METHOD FOR COEXISTING 1,2-DIFLUOROETHYLENE (HFO-1132) AND OXYGEN IN GAS PHASE, AND STORAGE CONTAINER AND REFRIGERATOR CONTAINING HFO-1132 AND OXYGEN

Information

  • Patent Application
  • 20220112417
  • Publication Number
    20220112417
  • Date Filed
    December 17, 2021
    2 years ago
  • Date Published
    April 14, 2022
    2 years ago
Abstract
An object is to suppress the polymerization reaction or self-decomposition reaction of 1,2-difluoroethylene. Provided as a means for achieving the object is a method for allowing 1,2-difluoroethylene (HFO-1132) and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.
Description
TECHNICAL FIELD

The present disclosure relates to a method for allowing 1,2-difluoroethylene (HFO-1132) and oxygen to coexist in a gas phase, and a storage container and refrigerating machine that comprise HFO-1132 and oxygen.


BACKGROUND ART

Various mixed refrigerants containing HFO-1132 have been proposed as low-GWP mixed refrigerants that can replace R410A (Patent Literature 1).


CITATION LIST
Patent Literature



  • PTL 1: WO2015/141678



SUMMARY

A method for allowing a refrigerant comprising 1,2-difluoroethylene (HFO-1132) and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


Advantageous Effects

The present disclosure improves the stability of HFO-1132 in a refrigerant containing HFO-1132 during storage and during operation of a refrigerating machine comprising the refrigerant.





BRIEF DESCRIPTION OF DRAWINGS


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



FIG. 2 is a diagram showing points A to M and O, 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 %.



FIG. 3 is a diagram showing points A to C, B′, and O, 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 %.



FIG. 4 is a diagram showing points A to C, B′, and O, 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 95 mass % (R32 is present in an amount of 5 mass %).



FIG. 5 is a diagram showing points A to C, B′, and O, 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 90 mass % (R32 is present in an amount of 10 mass %).



FIG. 6 is a diagram showing points A to C, B′, and O, 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 85.7 mass % (R32 is present in an amount of 14.3 mass %).



FIG. 7 is a diagram showing points A to C, B′, and O, 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 83.5 mass % (R32 is present in an amount of 16.5 mass %).



FIG. 8 is a diagram showing points A to C, B′, and O, 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 80.8 mass % (R32 is present in an amount of 19.2 mass %).



FIG. 9 is a diagram showing points A to C, B′, and O, 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 78.2 mass % (R32 is present in an amount of 21.8 mass %).



FIG. 10 is a diagram showing points A to K and O to R, and line segments that connect these points in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass %.



FIG. 11 is a diagram showing points A to D, A′ to D′, and O, and line segments that connect these points in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R32 is 100 mass %.



FIG. 12 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 100 mass %.



FIG. 13 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 99.4 mass % (CO2 is present in an amount of 0.6 mass %).



FIG. 14 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 98.8 mass % (CO2 is present in an amount of 1.2 mass %).



FIG. 15 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 98.7 mass % (CO2 is present in an amount of 1.3 mass %).



FIG. 16 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 97.5 mass % (CO2 is present in an amount of 2.5 mass %).



FIG. 17 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 96 mass % (CO2 is present in an amount of 4 mass %).



FIG. 18 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 94.5 mass % (CO2 is present in an amount of 5.5 mass %).



FIG. 19 is a diagram showing points and line segments that define the refrigerant according to the present disclosure in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is 93 mass % (CO2 is present in an amount of 7 mass %).



FIG. 20 is a schematic view of an experimental apparatus for examining flammability (flammable or non-flammable).





DESCRIPTION OF EMBODIMENTS

The present inventors conducted intensive studies to solve the above problem, and consequently found that the problem can be solved by a method for allowing a refrigerant comprising HFO-1132 and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


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, when only a compound name (e.g., “HFO-1132”) is described for a compound that has isomers, without specifying the isomers, the sum of the isomers of the compound contained in the refrigerant used in the present disclosure is intended, unless there are special circumstances. For example, when the refrigerant used in the present disclosure contains HFO-1132(E) alone, “HFO-1132” refers to HFO-1132(E), and when the refrigerant used in the present disclosure contains both HFO-1132(E) and HFO-1132(Z), “HFO-1132” refers to the sum of HFO-1132(E) and HFO-1132(Z).


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 terms 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 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.


1. Refrigerant Comprising HFO-1132

The refrigerant used in the present disclosure may be a refrigerant comprising HFO-1132. The refrigerant used in the present disclosure may be a refrigerant consisting of HFO-1132.


HFO-1132 may be trans-1,2-difluoroethylene (HFO-1132(E)) or cis-1,2-difluoroethylene (HFO-1132(Z)), or may be a mixture thereof.


The refrigerant used in the present disclosure may be a mixed refrigerant comprising HFO-1132 and further comprising an additional refrigerant.


Examples of additional refrigerants include trifluoroethylene (HFO-1123), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), 1,3,3,3-tetrafluoro-1-propene (R1234ze), CO2, and the like. R1234ze may be trans-1,3,3,3-tetrafluoro-1-propene (R1234ze(E)), cis-1,3,3,3-tetrafluoro-1-propene (R1234ze(Z)), or a mixture thereof.


The refrigerant used in the present disclosure may further comprise other additional refrigerants in addition to the above specific additional refrigerants. The refrigerant according to the present disclosure may comprise HFO-1132 and the above specific additional refrigerants 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. The refrigerant according to the present disclosure may comprise HFO-1132 in an amount of 99.5 mass % or more, 99.75 mass % or more, or 99.9 mass % or more, based on the entire refrigerant.


Examples of the mixed refrigerant include those containing at least one member selected from the group consisting of the above additional refrigerants. Examples of the mixed refrigerant include a mixed refrigerant of HFO-1132 and HFO-1123, a mixed refrigerant of HFO-1132, HFO-1123, and R32, a mixed refrigerant of HFO-1132, HFO-1123, and R1234yf, a mixed refrigerant of HFO-1132, R32, and R1234yf, a mixed refrigerant of HFO-1132, HFO-1123, R32, and R1234yf, a mixed refrigerant of HFO-1132, HFO-1123, and R1234ze, a mixed refrigerant of HFO-1132, R32, and R1234ze, a mixed refrigerant of HFO-1132, HFO-1123, R32, and R1234ze, a mixed refrigerant of HFO-1132, HFO-1123, R1234yf, and R1234ze, a mixed refrigerant of HFO-1132, R32, R1234yf, and R1234ze, a mixed refrigerant of HFO-1132, HFO-1123, R32, R1234yf, and R1234ze, a mixed refrigerant of HFO-1132, R32, R1234yf, and CO2, a mixed refrigerant of HFO-1132, R32, R1234ze, and CO2, a mixed refrigerant of HFO-1132, R32, R1234yf, R1234ze, and CO2, a mixed refrigerant of HFO-1132 and R1234yf, and the like. More specific examples include Refrigerants A to E and Refrigerants 1 to 5 described below.


According to the present disclosure, the stability of HFO-1132 can be improved by setting the concentration of oxygen coexisting with HFO-1132 in the gas phase to a specific concentration or lower. It will be understood that in order to obtain this effect, it is important to set the oxygen concentration of the gas phase containing HFO-1132 to a specific concentration or less. Therefore, it will be understood that the same effect would be obtained regardless of the type of additional refrigerant contained in the refrigerant.


2. Method for Allowing Refrigerant Comprising HFO-1132 and Oxygen to Coexist in Gas Phase

The present disclosure relates to a method for allowing a refrigerant comprising HFO-1132 and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


According to the above method, the stability of HFO-1132 can be improved by setting the concentration of oxygen coexisting with HFO-1132 in the gas phase to a specific concentration or lower. Improvement of the stability of HFO-1132 means that the polymerization reaction and/or self-decomposition reaction is suppressed.


In terms of easily obtaining this effect, the temperature of the gas phase is preferably less than 80° C., more preferably less than 60° C., and even more preferably less than 40° C.


In the present disclosure, a refrigerant comprising HFO-1132 and oxygen can be allowed to coexist in the gas phase in a closed container. In this case, the refrigerant comprising HFO-1132 can be stored in a closed container while improving the stability of HFO-1132. When the refrigerant comprising HFO-1132 is stored in a closed container in this way, the polymerization reaction that may occur during storage can be suppressed. In terms of suppressing the polymerization reaction, the concentration of oxygen in the gas phase at a temperature of 25° C. is preferably 1000 volume ppm or less, more preferably 400 volume ppm or less, and even more preferably 200 volume ppm or less.


When the refrigerant comprising HFO-1132 is stored in a closed container in this way, the gas phase preferably coexists with a liquid phase containing the refrigerant; that is, the refrigerant is preferably present in a gas-liquid state. In this case, the refrigerant comprising HFO-1132 has a saturation vapor pressure in the gas phase.


When the refrigerant comprising HFO-1132 is stored in a closed container, the storage period can be, for example, 1 day or more. The storage period is preferably 10 days or more, more preferably 100 days or more, and even more preferably 1000 days or more. The storage temperature can be set so that the temperature of the gas phase is −50° C. to 200° C., for example. As the storage temperature, the temperature of the gas phase is preferably −20° C. to 180° C. etc., more preferably 0° C. to 180° C. etc., and even more preferably 15° C. to 180° C. etc.


As the closed container, a wide range of closed containers generally used for storing refrigerants can be used. Such a closed container is generally a closed container capable of enclosing a gas-liquid mixture under internal pressure. The closed container may be a storage tank used after being fixed, or a filling cylinder used for transportation. Filling cylinders include secondary filling cylinders. The material of the part of the closed container that comes into contact with the refrigerant is not limited, and examples include carbon steels, manganese steels, stainless steels, low alloy steels, aluminum alloys, and the like. Examples of low alloy steels include chromium molybdenum steels.


In the present disclosure, the refrigerant comprising HFO-1132 and oxygen may be allowed to coexist in the gas phase in a refrigerating machine. In this case, the refrigerating machine can be operated using the refrigerant as a working fluid. When the refrigerating machine is operated in this way using the refrigerant comprising HFO-1132 as a working fluid, the self-decomposition reaction that may occur during operation can be suppressed. The self-decomposition reaction is facilitated by the decomposition of the refrigerant by a dehydrofluorination reaction in the presence of oxygen at a high temperature in the refrigerating machine, resulting in the formation of radicals. In terms of suppressing the self-decomposition reaction, the concentration of oxygen in the gas phase at a temperature of 25° C. is preferably 1000 volume ppm or less, more preferably 400 volume ppm or less, and even more preferably 200 volume ppm or less.


When the refrigerating machine is operated in this way using the refrigerant comprising HFO-1132 as a working fluid, the gas phase preferably coexists with a liquid phase containing the refrigerant in at least part of the refrigerating machine; that is, the refrigerant is preferably present in a gas-liquid state. In this case, the refrigerant comprising HFO-1132 has a saturation vapor pressure in the gas phase.


As the refrigerating machine, general refrigerating machines can be widely used.


3. Storage Container

The storage container according to the present disclosure is a storage container of a refrigerant comprising HFO-1132, in which the refrigerant and oxygen coexist in the gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


As described above, the stability of HFO-1132 is improved in the storage container.


4. Refrigerants A to E

Refrigerants A to E used in the present disclosure are described in detail below.


The disclosures of Refrigerant A, Refrigerant B, Refrigerant C, Refrigerant D, and Refrigerant E are independent from each other. Thus, the alphabetical letters used for points and line segments, as well as the numbers used for Examples and Comparative Examples, are all independent in each of Refrigerant A, Refrigerant B, Refrigerant C, Refrigerant D, and Refrigerant E. For example, Example 1 of Refrigerant A and Example 1 of Refrigerant B each represent an example according to a different embodiment.


4.1. Refrigerant A

Refrigerant A 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).


Refrigerant A 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.


Refrigerant A 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 A also 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.


Requirements

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, 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment GH is represented by coordinates (−0.0134z2−1.0825z+56.692, 0.0134z2+0.0825z+43.308, z), and


the lines HO and OD are straight lines.


When the requirements above are satisfied, Refrigerant A 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.


Refrigerant A 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment GH is represented by coordinates (−0.0134z2−1.0825z+56.692, 0.0134z2+0.0825z+43.308, z), and


the line segments HI and IL are straight lines.


When the requirements above are satisfied, Refrigerant A 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 slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant A 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment EF is represented by coordinates (−0.0064z2−1.1565z+65.501, 0.0064z2+0.1565z+34.499, z), and


the line segments FO and OD are straight lines.


When the requirements above are satisfied, Refrigerant A 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.


Refrigerant A 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment EF is represented by coordinates (−0.0134z2−1.0825z+56.692, 0.0134z2+0.0825z+43.308, z), and


the line segments FI and IL are straight lines.


When the requirements above are satisfied, Refrigerant A 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 slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant A 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 (0.0052y2−1.5588y+93.385, y, −0.0052y2+0.5588y+6.615),


the line segment BC is represented by coordinates (−0.0032z2−1.1791z+77.593, 0.0032z2+0.1791z+22.407, z), and


the line segments CO and OA are straight lines.


When the requirements above are satisfied, Refrigerant A 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.


Refrigerant A 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 (0.0052y2−1.5588y+93.385, y, and −0.0052y2+0.5588y+6.615),


the line segment BJ is represented by coordinates (−0.0032z2−1.1791z+77.593, 0.0032z2+0.1791z+22.407, z), and


the line segment JK is a straight line.


When the requirements above are satisfied, Refrigerant A 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 slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant A according to the present disclosure may further comprise difluoromethane (R32) in addition to HFO-1132(E), HFO-1123, and R1234yf as long as the above properties and effects are not impaired. The content of R32 based on the entire Refrigerant A according to the present disclosure is not particularly limited and can be selected from a wide range. For example, when the R32 content of Refrigerant A according to the present disclosure is 21.8 mass %, the mixed refrigerant has a GWP of 150. Therefore, the R32 content can be 21.8 mass % or less. The R32 content of Refrigerant A according to the present disclosure may be, for example, 5 mass % or more, based on the entire refrigerant.


When Refrigerant A according to the present disclosure further contains R32 in addition to HFO-1132(E), HFO-1123, and R1234yf, the refrigerant may be a refrigerant wherein


when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32 based on their sum is respectively represented by x, y, z, and a,


if 0<a≤10.0, coordinates (x,y,z) in a ternary composition diagram (FIGS. 3 to 9) in which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass % are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.02a2−2.46a+93.4, 0, −0.02a2+2.46a+6.6),


point B′ (−0.008a2−1.38a+56, 0.018a2−0.53a+26.3, −0.01a2+1.91a+17.7),


point C (−0.016a2+1.02a+77.6, 0.016a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C);


if 10.0<a≤16.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0244a2−2.5695a+94.056, 0, −0.0244a2+2.5695a+5.944),


point B′ (0.1161a2−1.9959a+59.749, 0.014a2−0.3399a+24.8, −0.1301a2+2.3358a+15.451),


point C (−0.0161a2+1.02a+77.6, 0.0161a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C); or


if 16.5<a≤21.8, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0161a2−2.3535a+92.742, 0, −0.0161a2+2.3535a+7.258),


point B′ (−0.0435a2−0.0435a+50.406, −0.0304a2+1.8991a−0.0661, 0.0739a2−1.8556a+49.6601),


point C (−0.0161a2+0.9959a+77.851, 0.0161a2−0.9959a+22.149, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C).


