refrigerant can be determined to have a WCF lower flammability.

The results in Tables 36 clearly indicate that in a ternary composition diagram of a mixed refrigerant of HFO-1132(E), HFO-1123, and R1234yf in which their sum is 100 mass %, and a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base,

when coordinates (x,y,z) are on or below the line segments JP, PN, and NK connecting the following 6 points:

point J (47.1, 52.9, 0.0),

point P (55.8, 42.0, 2.2),

point L (63.1,31.9,5.0)

point N (68.6, 16.3, 15.1)

point N′ (65.0,7.7,27.3) and

point K (61.3, 5.4, 33.3),

the refrigerant can be determined to have a WCF lower flammability, and a WCFF lower flammability.

In the diagram, the line segment PN is represented by coordinates (x, −0.1135x 2 +12.112x−280.43, 0.1135x 2 −13.112x+380.43),

and the line segment NK is represented by coordinates (x, 0.2421x 2 −29.955x+931.91, −0.2421x 2 +28.955x−831.91).

The point on the line segment PN was determined by obtaining an approximate curve connecting three points, i.e., points P, L, and N, by the least square method.

The point on the line segment NK was determined by obtaining an approximate curve connecting three points, i.e., points N, N′, and K, by the least square method.

Description of Reference Numerals

1 : Sample cell

2 : High-speed camera

3 : Xenon lamp

4 : Collimating lens

5 : Collimating lens

6 : Ring filter