Note that when point B in the ternary composition diagram is defined as a point where a refrigerating capacity ratio of 95% relative to that of R410A and a COP ratio of 95% relative to that of R410A are both achieved, point B′ is the intersection of straight line AB and an approximate line formed by connecting the points where the COP ratio relative to that of R410A is 95%. When the requirements above are satisfied, Refrigerant A 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.


Refrigerant A according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), HFO-1123, R1234yf, and R32 as long as the above properties and effects are not impaired. In this respect, Refrigerant A according to the present disclosure preferably comprises HFO-1132(E), HFO-1123, R1234yf, and R32 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 A.


Refrigerant A 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 A.


Refrigerant A according to the present disclosure may comprise HFO-1132(E), HFO-1123, R1234yf, and R32 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 A.


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.


Refrigerant A according to the present disclosure is suitable for use as an alternative refrigerant for R410A.


Examples of Refrigerant A

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


Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1123, and R1234yf at mass % based on their sum shown in Tables 1 to 5.


The COP ratio and the refrigerating capacity ratio of the mixed refrigerants relative to those of R410 were determined. The calculation conditions were as follows.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Degree of superheating: 1 K


Degree of subcooling: 5 K


Ecomp (compressive modulus): 0.7 kWh


Tables 1 to 5 show these values together with the GWP of each mixed refrigerant.

















TABLE 1







Comp.
Example 1




Example 6


Item
Unit
Ex. 1
A
Example 2
Example 3
Example 4
Example 5
B























HFO-1132(E)
mass %
R410A
93.4
85.7
78.3
71.2
64.3
55.6


HFO-1123
mass %

0.0
5.0
10.0
15.0
20.0
26.6


R1234yf
mass %

6.6
9.3
11.7
13.8
15.7
17.8


GWP

2088
1
1
1
1
1
2


COP ratio
% (relative
100
98.0
97.5
96.9
96.3
95.8
95.0



to R410A)


Refrigerating
% (relative
100
95.0
95.0
95.0
95.0
95.0
95.0


capacity ratio
to R410A)





















TABLE 2







Comp.







Ex. 2
Example
Example
Example


Item
Unit
C
7
8
9




















HFO-1132(E)
mass %
77.6
71.6
65.5
59.2


HFO-1123
mass %
22.4
23.4
24.5
25.8


R1234yf
mass %
0.0
5.0
10.0
15.0


GWP

1
1
1
1


COP ratio
%
95.0
95.0
95.0
95.0



(relative



to R410A)


Refrigerating
%
102.5
100.5
98.4
96.3


capacity ratio
(relative



to R410A)
























TABLE 3







Example 10





Example 16


Item
Unit
D
Example 11
Example 12
Example 13
Example 14
Example 15
G























HFO-1132(E)
mass %
87.6
72.9
59.1
46.3
34.4
23.5
18.2


HFO-1123
mass %
0.0
10.0
20.0
30.0
40.0
50.0
55.1


R1234yf
mass %
12.4
17.1
20.9
23.7
25.6
26.5
26.7


GWP

1
2
2
2
2
2
2


COP ratio
% (relative
98.2
97.1
95.9
94.8
93.8
92.9
92.5



to R410A)


Refrigerating
% (relative
92.5
92.5
92.5
92.5
92.5
92.5
92.5


capacity ratio
to R410A)
























TABLE 4







Comp.


Comp.







Ex. 3


Ex. 4


Example 21


Item
Unit
H
Example 17
Example 18
F
Example 19
Example 20
E























HFO-1132(E)
mass %
56.7
44.5
29.7
65.5
53.3
39.3
31.1


HFO-1123
mass %
43.3
45.5
50.3
34.5
36.7
40.2
42.9


R1234yf
mass %
0.0
10.0
20.0
0.0
10.0
20.0
26.0


GWP

1
1
2
1
1
2
2


COP ratio
% (relative
92.5
92.5
92.5
93.5
93.5
93.5
93.5



to R410A)


Refrigerating
% (relative
105.8
101.2
96.2
104.5
100.2
95.5
92.5


capacity ratio
to R410A)






















TABLE 5







Comp.



Comp.




Ex. 5
Example 22
Example 23
Example 24
Ex. 6


Item
Unit
I
J
K
L
M





















HFO-1132(E)
mass %
72.5
72.5
72.5
72.5
72.5


HFO-1123
mass %
27.5
23.2
14.1
10.2
0.0


R1234yf
mass %
0.0
4.3
13.4
17.3
27.5


GWP

1
1
1
2
2


COP ratio
% (relative
94.4
95.0
96.4
97.1
98.8



to R410A)


Refrigerating
% (relative
103.5.
100.8
95.0
92.5
85.7


capacity ratio
to R410A)









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 (FIG. 2) 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 refrigerant 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.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 2) 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 refrigerant 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.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 2) 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 refrigerant 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.


R1234yf contributes to reduction of flammability and deterioration of polymerization etc. in these compositions. Therefore, the composition according to the present disclosure preferably contains R1234yf.


Further, the burning velocity of these mixed refrigerants was measured according to ANSI/ASHRAE Standard 34-2013. Compositions that showed a burning velocity of 10 cm/s or less were determined to be Class 2L (slight flammability). These results clearly indicate that when the content of HFO-1132(E) in a mixed refrigerant of HFO-1132(E), HFO-1123, and R1234yf is 72.5 mass % or less based on their sum, the refrigerant can be determined to be Class 2L (slight 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. Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1123, R1234yf, and R32 in amounts shown in Tables 6 to 12, in terms of mass %, based on their sum.


The COP ratio and the refrigerating capacity ratio of these mixed refrigerants relative to those of R410A were determined. The calculation conditions were the same as described above. Tables 6 to 12 show these values together with the GWP of each mixed refrigerant.



















TABLE 6








Comp.



Comp.


Comp.




Comp.
Ex. 7
Comp.
Comp.
Example 25
Ex. 10


Ex. 11


Item
Unit
Ex. 1
A
Ex. 8
Ex. 9
B′
B
Example 26
Example 27
C

























HFO-1132(E)
mass %
R410A
93.4
78.3
64.3
56.0
55.6
60.0
70.0
77.6


HFO-1123
mass %

0.0
10.0
20.0
26.3
26.6
25.6
23.7
22.4


R1234yf
mass %

6.6
11.7
15.7
17.7
17.8
14.4
6.3
0.0


R32
mass %

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


GWP

2088
1
1.4
1.5
1.5
1.5
1.4
1.2
1.0


COP ratio
% (relative
100
98.0
96.9
95.8
95.0
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
100
95.0
95.0
95.0
95.0
95.0
96.5
100.0
102.5


capacity ratio
to R410A)

























TABLE 7







Comp.



Comp.


Comp.




Ex. 12
Comp.
Comp.
Example 28
Ex. 15


Ex. 16


Item
Unit
A
Ex. 13
Ex. 14
B′
B
Example 29
Example 30
C
























HFO-1132(E)
mass %
81.6
67.3
53.9
48.9
47.2
60.0
70.0
77.3


HFO-1123
mass %
0.0
10.0
20.0
24.1
25.3
21.6
19.2
17.7


R1234yf
mass %
13.4
17.7
21.1
22.0
22.5
13.4
5.8
0.0


R32
mass %
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0


GWP

35
35
35
35
35
35
35
35


COP ratio
% (relative
97.6
96.6
95.5
95.0
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
104.4
95.0
99.0
102.1
104.4


capacity ratio
to R410A)

























TABLE 8







Comp.


Example
Comp.


Comp.




Ex. 17
Comp.
Comp.
31
Ex. 20
Example
Example
Ex. 21


Item
Unit
A
Ex. 18
Ex. 19
B′
B
32
33
C
























HFO-1132(E)
mass %
70.8
57.2
44.5
41.4
36.4
60.0
70.0
76.2


HFO-1123
mass %
0.0
10.0
20.0
22.8
26.7
18.0
15.3
13.8


R1234yf
mass %
19.2
22.8
25.5
25.8
26.9
12.0
4.7
0.0


R32
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


GWP

69
69
69
69
69
69
69
68


COP ratio
% (relative
97.4
96.5
95.6
95.0
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
106.2
95.0
101.5
104.4
106.2


capacity ratio
to R410A)

























TABLE 9







Comp.



Comp.


Comp.




Ex. 22
Comp.
Comp.
Example 34
Ex. 25


Ex. 26


Item
Unit
A
Ex. 23
Ex. 24
B′
B
Example 35
Example 36
C
























HFO-1132(E)
mass %
62.3
49.3
37.1
34.5
24.9
60.0
70.0
74.5


HFO-1123
mass %
0.0
10.0
20.0
22.8
30.7
15.4
12.4
11.2


R1234yf
mass %
23.4
26.4
28.6
28.4
30.1
10.3
3.3
0.0


R32
mass %
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3


GWP

98
98
98
98
98
98
97
97


COP ratio
% (relative
97.3
96.5
95.7
95.5
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
95.4
95.0
103.7
106.5
107.7


capacity ratio
to R410A)

























TABLE 10







Comp



Comp.


Comp.




Ex. 27
Comp.
Comp.
Example 37
Ex. 30


Ex. 31


Item
Unit
A
Ex. 28
Ex. 29
B′
B
Example 38
Example 39
C
























HFO-1132(E)
mass %
58.3
45.5
33.5
31.2
16.5
60.0
70.0
73.4


HFO-1123
mass %
0.0
10.0
20.0
23.0
35.5
14.2
11.1
10.1


R1234yf
mass %
25.2
28.0
30.0
29.3
31.5
9.3
2.4
0.0


R32
mass %
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5


GWP

113.0
113.1
113.1
113.1
113.2
112.5
112.3
112.2


COP ratio
% (relative
97.4
96.6
95.9
95.6
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
95.7
95.0
104.9
107.6
108.5


capacity ratio
to R410A)

























TABLE 11







Comp.



Comp.


Comp.




Ex. 32
Comp.
Comp.
Example 40
Ex. 35


Ex. 36


Item
Unit
A
Ex. 33
Ex. 34
B′
B
Example 41
Example 42
C
























HFO-1132(E)
mass %
53.5
41.0
29.3
25.8
0.0
50.0
60.0
71.7


HFO-1123
mass %
0.0
10.0
20.0
25.2
48.8
16.8
12.9
9.1


R1234yf
mass %
27.3
29.8
31.5
29.8
32.0
14.0
7.9
0.0


R32
mass %
19.2
19.2
19.2
19.2
19.2
19.2
19.2
19.2


GWP

131.2
131.3
131.4
131.3
131.4
130.8
130.6
130.4


COP ratio
% (relative
97.4
96.7
96.1
97.8
95.0
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
96.3
95.0
104.0
106.4
109.4


capacity ratio
to R410A)

























TABLE 12







Comp.



Comp.


Comp.




Ex. 37
Comp.
Comp.
Example 43
Ex. 40


Ex. 41


Item
Unit
A
Ex. 38
Ex. 39
B′
B
Example 44
Example 45
C
























HFO-1132(E)
mass %
49.1
36.9
25.5
20.0
0.0
50.0
60.0
69.7


HFO-1123
mass %
0.0
10.0
20.0
26.9
45.3
15.8
11.9
8.5


R1234yf
mass %
29.1
31.3
20.0
31.3
32.9
12.4
6.3
0.0


R32
mass %
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8


GWP

148.8
148.9
148.9
148.9
148.9
148.3
148.1
147.9


COP ratio
% (relative
97.6
96.9
96.4
95.9
95.5
95.0
95.0
95.0



to R410A)


Refrigerating
% (relative
95.0
95.0
95.0
98.4
95.0
105.6
108.0
110.3


capacity ratio
to R410A)









These results indicate that the refrigerants according to the present disclosure that satisfy the following conditions have 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:


when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32 based on their sum is respectively represented by x, y, z, and a,


if 0<a≤10.0, coordinates (x,y,z) in a ternary composition diagram (FIGS. 3 to 9) in which the sum of HFO-1132(E), HFO-1123, and R1234yf is (100-a) mass % are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.02a2−2.46a+93.4, 0, −0.02a2+2.46a+6.6),


point B′ (−0.008a2−1.38a+56, 0.018a2−0.53a+26.3, −0.01a2+1.91a+17.7),


point C (−0.016a2+1.02a+77.6, 0.016a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C);


if 10.0<a≤16.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0244a2−2.5695a+94.056, 0, −0.0244a2+2.5695a+5.944),


point B′ (0.1161a2−1.9959a+59.749, 0.014a2−0.3399a+24.8, −0.1301a2+2.3358a+15.451),


point C (−0.0161a2+1.02a+77.6, 0.0161a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C); or


if 16.5<a≤21.8, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0161a2−2.3535a+92.742, 0, −0.0161a2+2.3535a+7.258),


point B′ (−0.0435a2−0.0435a+50.406, −0.0304a2+1.8991a−0.0661, 0.0739a2−1.8556a+49.6601),


point C (−0.0161a2+0.9959a+77.851, 0.0161a2−0.9959a+22.149, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C).



FIGS. 3 to 9 show compositions whose R32 content a (mass %) is 0 mass %, 5 mass %, 10 mass %, 14.3 mass %, 16.5 mass %, 19.2 mass %, and 21.8 mass %, respectively.


Note that when point B in the ternary composition diagram is defined as a point where a refrigerating capacity ratio of 95% relative to that of R410A and a COP ratio of 95% relative to that of R410A are both achieved, point B′ is the intersection of straight line AB and an approximate line formed by connecting three points, including point C, where the COP ratio relative to that of R410A is 95%.


Points A, B′, and C were individually obtained by approximate calculation in the following manner.


Point A is a point where the HFO-1123 content is 0 mass % and a refrigerating capacity ratio of 95% relative to that of R410A is achieved. Three points corresponding to point A were obtained in each of the following three ranges by calculation, and their approximate expressions were obtained.












TABLE 13





Item
10.0 ≥ R32 ≥ 0
16.5 ≥ R32 ≥ 10.0
21.8 ≥ R32 ≥ 16.5
























R32
0.0
5.0
10.0
10.0
14.3
16.5
16.5
19.2
21.3


HFO-1132(E)
93.4
81.6
70.8
70.8
62.3
58.3
58.3
53.5
49.1


HFO-1123
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234yf
6.6
13.4
19.2
19.2
23.4
25.2
25.2
27.3
29.1










R32
x
x
x


HFO-1132(E)
0.02x2 − 2.46x + 93.4
0.0244x2 − 2.5695x + 94.056
0.0161x2 − 2.3535x + 92.742


approximate


expression


HFO-1123
0
0
0


approximate


expression


R1234yf
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)


approximate


expression









Point C is a point where the R1234yf content is 0 mass % and a COP ratio of 95% relative to that of R410A is achieved. Three points corresponding to point C were obtained in each of the following three ranges by calculation, and their approximate expressions were obtained.












TABLE 14





Item
10.0 ≥ R32 ≥ 0
16.5 ≥ R32 ≥ 10.0
21.8 ≥ R32 ≥ 16.5
























R32
0
5
10
10
14.3
16.5
16.5
19.2
21.8


HFO-1132(E)
77.6
77.3
76.2
76.2
74.5
73.4
73.4
71.7
69.7


HFO-1123
22.4
17.7
13.8
13.8
11.2
10.1
10.1
9.1
8.5


R1234yf
0
0
0
0
0
0
0
0
0










R32
x
x
x


HFO-1132(E)
100-R32HFO-1123
100-R32HFO-1123
100-R32HFO-1123


approximate


expression


HFO-1123
0.016x2 − 1.02x + 22.4
0.0161x2 − 0.9959x + 22.149
0.0161*2 − 0.9959* + 22.149


approximate


expression


R1234yf
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)


approximate


expression









Three points corresponding to point B′ were obtained in each of the following three ranges by calculation, and their approximate expressions were obtained.












TABLE 15





Item
10.0 ≥ R32 ≥ 0
16.5 ≥ R32 ≥ 10.0
21.8 ≥ R32 ≥ 16.5
























R32
0
5
10
10
14.3
16.5
16.5
19.2
21.8


HFO-1132(E)
56
48.9
41.4
41.4
34.5
31.2
31.2
25.8
20


HFO-1123
26.3
24.1
22.8
22.8
22.8
23
23
25.2
26.9


R1234yf
17.7
22
25.8
25.8
28.4
29.3
29.3
29.8
31.3










R32
x
x
x


HFO-1132(E)
−0.008*2 − 1.38*56
0.0161x2 − 1.9959x + 59.749
−0.0435x2 − 0.4456x + 50.406


approximate


expression


HFO-1123
0.018x2 − 0.53x + 26.3
0.014x2 − 0.3399x + 24.3
−0.0304*2 + 1.8991* − 0.0661


approximate


expression


R1234yf
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)
100-R32-HFO-1132(E)


approximate


expression









4.2. Refrigerant B

Refrigerant B according to the present disclosure is a mixed refrigerant comprising HFO-1132(E) and HFO-1123 in a total amount of 99.5 mass % or more based on the entire Refrigerant B, and comprising HFO-1132(E) in an amount of 62.5 mass % to 72.5 mass % based on the entire Refrigerant B. Refrigerant B according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., (1) a coefficient of performance that is equivalent to that of R410A, (2) a refrigerating capacity that is equivalent to that of R410A, (3) a sufficiently low GWP, and (4) a slight flammability (Class 2L) according to the ASHRAE standard. Refrigerant B according to the present disclosure is particularly preferably a mixed refrigerant comprising 72.5 mass % or less of HFO-1132(E), because it has a slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant B according to the present disclosure is more preferably a mixed refrigerant comprising 62.5 mass % or more of HFO-1132(E). In this case, Refrigerant B according to the present disclosure has a higher ratio of coefficient of performance relative to that of R410A, further suppresses the polymerization reaction of HFO-1132(E) and/or HFO-1123, and has more excellent stability.


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


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.


Refrigerant B according to the present disclosure is suitable for use as an alternative refrigerant for HFC refrigerants such as R410A, R407C, and R404A, as well as HCFC refrigerants such as R22.


Examples of Refrigerant B

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


Mixed refrigerants were prepared by mixing HFO-1132(E) and HFO-1123 at mass % based on their sum shown in Tables 16 and 17.


The GWP of compositions each comprising a mixture of R410A (R32=50%/R125=50%) was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth assessment report. The GWP of HFO-1132(E), which was not stated in the report, 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 compositions each comprising R410A and a mixture of HFO-1132(E) and HFO-1123 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.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Superheating temperature: 1 K


Subcooling temperature: 5 K


Compressor efficiency: 70%


Tables 1 and 2 shows GWP, COP, and refrigerating capacity, which were calculated based on these results. The COP and refrigerating capacity are ratios relative to R410A.


The coefficient of performance (COP) was determined by the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


Further, as for flammability, the burning velocity of these mixed refrigerants was measured according to ANSI/ASHRAE Standard 34-2013. Compositions that showed a burning velocity of 10 cm/s or less were determined to be Class 2L (slight 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.
















TABLE 16







Comp.
Comp.








Ex. 1
Ex. 2
Comp.


Item
Unit
R410A
HFO-1132E
Ex. 3
Example 1
Example 2
Example 3






















HFO-1132E
mass %
0
100
80
72.5
70
67.5


HFO-1123
mass %
0
0
20
27.5
30
32.5


GWP

2088
1
1
1
1
1


COP ratio
% (relative
100
98
95.3
94.4
94.1
93.8



to R410A)


Refrigerating
% (relative
100
98
102.1
103.5
103.9
104.3


capacity ratio
to R410A)


Discharge
MPa
2.7
2.7
2.9
3.0
3.0
3.1


pressure


Burning
cm/sec
Non-
20
13
10
9
9 or less


velocity

flammable























TABLE 17












Comp.






Comp.
Comp.
Comp.
Ex. 7


Item
Unit
Example 4
Example 5
Ex. 4
Ex. 5
Ex. 6
HFO-1123






















HFO-1132E
mass %
65
62.5
60
50
25
0


HFO-1123
mass %
35
37.5
40
50
75
100


GWP

1
1
1
1
1
1


COP ratio
% (relative
93.5
93.2
92.9
91.8
89.9
89.9



to R410A)


Refrigerating
% (relative
104.7
105.0
105.4
106.6
108.1
107.0


capacity ratio
to R410A)


Discharge
MPa
3.1
3.1
3.1
3.2
3.4
3.4


pressure


Burning
cm/sec
9 or less
9 or less
9 or less
9 or less
9 or less
5


velocity









Compositions comprising HFO-1132(E) in an amount of 62.5 mass % to 72.5 mass % based on the entire composition are stable while having a low GWP (GWP=1), and ensures ASHRAE flammability 2L. Furthermore, surprisingly, the compositions can ensure performance equivalent to that of R410A.


4.3. Refrigerant C

Refrigerant C according to the present disclosure is a mixed refrigerant comprising HFO-1132(E), R32, and 2,3,3,3-tetrafluoro-1-propene (R1234yf).


Refrigerant C according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., a cooling capacity that is equivalent to that of R410A, a sufficiently low GWP, and a slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant C according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AC, CF, FD, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point C (36.5, 18.2, 45.3),


point F (47.6, 18.3, 34.1), and


point D (72.0, 0.0, 28.0),


or on the line segments AC, CF, FD, and DA;


the line segment AC is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904),


the line segment FD is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28), and


the line segments CF and DA are straight lines.


When the requirements above are satisfied, Refrigerant C according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, a GWP of 125 or less, and a slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant C according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AB, BE, ED, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point B (42.6, 14.5, 42.9),


point E (51.4, 14.6, 34.0), and


point D (72.0, 0.0, 28.0),


or on the line segments AB, BE, ED, and DA;


the line segment AB is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904),


the line segment ED is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28), and


the line segments BE and DA are straight lines.


When the requirements above are satisfied, Refrigerant C according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, a GWP of 100 or less, and a slight flammability (Class 2L) according to the ASHRAE standard.


Refrigerant C according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments GI, IJ, and JK that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point I (55.1, 18.3, 26.6), and


point J (77.5. 18.4, 4.1),


or on the line segments GI, IJ, and JK;


the line segment GI is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604), and


the line segments IJ and JK are straight lines.


When the requirements above are satisfied, Refrigerant C according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to that of R410A and a GWP of 100 or less, is less likely to undergo changes such as polymerization and degradation, and has excellent stability.


Refrigerant C according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments GH, HK, and KG that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point H (61.8, 14.6, 23.6), and


point K (77.5, 14.6, 7.9),


or on the line segments GH, HK, and KG;


the line segment GH is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604), and


the line segments HK and KG are straight lines.


When the requirements above are satisfied, Refrigerant C according to the present disclosure has a refrigerating capacity ratio of 95% or more relative to that of R410A and a GWP of 100 or less, is less likely to undergo changes such as polymerization and degradation, and has excellent stability.


Refrigerant C according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), R32, and R1234yf as long as the above properties and effects are not impaired. In this respect, Refrigerant C according to the present disclosure preferably comprises HFO-1132(E), R32, and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and even more preferably 99.9 mass % or more, based on the entire Refrigerant C.


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.


Refrigerant C according to the present disclosure is suitable for use as an alternative refrigerant for R410A.


Examples of Refrigerant C

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


The burning velocity of the mixed refrigerants of HFO-1132(E), R32, and R1234yf was measured according to ANSI/ASHRAE Standard 34-2013. While changing the concentration of R32 by 5 mass %, compositions showing a burning velocity of 10 cm/s were found. Table 18 shows the found compositions.


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.















TABLE 18








R32 = 5
R32 = 10
R32 = 15
R32 = 20


Item
Unit
Point D
mass %
mass %
mass %
mass %





















HFO-1132E
Mass %
72
64
57
51
46


R32
Mass %
0
5
10
15
20


R1234yf
Mass %
28
31
33
34
34


Burning Velocity
cm/s
10
10
10
10
10









These results indicate that under the condition that the mass % of HFO-1132(E), R32, and R1234yf based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram (FIG. 10) in which the sum of HFO-1132(E), R32, and R1234yf is 100 mass % are on or on the right side of the line segments that connect 5 points shown in Table 18, the refrigerant has a slight flammability (Class 2L) according to the ASHRAE standard. This is because it has been known that the burning velocity of R1234yf is lower than that of both HFO-1132(E) and R32.


Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and R1234yf at mass % based on their sum shown in Tables 19 to 23. The coefficient of performance (COP) ratio and the refrigerating capacity ratio of the mixed refrigerants of Tables 19 to 23 relative to those of R410 were determined. The calculation conditions were as follows.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Degree of superheating: 1 K


Degree of subcooling: 5 K


Ecomp (compressive modulus): 0.7 kWh


Tables 19 to 23 show these values together with the GWP of each mixed refrigerant.
















TABLE 19








Comp.








Comp.
Ex. 2


Example 3
Example 4


Item
Unit
Ex. 1
A
Example 1
Example 2
B
C






















HFO-1132E
Mass %
R410A
71.1
60.4
50.6
42.6
36.5


R32
Mass %

0.0
5.0
10.0
14.5
18.2


R1234yf
Mass %

28.9
34.6
39.4
42.9
45.3


GWP

2088
2
36
70
100
125


COP Ratio
% (relative
100
98.9
98.7
98.7
98.9
99.1



to R410A)


Refrigerating
% (relative
100
85.0
85.0
85.0
85.0
85.0


Capacity Ratio
to R410A)





















TABLE 20







Comp.
Comp.
Comp.
Comp.




Ex. 3
Ex. 4
Ex. 5
Ex. 6


Item
Unit
O
P
Q
R




















HFO-1132E
Mass %
85.3
0.0
81.6
0.0


R32
Mass %
14.7
14.3
18.4
18.1


R1234yf
Mass %
0
85.7
0.0
81.9


GWP

100
100
125
125


COP Ratio
% (relative
96.2
103.4
95.9
103.4



to R410A)


Refrigerating
% (relative
105.7
57.3
107.4
60.9


Capacity Ratio
to R410A)
























TABLE 21







Comp.










Ex. 7


Example 7

Example 9
Comp.


Item
Unit
D
Example 5
Example 6
E
Example 8
F
Ex. 8























HFO-1132E
Mass %
72.0
64.0
57.0
51.4
51.0
47.6
46.0


R32
Mass %
0.0
5.0
10.0
14.6
15.0
18.3
20.0


R1234yf
Mass %
28.0
31.0
33.0
34.0
34.0
34.1
34.0


GWP

1.84
36
69
100
103
125
137


COP Ratio
% (relative
98.8
98.5
98.2
98.1
98.1
98.0
98.0



to R410A)


Refrigerating
% (relative
85.4
86.8
88.3
89.8
90.0
91.2
91.8


Capacity Ratio
to R410A)
























TABLE 22







Comp.










Ex. 7


Example 7

Example 9
Comp.


Item
Unit
D
Example 5
Example 6
E
Example 8
F
Ex. 8























HFO-1132E
Mass %
72.0
64.0
57.0
51.4
51.0
47.6
46.0


R32
Mass %
0.0
5.0
10.0
14.6
15.0
18.3
20.0


R1234yf
Mass %
28.0
31.0
33.0
34.0
34.0
34.1
34.0


GWP

1.84
36
69
100
103
125
137


COP Ratio
% (relative
98.8
98.5
98.2
98.1
98.1
98.0
98.0



to R410A)


Refrigerating
% (relative
85.4
86.8
88.3
89.8
90.0
91.2
91.8


Capacity Ratio
to R410A)






















TABLE 23







Comp.
Example 13
Example 14
Example 15
Comp.


Item
Unit
Ex. 11
J
K
G
Ex. 12





















HFO-1132E
Mass %
77.5
77.5
77.5
77.5
77.5


R32
Mass %
22.5
18.4
14.6
6.9
0.0


R1234yf
Mass %
0.0
4.1
7.9
15.6
22.5


GWP

153
125
100
48.0
2


COP Ratio
% (relative
95.8
96.1
96.5
97.5
98.6



to R410A)


Refrigerating
% (relative
109.1
105.6
102.3
95.0
88.0


Capacity Ratio
to R410A)









These results indicate that under the condition that the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure (FIG. 10) surrounded by line segments AC, CF, FD, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point C (36.5, 18.2, 45.3),


point F (47.6, 18.3, 34.1), and


point D (72.0, 0.0, 28.0),


or on the line segments AC, CF, FD, and DA, the refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, a GWP of 125 or less, and a slight flammability (Class 2L) according to the ASHRAE standard.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 10) surrounded by line segments AB, BE, ED, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point B (42.6, 14.5, 42.9),


point E (51.4, 14.6, 34.0), and


point D (72.0, 0.0, 28.0),


or on the line segments AB, BE, ED, and DA, the refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, a GWP of 100 or less, and a slight flammability (Class 2L) according to the ASHRAE standard.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 10) surrounded by line segments GI, IJ, and JK that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point I (55.1, 18.3, 26.6), and


point J (77.5. 18.4, 4.1),


or on the line segments GI, IJ, and JK, the refrigerant has a refrigerating capacity ratio of 95% or more ratio relative to that of R410A and a GWP of 125 or less, is less likely to undergo changes such as polymerization and degradation, and has excellent stability.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 10) surrounded by line segments GH, HK, and KG that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point H (61.8, 14.6, 23.6), and


point K (77.5, 14.6, 7.9),


or on the line segments GH, HK, and KG, the refrigerant has a refrigerating capacity ratio of 95% or more relative to that of R410A and a GWP of 100 or less, is less likely to undergo changes such as polymerization and degradation, and has excellent stability.


4.4 Refrigerant D

Refrigerant D according to the present disclosure is a mixed refrigerant comprising HFO-1132(E), HFO-1123, and R32. Refrigerant D according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., a coefficient of performance that is equivalent to that of R410A, and a sufficiently low GWP.


Refrigerant D according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC′, C′D′, D′E′, E′A′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5),


point E′ (41.8, 39.8, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments C′D′, D′E′, and E′A′ (excluding the points C′ and A′);


the line segment C′D′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2+1.1915z+43.3, z),


the line segment D′E′ is represented by coordinates (−0.0535z2+0.3229z+53.957, 0.0535z2+0.6771z+46.043, z), and


the line segments OC′, E′A′, and A′O are straight lines.


When the requirements above are satisfied, Refrigerant D according to the present disclosure has a COP ratio of 92.5% or more relative to that of R410A, and a GWP of 125 or less.


Refrigerant D according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC, CD, DE, EA′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5),


point E (72.2, 9.4, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments CD, DE, and EA′ (excluding the points C and A′);


the line segment CDE is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2+0.9852z+22.316, z), and


the line segments OC, EA′ and A′O are straight lines.


When the requirements above are satisfied, Refrigerant D according to the present disclosure has a COP ratio of 95% or more relative to that of R410A, and a GWP of 125 or less.


Refrigerant D according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC′, C′D′, D′A, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments C′D′ and D′A (excluding the points C′ and A);


the line segment C′D′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2+1.1915z+43.3, z), and


the line segments OC′, D′A, and AO are straight lines.


When the requirements above are satisfied, Refrigerant D according to the present disclosure has a COP ratio of 93.5% or more relative to that of R410A, and a GWP of 65 or less.


Refrigerant D according to the present disclosure is preferably a refrigerant wherein


when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC, CD, DA, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments CD and DA (excluding the points C and A);


the line segment CD is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2+0.9852z+22.316, z), and


the line segments OC, DA, and AO are straight lines.


When the requirements above are satisfied, Refrigerant D according to the present disclosure has a COP ratio of 95% or more relative to that of R410A, and a GWP of 65 or less.


Refrigerant D according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), HFO-1123, and R32 as long as the above properties and effects are not impaired. In this respect, Refrigerant D according to the present disclosure preferably comprises HFO-1132(E), HFO-1123, and R32 in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and even more preferably 99.9 mass % or more, based on the entire Refrigerant D.


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.


Refrigerant D according to the present disclosure is suitable for use as an alternative refrigerant for R410A.


Examples of Refrigerant D

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


Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1123, and R32 at mass % based on their sum shown in Tables 24 to 26.


The COP ratio and the refrigerating capacity (also referred to as “cooling capacity” or “capacity”) ratio of the mixed refrigerants relative to those of R410 were determined. The calculation conditions were as follows.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Degree of superheating: 1 K


Degree of subcooling: 5 K


Ecomp (compressive modulus): 0.7 kWh


Tables 24 to 26 show these values together with the GWP of each mixed refrigerant.

















TABLE 24








Comp.




Comp.




Comp.
Ex. 2

Example 2

Example 4
Ex. 3


Item
Unit
Ex. 1
C
Example 1
D
Example 3
E
O























HFO-1132(E)
mass %
R410A
77.7
77.3
76.3
74.6
72.2
100.0


HFO-1123
mass %

22.3
17.7
14.2
11.4
9.4
0.0


R32
mass %

0.0
5.0
9.5
14.0
18.4
0.0


GWP

2088
1
35
65
95
125
1


COP ratio
% (relative
100.0
95.0
95.0
95.0
95.0
95.0
97.8



to R410A)


Refrigerating
% (relative
100.0
102.5
104.4
106.0
107.6
109.1
97.8


capacity ratio
to R410A)
























TABLE 25







Comp.




Comp.
Comp.




Ex. 4

Example 6

Example 8
Ex. 5
Ex. 6


Item
Unit
C
Example 5
D′
Example 7
E′
A
B























HFO-1132(E)
mass %
56.7
55.0
52.2
48.0
41.8
90.5
0.0


HFO-1123
mass %
43.3
40.0
38.3
38.0
39.8
0.0
90.5


R32
mass %
0.0
5.0
9.5
14.0
18.4
9.5
9.5


GWP

1
35
65
95
125
65
65


COP ratio
% (relative
92.5
92.5
92.5
92.5
92.5
96.6
90.8



to R410A)


Refrigerating
% (relative
105.8
107.9
109.7
111.5
113.2
103.2
111.0


capacity ratio
to R410A)
























TABLE 26







Comp.
Comp.









Ex. 7
Ex. 8



Comp.
Comp.


Item
Unit
A′
B′
Example 9
Example 10
Example 11
Ex. 9
Ex. 10























HFO-1132(E)
mass %
81.6
0.0
85.0
65.0
70.0
50.0
20.0


HFO-1123
mass %
0.0
81.6
10.0
30.0
15.0
20.0
20.0


R32
mass %
18.4
18.4
5.0
5.0
15.0
30.0
60.0


GWP

125
125
35
35
102
203
405


COP ratio
% (relative
95.9
91.9
95.9
93.6
94.6
94.3
97.6



to R410A)


Refrigerating
% (relative
107.4
113.8
102.9
106.5
108.7
114.6
117.6


capacity ratio
to R410A)









These results indicate that under the condition that the mass % of HFO-1132(E), HFO-1123, and R32 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 (FIG. 11) surrounded by line segments OC′, C′D′, D′E′, E′A′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5),


point E′ (41.8, 39.8, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments C′D′, D′E′, and E′A′ (excluding the points C′ and A′), the refrigerant has a COP ratio of 92.5% or more relative to that of R410A, and a GWP of 125 or less.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 11) surrounded by line segments OC, CD, DE, EA′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5),


point E (72.2, 9.4, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments CD, DE, and EA′ (excluding the points C and A′), the refrigerant has a COP ratio of 95% or more relative to that of R410A, and a GWP of 125 or less.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 11) surrounded by line segments OC′, C′D′, D′A, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments C′D′ and D′A (excluding the points C′ and A), the refrigerant has a COP ratio of 92.5% or more relative to that of R410A, and a GWP of 65 or less.


Likewise, the results indicate that when coordinates (x,y,z) are within the range of a figure (FIG. 11) surrounded by line segments OC, CD, DA, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments CD and DA (excluding the points C and A), the refrigerant has a COP ratio of 95% or more relative to that of R410A, and a GWP of 65 or less.


In contrast, as shown in Comparative Examples 2, 3, and 4, when R32 is not contained, the concentrations of HFO-1132(E) and HFO-1123, which have a double bond, become relatively high; this undesirably leads to deterioration, such as decomposition, or polymerization in the refrigerant compound.


Moreover, as shown in Comparative Examples 3, 5, and 7, when HFO-1123 is not contained, the combustion-inhibiting effect thereof cannot be obtained; thus, undesirably, a composition having slight flammability cannot be obtained.


4.5. Refrigerant E

Refrigerant E according to the present disclosure is a mixed refrigerant comprising CO2, R32, HFO-1132(E), and R1234yf. Refrigerant E according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., a cooling capacity that is equivalent to that of R410A, a sufficiently low GWP, and a slight flammability.


Refrigerant E according to the present disclosure is a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5),


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight lines B″D and CI);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (51.6, 0.0, 48.4-w),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight lines B″D and CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (51.6, 0.0, 48.4-w),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight lines B″D and CI);


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w),


the curve JK is represented by coordinates (x, 0.0095x2−1.2222x+67.676, −0.0095x2+0.2222x+32.324-w), and


the curve KL is represented by coordinates (x, 0.0049x2−0.8842x+61.488, −0.0049x2−0.1158x+38.512).


Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A and a GWP of 350 or less, and further ensures a WCF slight flammability.


Refrigerant E according to the present disclosure is preferably a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤1.2, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 5 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight line CI);


if 1.2<w≤1.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 5 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point F (36.6, −3w+3.9, 2w+59.5), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI);


if 1.3<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KB′, B′D, DC, and CI that connect the following 6 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KB′, B′D, DC, and CI that connect the following 6 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CI);


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w), and


the curve JK is represented by coordinates (x, 0.0095x2−1.2222x+67.676, −0.0095x2+0.2222x+32.324-w).


When the requirements above are satisfied, Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A and a GWP of 250 or less, and further ensures a WCF slight flammability.


Refrigerant E according to the present disclosure is preferably a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤1.2, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (18.2, −1.1111w2−3.1667w+31.9, 1.1111w2+2.1667w+49.9), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight line CI);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (−0.0365w+18.26, 0.0623w2−4.5381w+31.856, −0.0623w2+3.5746w+49.884), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (18.1, 0.0444w2−4.3556w+31.411, −0.0444w2+3.3556w+50.489), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CI); and


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w).


When the requirements above are satisfied, Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A and a GWP of 125 or less, and further ensures a WCF slight flammability.


Refrigerant E according to the present disclosure is preferably a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤0.6, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves GO and OP, as well as straight lines PB″, B″D, and DG that connect the following 5 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2+1.4167w+26.2, −1.25w2+0.75w+51.6),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6),


point P (51.7, 1.1111w2+20.5, −1.1111w2−w+27.8),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5), and


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683),


or on the above line segments (excluding the points on the straight line B″D);


if 0.6<w≤1.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves GN, NO, and OP, as well as straight lines PB″, B″D, and DG that connect the following 6 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2+1.4167w+26.2, −1.25w2+0.75w+51.6),


point N (18.2, 0.2778w2+3w+27.7, −0.2778w2−4w+54.1),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6),


point P (51.7, 1.1111w2+20.5, −1.1111w2−w+27.8),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5), and


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683),


or on the above line segments (excluding the points on the straight line B″D),


if 0<w≤0.6, the curve GO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y),


if 0.6<w≤1.2, the curve GN is represented by coordinates (x, (0.0122w2−0.0113w+0.0313)x2+(−0.3582w2+0.1624w−1.4551)x+2.7889w2+3.7417w+43.824, 100-w-x-y),


if 0.6<w≤1.2, the curve NO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y), and


if 0<w≤1.2, the curve OP is represented by coordinates (x, (0.0074w2−0.0133w+0.0064)x2+(−0.5839w2+1.0268w−0.7103)x+11.472w2−17.455w+40.07, 100-w-x-y);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, NO, and OP, as well as straight lines PB″, B″D, DC, and CM that connect the following 8 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+44.422, 0.3645w2−4.5024w+55.57),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point P (51.7, −0.2381w2+1.881w+20.186, 0.2381w2−2.881w+28.114),


point B″ (51.6, 0.0, −w+48.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight lines B″D and CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y),


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0375w2−0.239w−0.4977)x−0.8575w2+6.4941w+36.078, 100-w-x-y), and


the curve OP is represented by coordinates (x, (−0.000463w2+0.0024w−0.0011)x2+(0.0457w2−0.2581w−0.075)x−1.355w2+8.749w+27.096, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, NO, and OP, as well as straight lines PB″, B″D, DC, and CM that connect the following 8 points:


point M (0.0, −0.0667w2+0.8333w+58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point O (36.8, −0.0444w2+0.6889w+25.956, 0.0444w2−1.6889w+37.244),


point P (51.7, −0.0667w2+0.8333w+21.633, 0.0667w2−1.8333w+26.667),


point B″ (51.6, 0.0, −w+48.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight lines B″D and CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y),


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y),


the curve NO is represented by coordinates (x, 0.0082x2+(0.0022w2−0.0345w−0.7521)x−0.1307w2+2.0247w+42.327, 100-w-x-y), and


the curve OP is represented by coordinates (x, (−0.0006258w2+0.0066w−0.0153)x2+(0.0516w2−0.5478w+0.9894)x−1.074w2+11.651w+10.992, 100-w-x-y).


When the requirements above are satisfied, Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A, a GWP of 350 or less, and further ensures an ASHRAE slight flammability.


Refrigerant E according to the present disclosure is preferably a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤0.6, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-a) mass % are within the range of a figure surrounded by curve GO and straight lines OF and FG that connect the following 3 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2−1.4167w+26.2, −1.25w2+3.5834w+51.6),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6), and


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997),


or on the above line segments, and


the curve GO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072) x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y);


if 0.6<w≤1.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves GN and NO, as well as straight lines OF and FG that connect the following 4 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2−1.4167w+26.2, −1.25w2+3.5834w+51.6),


point N (18.2, 0.2778w2+3.0w+27.7, −0.2.778w2−4.0w+54.1),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6), and


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997),


or on the above line segments,


if 0.6<w≤1.2, the curve GN is represented by coordinates (x, (0.0122w2−0.0113w+0.0313)x2+(−0.3582w2+0.1624w−1.4551)x+2.7889w2+3.7417w+43.824, 100-w-x-y), and


if 0.6<w≤1.2, the curve NO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y);


if 1.2<w≤1.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OF, FC, and CM that connect the following 6 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point F (36.6, −3w+3.9, 2w+59.5), and


point C (0.1081w2−5.169w+58.447, 0.0, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y), and


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0375w2−0.239w−0.4977)x−0.8575w2+6.4941w+36.078, 100-w-x-y);


if 1.3<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OB′, B′D, DC, and CM that connect the following 7 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y), and


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0457w2−0.2581w−0.075)x−1.355w2+8.749w+27.096, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OB′, B′D, DC, and CM that connect the following 7 points:


point M (0.0, −0.0667w2+0.8333w58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point O (36.8, −0.0444w2+0.6889w+25.956, 0.0444w2−1.6889w+37.244),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y),


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y), and


the curve NO is represented by coordinates (x, (0.0082x2+(0.0022w2−0.0345w−0.7521)x−0.1307w2+2.0247w+42.327, 100-w-x-y).


When the requirements above are satisfied, Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A and a GWP of 250 or less, and further ensures an ASHRAE slight flammability.


Refrigerant E according to the present disclosure is preferably a refrigerant wherein


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 1.2<w≤4.0, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-a) mass % are within the range of a figure surrounded by curves MW and WN, as well as straight lines NE, EC, and CM that connect the following 5 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point E (−0.0365w+18.26, 0.0623w2−4.5381w+31.856, −0.0623w2+3.5746w+49.884), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553), or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y), and


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW and WN, as well as straight lines NE, EC, and CM that connect the following 5 points:


point M (0.0, −0.0667w2+0.8333w+58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point E (18.1, 0.0444w2−4.3556w+31.411, −0.0444w2+3.3556w+50.489), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y), and


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y).


When the requirements above are satisfied, Refrigerant E according to the present disclosure has a refrigerating capacity ratio of 80% or more relative to that of R410A and a GWP of 125 or less, and further ensures an ASHRAE slight flammability.


Refrigerant E according to the present disclosure may further comprise other additional refrigerants in addition to CO2, R32, HFO-1132(E), and R1234yf as long as the above properties and effects are not impaired. In this respect, Refrigerant E according to the present disclosure preferably comprises CO2, R32, HFO-1132(E), and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and even more preferably 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.


Refrigerant E 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.


Examples of Refrigerant E

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


The burning velocity of the mixed refrigerants of CO2, R32, HFO-1132(E), and R1234yf was measured according to ANSI/ASHRAE Standard 34-2013. While changing the concentration of CO2, compositions showing a burning velocity of 10 cm/s were found. Tables 27 to 29 shows the found compositions.


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.









TABLE 27







0% CO2

















Comp.

Comp.

Comp.

Comp.




Ex. 13
Comp.
Ex. 15
Comp.
Ex. 17
Comp.
Ex. 19


Item
Unit
I
Ex. 14
J
Ex. 16
K
Ex. 18
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
28.0
32.8
33.2
31.2
27.6
23.8
19.4


CO2
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










0.6% CO2

















Example 3

Example 5

Example 7

Example 9


Item
Unit
I
Example 4
J
Example 6
K
Example 8
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
27.4
32.6
32.6
30.6
27.0
23.3
10.8


CO2
mass %
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










1.2% CO2

















Comp.










Ex. 48

Example 18

Example 20

Example 22


Item
Unit
I
Example 17
J
Example 19
K
Example 21
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
26.8
31.6
32.0
30.0
26.4
22.7
18.2


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










1.3% CO2

















Comp.










Ex. 59

Example 30

Example 32

Example 34


Item
Unit
I
Example 29
J
Example 31
K
Example 33
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
26.7
31.5
31.9
29.9
26.3
22.6
18.1


CO2
mass %
1.3
1.3
1.3
1.3
1.3
1.3
1.3


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










2.5% CO2

















Comp.










Ex. 69

Example 45

Example 47

Example 49


Item
Unit
I
Example 44
J
Example 46
K
Example 48
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
25.5
30.3
30.7
28.7
25.1
21.3
16.9


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










4.0 CO2

















Comp.










Ex. 79

Example 60

Example 62

Example 64


Item
Unit
I
Example 59
J
Example 61
K
Example 63
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
24.0
28.8
29.2
27.2
23.6
19.8
15.4


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










5.5 CO2

















Comp.










Ex. 89

Example 75

Example 77

Example 79


Item
Unit
I
Example 74
J
Example 76
K
Example 78
L





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
22.5
27.3
27.7
25.7
22.1
183
13.9


CO2
mass %
5.5
5.5
5.5
5.5
5.5
5.5
5.5


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)










7.0 CO2

















Comp.










Ex. 99

Example 90

Example 92

Example 94


Item
Unit
I
Example 89
J
Example 91
K
Example 93
L





HFO-1132(E)
mass %
72.0
57.2
48.5
412
35.6
32.0
28.9


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
21.0
25.8
26.2
24.2
20.6
16.8
12.4


CO2
mass %
7.0
7.0
7.0
7.0
7.0
7.0
7.0


Burning
cm/s
10
10
10
10
10
10
10


velocity


(WCF)
















TABLE 28







0% CO2













Comp.

Comp.

Comp.



Ex. 20
Comp.
Ex. 22
Comp.
Ex. 24


Item
M
Ex. 21
W
Ex. 23
N

















WCF
HFO-1132(E)
mass %
52.6
39.2
32.4
29.3
27.7



R32
mass %
0.0
5.0
10.0
14.5
18.2



R1234yf
mass %
47.4
55.8
57.6
56.2
54.1



CO2
mass %
0.0
0.0
0.0
0.0
0.0












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



0%, at release,
0%, at release,
0%, at release,
0%, at release,
0%, at release,



gas phase
gas phase
gas phase
gas phase
gas phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
57.8
48.7
43.6
40.6



R32
mass %
0.0
9.5
17.9
24.2
28.7



R1234yf
mass %
28.0
32.7
33.4
32.2
30.7



CO2
mass %
0.0
0.0
0.0
0.0
0.0













Burning velocity
cm/s
≤8
≤8
≤8
≤8
≤8


(WCF)


Burning velocity
cm/s
10
10
10
10
10


(WCFR)










0% CO2













Comp.

Comp.



Comp.
Ex. 26
Comp.
Ex. 28













Item
Ex. 25
O
Ex. 27
P



















WCF
HFO-1132(E)
mass %
24.5
22.6
21.2
20.5




R32
mass %
27.6
36.8
44.2
51.7




R1234yf
mass %
47.9
40.6
34.6
27.8




CO2
mass %
0.0
0.0
0.0
0.0













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




0%, at release,
0%, at release,
0%, at release,
0%, at release,




gas phase
gas phase
gas phase
gas phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
34.9
31.4
292
27.1




R32
mass %
38.1
45.7
51.1
56.4




R1234yf
mass %
27.0
23.0
19.7
16.5




CO2
mass %
0.0
0.0
0.0
0.0














Burning velocity
cm/s
≤8
≤8
≤8
≤8



(WCF)



Burning velocity
cm/s
10
10
10
10



(WCFR)











0.6% CO2













Comp.

Comp.





Ex. 35
Comp.
Ex. 38
Comp.
Example 1












Item
C = M
Ex. 37
W
Ex. 39
N(=E = G)

















WCF
HFO-1132(E)
mass %
55.4
42.4
35.1
31.6
29.6



R32
mass %
0.0
5.0
10.0
14.5
18.2



R1234yf
mass %
44.0
52.0
54.3
53.3
51.6



CO2
mass %
0.6
0.6
0.6
0.6
0.6












Leak conditions to make WCFF
Storage/
Storage/
Storage/
Storage/
Storage/



transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



0%, at release,
0%, at release,
0%, at release,
0%, at release,
0%, at release,



gas phase
gas phase
liquid phase
liquid phase
gas phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
58.6
49.7
44.5
41.3



R32
mass %
0.0
8.9
16.9
23.0
27.4



R1234yf
mass %
2.7
29.1
30.2
29.4
28.3



CO2
mass %
3.3
3.4
3.2
3.1
3.0













Burning velocity (WCF)
cm/s
≤8
≤8
≤8
≤8
≤8


Burning velocity (WCFF)
cm/s
10
10
10
10
10










0.6% CO2











Example 11

Example 13













Item
Example 10
O
Example 12
P



















WCF
HFO-1132(E)
mass %
26.3
24.0
22.4
20.9




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
45.5
38.6
33.0
26.8




CO2
mass %
0.6
0.6
0.6
0.6













Leak conditions to make WCFF
Storage/
Storage/
Storage/
Storage/




transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




0%, at release,
0%, at release,
0%, at release,
0%, at release,




gas phase
liquid phase
liquid phase
liquid phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
35.8
32.1
29.8
27.8




R32
mass %
36.6
44.1
49.4
54.7




R1234yf
mass %
24.8
21.1
18.2
14.9




CO2
mass %
2.8
2.7
2.6
2.6














Burning velocity (WCF)
cm/s
≤8
≤8
≤8
≤8



Burning velocity (WCFF)
cm/s
10
10
10
10











1.2% CO2













Comp.







Ex. 49
Comp.
Example 16

Example 24












Item
M
Ex. 50
G = W
Example 23
N

















WCF
HFO-1132(E)
mass %
58.0
45.2
38.1
34.0
31.7



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
40.8
48.6
50.7
48.9
48.9



CO2
mass %
1.2
1.2
1.2
1.2
1.2












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



0%, at release,
6%, at release,
6%, at release,
4%, at release,
4%, at release,



gas phase
gas phase
liquid phase
liquid phase
liquid phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
59.3
50.9
45.6
42.2



R32
mass %
0.0
8.3
15.8
21.7
26.2



R1234yf
mass %
24.8
28.0
28.5
27.7
26.7



CO2
mass %
3.2
4.4
4.8
5.0
4.9













Burning velocity
cm/s
≤8
≤8
≤8
≤8
≤8


(WCF)


Burning velocity
cm/s
10
10
10
10
10


(WCFF)










1.2% CO2











Example 26

Example 28













Item
Example 25
O
Example 27
P



















WCF
HFO-1132(E)
mass %
27.9
25.4
23.7
22.1




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
43.3
36.0
31.1
25.0




CO2
mass %
1.2
1.2
1.2
1.2













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




4%, at release,
4%, at release,
4%, at release,
4%, at release,




liquid phase
liquid phase
liquid phase
liquid phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
36.4
32.7
30.3
28.3




R32
mass %
35.3
42.8
48.1
53.4




R1234yf
mass %
23.6
20.0
17.1
13.9




CO2
mass %
4.7
4.5
45
4.4














Burning velocity
cm/s
≤8
≤8
≤8
≤8



(WCF)



Burning velocity
cm/s
10
10
10
10



(WCFF)











1.3% CO2













Comp.







Ex. 60

Example 36

Example 38












Item
M
Example 35
W
Example 37
N

















WCF
HFO-1132(E)
mass %
58.2
45.5
38.4
34.3
31.9



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
40.5
48.2
50.3
50.0
48.6



CO2
mass %
1.3
1.3
1.3
1.3
1.3












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



0%, at release,
8%, at release,
6%, at release,
6%, at release,
6%, at release,



gas phase
gas phase
liquid phase
liquid phase
liquid phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
59.4
51.0
45.7
42.2



R32
mass %
0.0
8.2
15.8
21.5
26.0



R1234yf
mass %
25.0
27.6
28.1
27.8
26.9



CO2
mass %
3.0
4.8
5.1
5.0
4.9













Burning velocity
cm/s
≤8
≤8
≤8
≤8
≤8


(WCF)


Burning velocity
cm/s
10
10
10
10
10


(WCFF)










1.3% CO2











Example 40

Example 42













Item
Example 39
O
Example 41
P



















WCF
HFO-1132(E)
mass %
28.1
25.6
23.9
22.3




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
43.0
36.3
30.8
24.7




CO2
mass %
1.3
1.3
1.3
1.3













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




4%, at release,
4%, at release,
4%, at release,
4%, at release,




liquid phase
liquid phase
liquid phase
liquid phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
36.5
32.8
30.4
28.4




R32
mass %
35.1
42.6
47.9
53.2




R1234yf
mass %
26.3
19.7
16.9
13.6




CO2
mass %
5.1
4.9
4.8
4.8














Burning velocity
cm/s
≤8
≤8
≤8
≤8



(WCF)



Burning velocity
cm/s
10
10
10
10



(WCFF)

















TABLE 29







2.5% CO2













Comp.







Ex. 70

Example 51

Example 53












Item
M
Example 50
W
Example 52
N

















WCF
HFO-1132(E)
mass %
59.7
48.1
40.9
36.9
34.2



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
37.8
44.4
46.6
46.2
45.1



CO2
mass %
2.5
2.5
2.5
2.5
2.5












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



26%, at release,
20%, at release,
20%, at release,
20%, at release,
18%, at release,



gas phase
gas phase
gas phase
gas phase
liquid phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
60.3
52.1
46.9
43.2



R32
mass %
0.0
7.5
14.6
20.2
24.7



R1234yf
mass %
24.9
27.4
28.4
28.0
26.7



CO2
mass %
3.1
4.8
4.9
4.9
5.4













Burning
cm/s
≤8
≤8
≤8
≤8
≤8


velocity (WCF)


Burning
cm/s
10
10
10
10
10


velocity (WCFF)










2.5% CO2











Example 55

Example 57













Item
Example 54
O
Example 56
P



















WCF
HFO-1132(E)
mass %
29.9
27.2
25.2
23.4




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
40.0
33.5
28.1
22.4




CO2
mass %
2.5
2.5
2.5
2.5













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




18%, at release,
18%, at release,
20%, at release,
22%, at release,




liquid phase
liquid phase
gas phase
gas phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
37.1
33.2
30.6
28.3




R32
mass %
34.1
41.8
47.6
53.4




R1234yf
mass %
23.4
19.7
16.9
13.8




CO2
mass %
5.4
5.4
4.9
4.5














Burning
cm/s
≤8
≤8
≤8
≤8



velocity (WCF)



Burning
cm/s
10
10
10
10



velocity (WCFF)











4.0% CO2













Comp.







Ex. 80

Example 66

Example 68












Item
M
Example 65
W
Example 67
N

















WCF
HFO-1132(E)
mass %
60.4
49.6
42.6
38.3
35.5



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
35.6
41.4
43.4
43.3
42.3



CO2
mass %
4.0
4.0
4.0
4.0
4.0












Leak conditions to make WCFF
Storage/
Storage/
Storage/
Storage/
Storage/



transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



32%, at release,
28%, at release,
28%, at release,
28%, at release,
28%, at release,



gas phase
gas phase
gas phase
gas phase
gas phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
60.9
52.9
47.5
43.8



R32
mass %
0.0
7.1
13.9
19.4
23.9



R1234yf
mass %
24.5
27.0
28.0
27.8
26.9



CO2
mass %
3.5
5.0
5.2
5.3
5.4













Burning velocity
cm/s
≤8
≤8
≤8
≤8
≤8


(WCF)


Burning velocity
cm/s
10
10
10
10
10


(WCFF)










4.0% CO2











Example 70

Example 72













Item
Example 69
O
Example 71
P



















WCF
HFO-1132(E)
mass %
31.0
28.0
25.9
23.9




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
37.4
31.2
26.1
20.4




CO2
mass %
4.0
4.0
4.0
4.0













Leak conditions to make WCFF
Storage/
Storage/
Storage/
Storage/




transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




28%, at release,
32%, at release,
32%, at release,
32%, at release,




gas phase
gas phase
gas phase
gas phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
37.4
33.1
30.5
28.1




R32
mass %
33.5
41.7
47.6
53.6




R1234yf
mass %
23.6
20.5
17.2
13.5




CO2
mass %
5.5
4.7
4.7
4.8














Burning velocity
cm/s
≤8
≤8
≤8
≤8



(WCF)



Burning velocity
cm/s
10
10
10
10



(WCFF)











5.5% CO2













Comp.







Ex. 90

Example 81

Example 83












Item
M
Example 80
W
Example 82
N

















WCF
HFO-1132(E)
mass %
60.7
50.3
43.3
39.0
36.3



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
33.8
39.2
41.2
41.1
40.0



CO2
mass %
5.5
5.5
5.5
5.5
5.5












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



36%, at release,
34%, at release,
34%, at release,
32%, at release,
34%, at release,



gas phase
gas phase
gas phase
gas phase
gas phase



side
side
side
side
side














WCFF
HFO-1132(E)
mass %
72.0
61.2
53.2
47.8
44.2



R32
mass %
0.0
6.8
13.5
19.0
23.4



R1234yf
mass %
24.5
27.0
28.1
27.7
26.8



CO2
mass %
3.5
5.0
5.2
5.5
5.6













Burning
cm/s
≤8
≤8
≤8
≤8
≤8


velocity (WCF)


Burning
cm/s
10
10
10
10
10


velocity (WCFF)










5.5% CO2











Example 85

Example 87













Item
Example 84
O
Example 86
P



















WCF
HFO-1132(E)
mass %
31.6
28.4
26.2
24.2




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
35.3
29.3
24.3
18.6




CO2
mass %
5.5
5.5
5.5
5.5













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




36%, at release,
38%, at release,
40%, at release,
40%, at release,




gas phase
gas phase
gas phase
gas phase




side
side
side
side















WCFF
HFO-1132(E)
mass %
37.6
33.2
30.3
27.9




R32
mass %
33.2
41.7
47.9
54.2




R1234yf
mass %
23.9
20.2
17.3
13.3




CO2
mass %
5.3
4.9
4.5
4.6














Burning
cm/s
≤8
≤8
≤8
≤8



velocity (WCF)



Burning
cm/s
10
10
10
10



velocity (WCFF)











7.0% CO2













Comp.







Ex. 100

Example 96

Example 98












Item
M
Example 95
W
Example 97
N

















WCF
HFO-1132(E)
mass %
60.7
50.3
43.7
39.5
36.7



R32
mass %
0.0
5.0
10.0
14.4
18.2



R1234yf
mass %
32.3
37.7
39.3
39.1
38.1



CO2
mass %
7.0
7.0
7.0
7.0
7.0












Leak conditions to make
Storage/
Storage/
Storage/
Storage/
Storage/


WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,



42%, at release,
34%, at release,
38%, at release,
40%, at release,
40%, at release,



gas phase
gas phase
gas phase
gas phase
gas phase



side
side
side
side
side














WCF
HFO-1132(E)
mass %
72.0
61.2
53.4
48.1
44.4



R32
mass %
0.0
6.8
13.3
18.7
23.2



R1234yf
mass %
24.4
27.0
27.8
28.1
27.1



CO2
mass %
3.6
5.0
5.5
5.1
5.3













Burning velocity
cm/s
≤8
≤8
≤8
≤8
≤8


(WCF)


Burning velocity
cm/s
10
10
10
10
10


(WCFF)










7.0% CO2











Example 100

Example 102













Item
Example 99
O
Example 101
P



















WCF
HFO-1132(E)
mass %
31.9
28.6
26.4
24.2




R32
mass %
27.6
36.8
44.0
51.7




R1234yf
mass %
33.5
27.6
22.6
17.1




CO2
mass %
7.0
7.0
7.0
7.0













Leak conditions to make
Storage/
Storage/
Storage/
Storage/



WCFF
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,
transport, −40° C.,




42%, at release,
42%, at release,
42%, at release,
44%, at release,




gas phase
gas phase
gas phase
gas phase




side
side
side
side















WCF
HFO-1132(E)
mass %
37.7
33.2
30.4
27.8




R32
mass %
33.1
41.7
47.9
54.6




R1234yf
mass %
24.1
19.8
16.3
12.7




CO2
mass %
5.1
5.3
5.4
4.9














Burning velocity
cm/s
≤8
≤8
≤8
≤8



(WCF)



Burning velocity
cm/s
10
10
10
10



(WCFF)










These results indicate that under the condition that the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z, when coordinates (x,y,z) in a ternary composition diagram (FIGS. 2 to 9) in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are on or below the line segments that connect points I, J, K, and L, the refrigerant has a WCF slight flammability.


Further, the results indicate that when coordinates (x,y,z) in the ternary composition diagram of FIG. 2 are on or below line segments that connect points M, N, O, and P, the refrigerant has an ASHRAE slight flammability.


Mixed refrigerants were prepared by mixing R32, HFO-1132(E), and R1234yf at mass % based on their sum shown in Tables 30 to 40. The coefficient of performance (COP) ratio and the refrigerating capacity ratio of the mixed refrigerants in Tables 30 to 37 relative to those of R410 were determined.


The GWP of compositions each comprising a mixture of R1234yf and R410A (R32=50%/R125=50%) was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth assessment report. The GWP of HFO-1132(E), which was not stated in the report, 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 compositions each comprising R410A and 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.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Degree of superheating: 5 K


Degree of subcooling: 5 K


Ecomp (compressive modulus): 0.7 kWh


Tables 30 to 37 show these values together with the GWP of each mixed refrigerant. Tables 30 to 37 respectively show the cases in which the CO2 concentrations are 0 mass %, 0.6 mass %, 1.2 mass %, 1.3 mass %, 2.5 mass %, 4 mass %, 5.5 mass %, and 7 mass %.









TABLE 30







0% CO2




















Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Comp.
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 6
Ex. 7
Ex. 8
Ex. 9


Item
Unit
Ex. 1
A
B
A′
B′
A″
B″
C
D





HFO-1132(E)
mass %
R410A
81.6
0.0
63.1
0.0
48.2
0.0
58.3
0.0


R32
mass %

18.4
18.1
36.9
36.7
51.8
51.5
0.0
40.3


R1234yf
mass %

0.0
81.9
0.0
63.3
0.0
49.5
41.7
59.7


CO2
mass %

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


GWP

2088
125
125
250
250
350
350
2
274


COP ratio
% (relative
100
98.7
103.6
98.7
102.3
99.2
102.1
100.3
102.2



to R410A)


Refrigerating
% (relative
100
105.3
62.5
109.9
77.5
112.1
87.0
80.0
80.0


capacity ratio
to R410A)


Condensation
° C.
0.1
0.3
6.8
0.1
4.5
0.0
2.7
2.9
4.0


glide







Comp.
Comp.
Comp.
Comp.

Comp.

Comp.





Ex. 10
Ex. 11
Ex. 12
Ex. 13
Comp.
Ex. 15
Comp.
Ex. 17
Comp.


Item
Unit
E
F
G
I
Ex. 14
J
Ex. 16
K
Ex. 18





HFO-1132(E)
mass %
31.9
5.2
26.2
72.0
57.2
48.5
41.2
35.6
32.0


R32
mass %
18.2
36.7
22.2
0.0
10.0
18.3
27.6
36.8
44.2


R1234yf
mass %
49.9
58.1
51.6
28.0
32.8
33.2
31.2
27.6
23.8


CO2
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


GWP

125
250
152
2
69
125
188
250
300


COP ratio
% (relative
100.3
101.8
100.5
99.9
99.5
99.4
99.5
99.6
99.8



to R410A)


Refrigerating
% (relative
82.3
80.8
82.4
86.6
88.4
90.9
94.2
97.7
100.5


capacity ratio
to R410A)


Condensation
° C.
4.4
4.3
4.5
1.7
2.6
2.7
2.4
1.9
1.6


glide























Comp.
Comp.

Comp.

Comp.

Comp.

Comp.




Ex. 19
Ex. 20
Comp.
Ex. 22
Comp.
Ex. 24
Comp.
Ex. 26
Comp.
Ex. 28


Item
Unit
L
M
Ex. 21
W
Ex. 23
N
Ex. 25
O
Ex. 27
P





HFO-1132(E)
mass %
28.9
52.6
39.2
32.4
29.3
27.7
24.5
22.6
21.2
20.5


R32
mass %
51.7
0.0
5.0
10.0
14.5
18.2
27.6
36.8
44.2
51.7


R1234yf
mass %
19.4
47.4
55.8
57.6
56.2
54.1
47.9
40.6
34.6
27.8


CO2
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


GWP

350
2
36
70
100
12.5
188
250
300
350


COP ratio
% (relative
100.1
100.5
100.9
100.9
100.8
100.7
100.4
100.4
100.5
100.6



to R410A)


Refrigerating
% (relative
103.3
77.1
74.8
75.6
77.8
80.0
85.5
91.0
95.0
99.1


capacity ratio
to R410A)


Condensation
° C.
1.2
3.4
4.7
5.2
5.1
4.9
4.0
3.0
2.3
1.7


glide
















TABLE 31







0.6% CO2



















Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Ex. 29
Ex. 30
Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35
Ex. 36
Example 1


Item
Unit
A
B
A′
B′
A″
B″
C = M
D
E = G = N





HFO-1132(E)
mass %
81.0
0.0
62.5
0.0
47.6
0.0
55.4
0.0
29.6


R32
mass %
18.4
18.1
36.9
36.7
51.8
51.6
0.0
38.6
18.2


R1234yf
mass %
0.0
81.3
0.0
62.7
0.0
47.8
44.0
60.8
51.6


CO2
mass %
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


GWP

125
125
250
250
350
350
2
263
125


COP ratio
% (relative
98.4
103.4
98.4
102.1
99.0
102.0
100.1
102.1
100.2



to R410A)


Refrigerating
% (relative
106.5
63.7
111.1
78.7
113.1
88.6
80.0
80.0
82.4


capacity ratio
to R410A)


Condensation
° C.
0.7
75
0.4
4.9
0.3
3.0
3.9
4.7
5.2


glide






















Example 2
Example 3

Example 5

Example 7

Example 9
Comp.


Item
Unit
F
I
Example 4
J
Example 6
K
Example 8
L
Ex. 37





HFO-1132(E)
mass %
2.7
72.0
57.2
48.5
41.2
35.6
32.0
28.9
42.4


R32
mass %
36.7
0.0
10.0
18.3
27.6
36.8
44.2
51.7
5.0


R1234yf
mass %
60.0
27.4
32.6
32.6
30.6
27.0
23.3
10.8
52.0


CO2
mass %
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


GWP

250
2
69
125
188
250
300
350
36


COP ratio
% (relative
101.8
99.5
99.2
99.1
99.2
99.4
99.6
99.7
100.3



to R410A)


Refrigerating
% (relative to
80.4
88.1
89.7
92.3
95.5
99.0
101.7
108.2
77.9


capacity ratio
R410A)


Condensation
° C.
4.8
5.2
2.4
3.2
3.1
2.8
2.3
1.9
3.9


glide



















Comp.









Ex. 38
Comp.

Example 11

Example 13


Item
Unit
W
Ex. 39
Example 10
O
Example 12
P





HFO-1132(E)
mass %
35.1
31.6
26.3
24.0
22.4
20.9


R32
mass %
10.0
14.5
27.6
36.8
44.0
51.7


R1234yf
mass %
54.3
53.3
45.5
38.6
33.0
26.8


CO2
mass %
0.6
0.6
0.6
0.6
0.6
0.6


GWP

70
100
188
250
299
350


COP ratio
% (relative
100.4
100.3
100.1
100.1
100.2
100.4



to R410A)


Refrigerating
% (relative
78.5
80.4
87.8
93.0
96.8
100.5


capacity ratio
to R410A)


Condensation
° C.
5.1
5.5
5.4
5.1
4.2
3.2


glide
















TABLE 6





1.2% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Example




Ex. 40
Ex. 41
Ex. 42
Ex. 43
Ex. 44
Ex. 45
Ex. 46
Ex. 47
14


Item
Unit
A
B
A′
B′
A″
B″
C
D
E





HFO-1132(E)
mass %
80.4
0.0
61.9
0.0
47.0
0.0
52.4
0.0
26.5


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
36.8
18.2


R1234yf
mass %
0.0
80.7
0.0
62.2
0.0
46.9
46.4
62.0
54.1


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

125
125
250
250
350
350
2
251
125


COP ratio
%
98.1
103.2
98.2
101.9
98.7
101.7
99.9
101.9
100.2



(relative to












R410A)











Refrigerating
%
107.7
65.0
112.2
79.8
114.2
89.9
80.0
80.0
82.0


capacity ratio
(relative to












R410A)











Condensation
° C.
1.2
8.1
0.8
5.4
0.6
3.4
4.9
5.3
6.0


glide






















Example
Example
Comp.

Example

Example

Example




15
16
Ex. 48
Example
18
Example
20
Example
22


Item
Unit
F
G = W
I
17
J
19
K
21
L





HFO-1132(E)
mass %
0.3
38.1
72.0
57.2
48.5
41.2
35.6
32.0
28.9


R32
mass %
36.6
10.0
0.0
10.0
18.3
27.6
36.8
44.2
51.7


R1234yf
mass %
61.9
50.7
26.8
31.6
32.0
30.0
26.4
22.7
18.2


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

250
70
2
69
125
188
250
300
350


COP ratio
%
101.9
99.9
99.2
98.9
98.8
98.9
99.1
99.4
99.6



(relative to












R410A)











Refrigerating
%
80.0
81.6
89.7
91.3
93.7
96.9
100.3
103.0
105.8


capacity ratio
(relative to












R410A)











Condensation
° C.
5.4
5.7
3.1
3.6
3.6
3.2
2.6
2.2
1.8


glide





















Comp.


Example

Example

Example




Ex. 49
Comp.
Example
24
Example
26
Example
28


Item
Unit
M
Ex. 50
23
N
25
O
27
P





HFO-1132(E)
mass %
58.0
45.2
34.0
31.7
27.9
25.4
23.7
22.1


R32
mass %
0.0
5.0
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
40.8
48.6
48.9
48.9
43.3
36.0
31.1
25.0


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

2
36
100
125
188
250
298
350


COP ratio
%
99.6
99.8
99.8
99.8
99.7
99.7
99.9
100.0



(relative to











R410A)










Refrigerating
%
82.9
80.9
83.6
84.9
90.0
953
98.7
102.4


capacity ratio
(relative to











R410A)










Condensation
° C.
4.3
5.4
5.6
5.4
4.4
3.4
2.8
2.2


glide
















TABLE 7





1.3% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55
Ex. 56
Ex. 57
Ex. 58
Ex. 59


Item
Unit
A
B
A′
B′ = D = F
A″
B″
C
E
I





HFO-1132(E)
mass %
803
0.0
61.8
0.0
46.9
0.0
51.9
26.1
72.0


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
18.2
0.0


R1234yf
mass %
0.0
80.6
0.0
62.1
0.0
47.1
46.8
54.4
26.7


CO2
mass %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3


GWP

125
125
250
250
350
350
2
125
2


COP ratio
%
98.0
103.2
98.1
101.9
98.7
101.7
99.8
100.2
99.1



(relative to












R410A)











Refrigerating
%
107.9
65.2
112.3
80.0
114.3
90.0
80.0
82.0
89.9


capacity ratio
(relative to












R410A)











Condensation
° C.
1.2
8.2
0.8
5.4
0.7
3.4
5.1
6.1
3.2


glide























Example

Example

Example
Comp.

Example




Example
30
Example
32
Example
34
Ex. 60
Example
36


Item
Unit
29
J
31
K
33
L
M
35
W





HFO-1132(E)
mass %
57.2
48.5
41.2
35.6
32.0
28.9
58.2
45.5
38.4


R32
mass %
10.0
18.3
27.6
36.8
44.2
51.7
0.0
5.0
10.0


R1234yf
mass %
31.5
31.9
29.9
26.3
22.6
18.1
40.5
48.2
50.3


CO2
mass %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3


GWP

69
125
188
250
300
350
2
36
70


COP ratio
%
98.9
98.8
98.9
99.1
99.3
99.6
99.5
99.8
99.8



(relative to












R410A)











Refrigerating
%
91.5
93.9
97.1
100.5
103.2
106.0
83.3
81.3
82.0


capacity ratio
(relative to












R410A)











Condensation
° C.
3.7
3.6
3.2
2.7
2.3
1.8
4.4
5.4
5.8


glide




















Example

Example

Example




Example
38
Example
40
Example
42


Item
Unit
37
N
39
O
41
P





HFO-1132(E)
mass %
34.3
31.9
28.1
25.6
23.9
22.3


R32
mass %
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
50.0
48.6
43.0
36.3
30.8
24.7


CO2
mass %
1.3
1.3
1.3
1.3
1.3
1.3


GWP

100
125
188
250
298
350


COP ratio
%
99.8
99.3
99.6
99.7
99.8
100.0



(relative to









R410A)








Refrigerating
%
83.5
85.2
90.3
95.4
99.0
102.7


capacity ratio
(relative to









R410A)








Condensation
° C.
6
5.4
4.5
3.5
2.9
2.3


glide
















TABLE 34





2.5% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Example




Ex. 61
Ex. 62
Ex. 63
Ex. 64
Ex. 65
Ex. 66
Ex. 67
Ex. 68
43


Item
Unit
A
B
A′
B′
A″
B″
C
D
E





HFO-1132(E)
mass %
79.1
0.0
60.6
0.0
45.7
0.0
46.2
0.0
20.9


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
33.2
18.2


R1234yf
mass %
0.0
79.4
0.0
60.9
0.0
45.9
51.3
64.3
58.4


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

125
125
250
250
350
350
3
227
125


COP ratio
%
97.4
102.7
97.6
101.5
98.3
101.3
99.6
101.6
100.2



(relative to












R410A)











Refrigerating
%
110.3
67.8
114.5
82.5
116.4
92.5
80.0
80.0
81.7


capacity ratio
(relative to












R410A)











Condensation
° C.
2.0
9.5
1.5
6.3
1.3
4.1
7.1
6.9
7.6


glide






















Comp.

Example

Example

Example
Comp.





Ex. 69
Example
45
Example
47
Example
49
Ex. 70
Example


Item
Unit
I
44
J
46
K
48
L
M
50





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9
59.7
48.1


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7
0.0
5.0


R1234yf
mass %
25.5
30.3
30.7
28.7
25.1
21.3
16.9
37.8
44.4


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

2
69
125
188
250
300
350
2
36


COP ratio
%
98.4
98.2
98.2
98.4
98.6
98.9
99.1
98.8
99.0



(relative to












R410A)











Refrigerating
%
93.1
94.5
96.7
99.8
103.1
105.9
108.6
87.1
85.7


capacity ratio
(relative to












R410A)











Condensation
° C.
4.4
4.7
4.5
3.9
3.3
2.8
2.4
5.6
6.3


glide




















Example

Example

Example

Example




51
Example
53
Example
55
Example
57


Item
Unit
W
52
N
54
O
56
P





HFO-1132(E)
mass %
40.9
36.9
34.2
29.9
27.2
25.2
23.4


R32
mass %
10.0
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
46.6
46.2
45.1
40.0
33.5
28.1
22.4


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

70
99
125
188
250
298
350


COP ratio
%
99.1
99.1
99.1
99.0
99.1
99.3
99.5



(relative to










R410A)









Refrigerating
%
86.2
87.7
89.2
94.0
98.8
102.4
105.8


capacity ratio
(relative to










R410A)









Condensation
° C.
6
6.3
6.0
5.0
4.0
3.4
2.8


glide
















TABLE 35





4% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Example




Ex. 71
Ex. 72
Ex. 73
Ex. 74
Ex. 75
Ex. 76
Ex. 77
Ex. 78
58


Item
Unit
A
B
A′
B′
A″
B″
C
D
E





HFO-1132(E)
mass %
77.6
0.0
59.1
0.0
44.2
0.0
39.5
0.0
14.7


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
28.9
18.1


R1234yf
mass %
0.0
77.9
0.0
59.4
0.0
44.4
56.5
67.1
63.2


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

125
125
250
249
350
350
3
198
125


COP ratio
%
96.7
102.2
97.0
101.0
97.7
100.8
99.4
101.3
100.4



(relative to












R410A)











Refrigerating
%
113.3
71.2
117.3
85.7
118.9
95.6
80.0
80.0
81.2


capacity ratio
(relative to












R410A)











Condensation
° C.
3.0
10.9
2.2
7.2
2.0
5.0
9.6
8.7
9.6


glide






















Comp.

Example

Example

Example
Comp.





Ex. 79
Example
60
Example
62
Example
64
Ex. 80
Example


Item
Unit
I
59
J
61
K
63
L
M
65





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9
60.4
49.6


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7
0.0
5.0


R1234yf
mass %
24.0
28.8
29.2
27.2
23.6
19.8
15.4
35.6
41.4


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

2
69
125
188
250
300
350
2
36


COP ratio
%
97.6
97.5
97.5
97.7
98.0
98.3
98.6
98.0
98.2



(relative to












R410A)











Refrigerating
%
97.0
98.1
100.2
103.2
106.5
109.1
111.8
91.3
90.2


capacity ratio
(relative to












R410A)











Condensation
° C.
5.8
5.8
5.4
4.7
4.0
3.5
3.1
6.9
7.4


glide




















Example

Example

Example

Example




66
Example
68
Example
70
Example
72


Item
Unit
W
67
N
69
O
71
P





HFO-1132(E)
mass %
42.6
38.3
35.5
31.0
28.0
25.9
23.9


R32
mass %
10.0
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
43.4
43.3
42.3
37.4
31.2
26.1
20.4


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

70
99
125
188
250
298
350


COP ratio
%
98.3
98.3
98.3
98.3
98.5
98.7
98.9



(relative to










R410A)









Refrigerating
%
90.7
92.0
93.4
97.9
102.5
105.9
109.3


capacity ratio
(relative to










R410A)









Condensation
° C.
7
7.2
6.9
5.8
4.7
4.0
3.4


glide
















TABLE 36





5.5% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Example




Ex. 81
Ex. 82
Ex. 83
Ex. 84
Ex. 85
Ex. 86
Ex. 87
Ex. 88
73


Item
Unit
A
B
A′
B′
A″
B″
C
D
E





HFO-1132(E)
mass %
76.1
0.0
57.6
0.0
42.7
0.0
33.0
0.0
8.8


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
24.7
18.1


R1234yf
mass %
0.0
76.4
0.0
57.9
0.0
42.9
61.5
69.8
67.6


CO2
mass %
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5


GWP

125
125
250
249
350
350
3
170
125


COP ratio
%
96.0
101.8
96.4
100.5
97.2
100.3
99.4
101.2
100.6



(relative to












R410A)











Refrigerating
%
116.2
74.6
119.9
88.9
121.5
98.7
80.0
80.0
80.8


capacity ratio
(relative to












R410A)











Condensation
° C.
3.7
12.3
2.9
8.2
2.6
5.8
12.1
10.8
11.5


glide






















Comp.

Example

Example

Example
Comp.





Ex. 89
Example
75
Example
77
Example
79
Ex. 90
Example


Item
Unit
I
74
J
76
K
78
L
M
80





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9
60.7
50.3


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7
0.0
5.0


R1234yf
mass %
22.5
27.3
27.7
25.7
22.1
18.3
13.9
33.8
39.2


CO2
mass %
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5


GWP

2
69
125
188
250
299
350
2
36


COP ratio
%
96.8
96.8
96.9
97.1
97.4
97.7
98.0
97.2
97.4



(relative to












R410A)











Refrigerating
%
100.9
101.8
103.8
106.6
109.8
112.4
115.0
95.4
94.3


capacity ratio
(relative to












R410A)











Condensation
° C.
6.9
6.7
6.2
5.4
4.7
4.1
3.7
8.1
8.5


glide




















Example

Example

Example

Example




81
Example
83
Example
85
Example
87


Item
Unit
W
82
N
84
O
86
P





HFO-1132(E)
mass %
43.3
39.0
36.3
31.6
28.4
26.2
24.2


R32
mass %
10.0
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
41.2
41.1
40.0
35.3
29.3
24.3
18.6


CO2
mass %
5.5
5.5
5.5
5.5
5.5
5.5
5.5


GWP

70
99
125
188
250
298
350


COP ratio
%
97.5
97.6
97.6
97.7
97.9
98.1
98.3



(relative to










R410A)









Refrigerating
%
94.7
95.9
97.4
101.6
106.1
109.3
112.6


capacity ratio
(relative to










R410A)









Condensation
° C.
8
8.1
7.6
6.5
5.4
4.7
4.0


glide
















TABLE 37





7% CO2



























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Example




Ex. 91
Ex. 92
Ex. 93
Ex. 94
Ex. 95
Ex. 96
Ex. 97
Ex. 98
88


Item
Unit
A
B
A′
B′
A″
B″
C
D
E





HFO-1132(E)
mass %
74.6
0.0
56.1
0.0
41.2
0.0
26.8
0.0
3.1


R32
mass %
18.4
18.1
36.9
36.6
51.8
51.6
0.0
20.5
18.1


R1234yf
mass %
0.0
74.9
0.0
56.4
0.0
41.4
66.2
72.5
71.8


CO2
mass %
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0


GWP

125
125
250
249
350
350
3
141
125


COP ratio
%
95.3
101.3
95.8
100.0
96.7
99.8
99.5
101.1
100.9



(relative to












R410A)











Refrigerating
%
119.0
78.0
122.6
92.2
124.0
101.9
80.0
80.0
80.3


capacity ratio
(relative to












R410A)











Condensation
° C.
4.4
13.6
3.4
9.0
3.1
6.5
14.6
13.0
13.3


glide






















Comp.

Example

Example

Example
Comp.





Ex. 99
Example
90
Example
92
Example
94
Ex. 100
Example


Item
Unit
I
89
J
91
K
93
L
M
95





HFO-1132(E)
mass %
72.0
57.2
48.5
41.2
35.6
32.0
28.9
60.7
50.3


R32
mass %
0.0
10.0
18.3
27.6
36.8
44.2
51.7
0.0
5.0


R1234yf
mass %
21.0
25.8
26.2
24.2
20.6
16.8
12.4
32.3
37.7


CO2
mass %
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0


GWP

2
69
125
188
250
299
350
2
36


COP ratio
%
96.0
96.1
96.2
96.5
96.8
97.1
97.5
96.5
96.7



(relative to












R410A)











Refrigerating
%
104.7
105.5
107.3
110.0
113.1
115.6
118.2
99.2
98.0


capacity ratio
(relative to












R410A)











Condensation
° C.
7.9
7.5
6.9
6.0
5.3
4.7
4.2
9.2
9.4


glide




















Example

Example

Example

Example




96
Example
98
Example
100
Example
102


Item
Unit
W
97
N
99
O
101
P





HFO-1132(E)
mass %
43.7
39.5
36.7
31.9
28.6
26.4
24.2


R32
mass %
10.0
14.4
18.2
27.6
36.8
44.0
51.7


R1234yf
mass %
39.3
39.1
38.1
33.5
27.6
22.6
17.1


CO2
mass %
7.0
7.0
7.0
7.0
7.0
7.0
7.0


GWP

70
99
125
188
250
298
350


COP ratio
%
96.9
96.9
97.0
97.1
97.3
97.5
97.8



(relative to










R410A)









Refrigerating
%
98.6
99.7
101.1
105.2
109.5
112.7
115.8


capacity ratio
(relative to










R410A)









Condensation
° C.
9
8.8
8.4
7.1
6.0
5.2
4.6


glide

























TABLE 38









Comp.
Comp.
Comp.
Example
Example
Comp.
Comp.
Comp.


Item
Unit
Ex. 101
Ex. 102
Ex. 103
103
104
Ex. 104
Ex. 105
Ex. 106





HFO-1132(E)
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
78.8
68.8
58.8
48.8
38.8
28.8
18.8
8.8


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

532
465
398
331
264
197
130
63


COP ratio
%
101.3
101.2
101.1
101.0
101.0
101.3
102.0
102.8



(relative to











R410A)










Refrigerating
%
108.5
104.1
99.2
93.6
87.2
80.1
72.2
63.1


capacity ratio
(relative to











R410A)










Condensation
° C.
1.1
1.6
2.2
3.1
4.3
5.8
7.4
8.4


glide





















Comp.
Comp.
Example
Example
Example
Comp.
Comp.
Comp.


Item
Unit
Ex. 107
Ex. 108
105
106
107
Ex. 109
Ex. 110
Ex. 111





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0


R32
mass %
68.8
58.8
48.8
38.8
28.8
18.8
8.8
58.8


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

465
398
331
264
197
130
62
398


COP ratio
%
100.6
100.5
100.4
100.3
100.4
100.9
101.8
100.0



(relative to











R410A)










Refrigerating
%
108.6
103.9
98.6
92.6
85.8
78.2
69.6
108.3


capacity ratio
(relative to











R410A)










Condensation
° C.
1.1
1.7
2.5
3.5
4.8
6.4
7.7
1.2


glide





















Example
Example
Example
Example
Comp.
Comp.
Comp.
Example


Item
Unit
108
109
110
111
Ex. 112
Ex. 113
Ex. 114
112





HFO-1132(E)
mass %
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0


R32
mass %
48.8
38.8
28.8
18.8
8.8
48.8
38.8
28.8


R1234yf
mass %
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

331
263
196
129
62
330
263
196


COP ratio
%
99.9
99.8
99.8
100.1
100.8
99.4
99.3
99.3



(relative to











R410A)










Refrigerating
%
103.2
97.5
91.0
83.7
75.6
107.5
102.0
95.8


capacity ratio
(relative to











R410A)










Condensation
° C.
1.8
2.7
3.8
5.2
6.6
1.3
2.0
2.9


glide





















Example
Example
Comp.
Comp.
Comp.
Example
Comp.
Comp.


Item
Unit
113
114
Ex. 115
Ex. 116
Ex. 117
115
Ex. 118
Ex. 119





HFO-1132(E)
mass %
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0


R32
mass %
18.8
8.8
38.8
28.8
18.8
8.8
28.8
18.8


R1234yf
mass %
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

129
62
263
196
129
62
195
128


COP ratio
%
99.5
100.0
99.0
98.9
99.0
99.4
98.7
98.7



(relative to











R410A)










Refrigerating
%
88.9
81.1
106.2
100.3
93.7
86.2
104.5
98.2


capacity ratio
(relative to











R410A)










Condensation
° C.
4.1
5.4
1.4
2.2
3.2
4.3
1.5
2.4


glide





















Comp.
Comp.
Comp.
Comp.
Example
Example
Example
Example


Item
Unit
Ex. 120
Ex. 121
Ex. 122
Ex. 123
116
117
118
119





HFO-1132(E)
mass %
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0


R32
mass %
8.8
18.8
8.8
8.8
48.8
46.3
43.8
41.3


R1234yf
mass %
30.0
10.0
20.0
10.0
35.0
37.5
40.0
42.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

61
128
61
61
331
314
297
281


COP ratio
%
99.0
98.5
98.8
98.6
100.7
100.7
100.6
100.6



(relative to











R410A)










Refrigerating
%
91.0
102.4
95.5
99.7
96.1
94.7
93.1
91.6


capacity ratio
(relative to











R410A)










Condensation
° C.
3.3
1.7
2.5
1.9
2.8
3.0
3.3
3.6


glide





















Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
120
121
122
123
124
125
126
127





HFO-1132(E)
mass %
15.0
15.0
15.0
15.0
15.0
17.5
17.5
17.5


R32
mass %
38.8
36.3
33.8
31.3
28.8
48.8
46.3
43.8


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
32.5
35.0
37.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

264
247
230
214
197
331
314
297


COP ratio
%
100.6
100.7
100.7
100.7
100.8
100.5
100.5
100.5



(relative to











R410A)










Refrigerating
%
89.9
88.3
86.6
84.8
83.0
97.4
95.9
94.4


capacity ratio
(relative to











R410A)










Condensation
° C.
3.9
4.2
4.6
4.9
5.3
2.6
2.9
3.1


glide

























TABLE 39









Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
128
129
130
131
132
133
134
135





HFO-1132(E)
mass %
17.5
17.5
17.5
17.5
17.5
17.5
17.5
20.0


R32
mass %
41.3
38.8
36.3
33.8
31.3
28.8
26.3
46.3


R1234yf
mass %
40.0
42.5
45.0
47.5
50.0
52.5
55.0
32.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

281
264
247
230
213
197
180
314


COP ratio
%
100.5
100.5
100.5
100.5
100.6
100.6
100.7
100.4



(relative to











R410A)










Refrigerating
%
92.9
91.3
89.6
87.9
86.2
84.4
82.6
97.1


capacity ratio
(relative to











R410A)










Condensation
° C.
3.4
3.7
4.0
4.3
4.7
5.1
5.4
2.7


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
136
137
138
139
140
141
142
143





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
20.0
22.5
22.5


R32
mass %
43.8
41.3
36.3
33.8
31.3
26.3
46.3
43.8


R1234yf
mass %
35.0
37.5
42.5
45.0
47.5
52.5
30.0
32.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

297
280
247
230
213
180
314
297


COP ratio
%
100.3
100.3
100.3
100.3
100.4
100.5
100.2
100.2



(relative to











R410A)










Refrigerating
%
95.7
94.1
90.9
89.3
87.5
84.0
98.4
96.9


capacity ratio
(relative to











R410A)










Condensation
° C.
2.9
3.2
3.8
4.1
4.4
5.2
2.5
2.7


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
144
145
146
147
148
149
150
151





HFO-1132(E)
mass %
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5


R32
mass %
41.3
38.8
36.3
33.8
31.3
28.8
26.3
23.8


R1234yf
mass %
35.0
37.5
40.0
42.5
45.0
47.5
50.0
52.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

280
264
247
230
213
197
180
163


COP ratio
%
100.2
100.2
100.2
100.2
100.2
100.3
100.3
100.4



(relative to











R410A)










Refrigerating
%
95.4
93.8
92.2
90.6
88.9
87.1
85.3
83.5


capacity ratio
(relative to











R410A)










Condensation
° C.
3.0
3.3
3.6
3.9
4.2
4.5
4.9
5.3


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
152
153
154
155
156
157
158
159





HFO-1132(E)
mass %
25.0
25.0
25.0
25.0
25.0
25.0
27.5
27.5


R32
mass %
33.8
31.3
28.8
26.3
23.8
21.3
21.9
21.9


R1234yf
mass %
40.0
42.5
45.0
47.5
50.0
52.5
45.0
47.5


CO2
mass %
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


GWP

230
213
196
180
163
146
150
150


COP ratio
%
100.0
100.0
100.1
100.1
100.2
100.3
100.0
100.1



(relative to











410A)










Refrigerating
%
91.8
90.2
88.4
86.7
84.8
83.0
86.3
85.4


capacity ratio
(relative to











410A)










Condensation
° C.
3.6
4.0
4.3
4.7
5.0
5.4
4.8
4.9


glide




















Example
Example
Example
Example
Example



Item
Unit
160
161
162
163
164






HFO-1132(E)
mass %
27.5
27.5
30.0
32.0
34.0



R32
mass %
21.9
21.9
21.9
21.9
13.8



R1234yf
mass %
50.0
52.5
52.5
51.0
51.0



CO2
mass %
1.2
1.2
1.2
1.2
1.2



GWP

150
150
150
150
96



COP ratio
%
100.1
100.2
100.1
100.0
100.1




(relative to









R410A)








Refrigerating
%
84.5
83.7
84.2
85.1
82.0



capacity ratio
(relative to









R410A)








Condensation
° C.
5.1
5.2
5.0
4.9
5.5



glide

























TABLE 40









Comp. Ex.
Comp. Ex
Comp. Ex.
Example
Example
Example
Comp. Ex.
Comp. Ex.


Item
Unit
125
126
127
166
167
168
128
129





HFO-1132(E)
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
77.5
67.5
57.5
47.5
37.5
275
17.5
7.5


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0


CO2
mass %
25
25
2.5
25
25
25
2.5
25


GWP

524
457
389
322
255
188
121
54


COP ratio
%
100.9
100.8
100.6
100.5
100.5
100.9
101.6
102.4



(relative to











R410A)










Refrigerating
%
110.6
106.2
101.2
95.5
89.1
81.9
74.0
64.8


capacity ratio
(relative to











R410A)










Condensation
° C.
1.8
2.3
3.0
4.0
5.3
7.0
8.8
10.1


glide







Comp. Ex.
Comp. Ex.
Example
Example
Example
Comp. Ex.
Comp. Ex.
Comp. Ex.


Item
Unit
130
131
169
170
171
132
133
134





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0


R32
mass %
67.5
57.5
47.5
37.5
27.5
17.5
7.5
57.5


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

456
389
322
255
188
121
54
389


COP ratio
%
100.1
100.0
99.9
99.8
100.0
100.5
101.3
99.5



(relative to











R410A)










Refrigerating
%
110.7
106.0
100.6
94.5
87.7
80.1
71.5
110.4


capacity ratio
(relative to











R410A)










Condensation
° C.
1.8
2.5
3.3
4.4
5.9
7.7
9.3
1.9


glide







Example
Example
Example
Example
Comp. Ex.
Comp. Ex.
Comp. Ex.
Example


Item
Unit
172
173
174
175
135
136
137
176





HFO-1132(E)
mass %
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0


R32
mass %
47.5
37.5
27.5
17.5
7.5
47.5
37.5
27.5


R1234yf
mass %
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

322
255
188
120
53
321
254
187


COP ratio
%
99.3
99.2
99.3
99.6
100.3
98.9
98.8
98.7



(relative to











R410A)










Refrigerating
%
105.3
99.5
93.0
85.7
77.5
109.6
104.1
97.9


capacity ratio
(relative to











R410A)










Condensation
° C.
2.6
3.6
4.8
6.4
8.1
2.0
2.8
3.9


glide







Example
Example
Comp. Ex
Comp. Ex.
Comp. Ex.
Example
Comp. Ex.
Comp. Ex.


Item
Unit
177
178
138
139
140
179
141
142





HFO-1132(E)
mass %
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0


R32
mass %
17.5
7.5
37.5
27.5
17.5
7.5
27.5
17.5


R1234yf
mass %
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

120
53
254
187
120
53
187
120


COP ratio
%
98.9
99.4
98.4
98.3
98.4
98.8
98.0
98.1



(relative to











R410A)










Refrigerating
%
91.0
83.1
108.4
102.5
95.9
88.4
106.8
100.4


capacity ratio
(relative to











R410A)










Condensation
° C.
5.3
6.8
2.2
3.1
4.3
5.6
2.4
3.4


glide







Example
Comp. Ex.
Comp. Ex.
Comp. Ex.
Example
Example
Example
Example


Item
Unit
180
143
144
145
181
182
183
184





HFO-1132 (E)
mass %
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0


R32
mass %
7.5
17.5
7.5
7.5
50.0
47.5
45.0
42.5


R1234yf
mass %
30.0
10.0
20.0
10.0
32.5
35.0
37.5
40.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

52
119
52
52
339
322
305
289


COP ratio
%
98.4
97.9
98.1
98.0
100.2
100.2
100.2
100.2



(relative to











R410A)










Refrigerating
%
93.3
104.7
97.8
102.1
99.6
98.1
96.6
95.1


capacity ratio
(relative to











R410A)










Condensation
° C.
4.6
2.7
3.8
3.0
3.4
3.6
3.9
4.2


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
185
186
187
188
189
190
191
192





HFO-1132(E)
mass %
15.0
15.0
15.0
15.0
15.0
15.0
15.0
17.5


R32
mass %
40.0
37.5
35.0
32.5
30.0
27.5
25.0
50.0


R1234yf
mass %
42.5
45.0
47.5
50.0
52.5
55.0
57.5
30.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

272
255
238
222
205
188
171
339


COP ratio
%
100.2
100.2
100.2
100.2
100.3
100.4
100.5
100.1



(relative to











R410A)










Refrigerating
%
93.5
91.9
90.2
88.5
86.7
84.3
83.0
100.8


capacity ratio
(relative to











R410A)










Condensation
° C.
4.5
4.8
5.2
5.6
6.0
6.4
6.9
3.2


glide

























TABLE 41









Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
193
194
195
196
197
198
199
200





HFO-1132(E)
mass %
17.5
17.5
17.5
17.5
17.5
17.5
17.5
17.5


R32
mass %
47.5
45.0
42.5
40.0
37.5
35.0
32.5
30.0


R1234yf
mass %
32.5
35.0
37.5
40.0
42.5
45.0
47.5
50.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

322
305
289
272
255
238
221
205


COP ratio
%
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.1



(relative to











R410A)










Refrigerating
%
99.4
97.9
96.4
94.8
93.2
91.5
89.8
88.1


capacity ratio
(relative to











R410A)










Condensation
° C.
3.5
3.7
4.0
4.3
4.6
5.0
5.3
5.7


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
201
202
203
204
205
206
207
208





HFO-1132(E)
mass %
17.5
17.5
17.5
20.0
20.0
20.0
20.0
20.0


R32
mass %
27.5
25.0
22.5
50.0
45.0
42.5
40.0
35.0


R1234yf
mass %
52.5
55.0
57.5
27.5
32.5
35.0
37.5
42.5


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

188
171
154
339
305
289
272
238


COP ratio
%
100.2
100.3
100.4
99.9
99.9
99.8
99.8
99.8



(relative to











R410A)










Refrigerating
%
86.3
84.4
82.6
102.0
99.2
97.7
96.1
92.9


capacity ratio
(relative to











R410A)










Condensation
° C.
6.2
6.6
7.0
3.1
3.5
3.8
4.1
4.7


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
209
210
211
212
213
214
215
216





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
22.5
22.5
22.5


R32
mass %
32.5
30.0
25.0
22.5
20.0
50.0
47.5
45.0


R1234yf
mass %
45.0
47.5
52.5
55.0
57.5
25.0
27.5
30.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

221
205
171
154
138
339
322
305


COP ratio
%
99.8
99.9
100.0
100.2
100.3
99.8
99.7
99.7



(relative to











R410A)










Refrigerating
%
91.2
89.5
85.9
84.0
82.1
103.2
101.8
100.4


capacity ratio
(relative to











R410A)










Condensation
° C.
5.1
5.5
6.3
6.7
7.2
2.9
3.1
3.4


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
217
218
219
220
221
222
223
224





HFO-1132(E)
mass %
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5


R32
mass %
42.5
40.0
37.5
35.0
32.5
30.0
27.5
25.0


R1234yf
mass %
32.5
35.0
37.5
40.0
42.5
45.0
47.5
50.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

288
272
255
238
221
205
188
171


COP ratio
%
99.7
99.7
99.7
99.7
99.7
99.7
99.8
99.8



(relative to











R410A)










Refrigerating
%
98.9
97.4
95.8
94.2
92.5
90.8
89.0
87.2


capacity ratio
(relative to











R410A)










Condensation
° C.
3.6
3.9
4.2
4.5
4.9
5.2
5.6
6.0


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
225
226
227
228
229
230
231
232





HFO-1132(E)
mass %
22.5
22.5
22.5
25.0
25.0
25.0
25.0
25.0


R32
mass %
22.5
20.0
17.5
40.0
37.5
35.0
32.5
30.0


R1234yf
mass %
52.5
55.0
57.5
32.5
35.0
37.5
40.0
42.5


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

154
137
121
272
255
238
221
204


COP ratio
%
99.9
100.1
100.2
99.5
99.5
99.5
99.5
99.5



(relative to











R410A)










Refrigerating
%
85.4
83.5
81.5
98.6
97.1
95.5
93.8
92.1


capacity ratio
(relative to











R410A)










Condensation
° C.
6.5
6.9
7.3
3.7
4.0
4.3
4.6
5.0


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
233
234
235
236
237
238
239
240





HFO-1132(E)
mass %
25.0
25.0
25.0
25.0
25.0
27.5
27.5
27.5


R32
mass %
27.5
25.0
22.5
20.0
17.5
32.5
30.0
27.5


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
37.5
40.0
42.5


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

188
171
154
137
121
221
204
188


COP ratio
%
99.6
99.6
99.7
99.9
100.0
99.4
99.4
99.4



(relative to











R410A)










Refrigerating
%
90.4
88.6
86.8
84.9
83.0
95.1
93.4
91.7


capacity ratio
(relative to











R410A)










Condensation
° C.
5.4
5.7
6.2
6.6
7.0
4.4
4.7
5.1


glide

























TABLE 42









Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
241
242
243
244
245
246
247
248





HFO-1132(E)
mass %
27.5
27.5
27.5
27.5
27.5
30.0
30.0
30.0


R32
mass %
25.0
22.5
20.0
17.5
15.0
25.0
22.5
20.0


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
42.5
45.0
47.5


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

171
154
137
121
104
171
154
137


COP ratio
%
99.5
99.5
99.6
99.8
99.9
99.3
99.4
99.5



(relative to











R410A)










Refrigerating
%
89.9
88.1
86.3
84.3
82.4
91.3
89.5
87.6


capacity ratio
(relative to











R410A)










Condensation
° C.
5.5
5.9
6.3
6.7
7.2
5.2
5.6
6.0


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
249
250
251
252
253
254
255
256





HFO-1132(E)
mass %
30.0
30.0
32.5
32.5
32.5
32.5
35.0
35.0


R32
mass %
15.0
12.5
20.0
17.5
15.0
12.5
15.0
12.5


R1234yf
mass %
52.5
55.0
45.0
47.5
50.0
52.5
47.5
50.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

104
87
137
120
104
87
104
87


COP ratio
%
99.7
99.9
99.3
99.4
99.5
99.7
99.3
99.5



(relative to











R410A)










Refrigerating
%
83.8
81.8
88.9
87.1
85.1
83.1
86.5
84.5


capacity ratio
(relative to











R410A)










Condensation
° C.
6.8
7.3
5.7
6.1
6.5
7.0
6.2
6.6


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
257
258
259
260
261
262
263
264





HFO-1132(E)
mass %
35.0
37.5
37.5
37.5
40.0
40.0
42.5
42.5


R32
mass %
10.0
12.5
10.0
7.5
10.0
5.0
7.5
5.0


R1234yf
mass %
52.5
47.5
50.0
52.5
47.5
52.5
47.5
50.0


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

70
87
70
53
70
36
53
36


COP ratio
%
99.6
99.3
99.4
99.6
99.3
99.6
99.3
99.4



(relative to











R410A)










Refrigerating
%
82.5
85.8
83.8
81.8
85.2
81.0
845
82.4


capacity ratio
(relative to











R410A)










Condensation
° C.
7.1
6.3
6.7
7.1
6.4
7.2
6.5
6.9


glide




















Example
Example
Example
Example
Example
Example
Example


Item
Unit
265
266
267
268
269
270
271





HFO-1132(E)
mass %
45.0
45.0
47.5
47.5
50.0
52.5
55.0


R32
mass %
5.0
2.5
4.0
1.5
2.5
1.5
1.0


R1234yf
mass %
47.5
50.0
46.0
48.5
45.0
43.5
41.5


CO2
mass %
2.5
2.5
2.5
2.5
2.5
2.5
2.5


GWP

36
19
29
13
19
12
9


COP ratio
%
99.3
99.4
99.2
99.3
99.1
99.1
99.0



(relative to










R410A)









Refrigerating
%
83.7
81.6
84.2
82.0
84.2
84.7
85.6


capacity ratio
(relative to










R410A)









Condensation
° C.
6.6
6.9
6.4
6.7
6.3
6.2
5.9


glide

























TABLE 43









Comp. Ex.
Comp. Ex.
Comp. Ex.
Example
Example
Example
Comp. Ex.
Comp. Ex.


Item
Unit
146
147
148
272
273
274
149
150





HFO-1132(E)
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
76.0
66.0
56.0
46.0
36.0
26.0
16.0
6.0


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

514
446
379
312
245
178
111
44


COP ratio
%
100.3
100.2
100.1
100.0
100.0
100.4
101.2
102.0



(relative to











R410A)










Refrigerating
%
113.0
108.6
103.5
97.8
91.3
84.1
76.1
66.8


capacity ratio
(relative to











R410A)










Condensation
° C.
2.5
3.1
3.9
5.0
6.4
8.3
10.4
12.2


glide







Comp. Ex.
Comp. Ex.
Example
Example
Example
Example
Comp. Ex.
Comp. Ex.


Item
Unit
146
147
275
276
277
278
153
154





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0


R32
mass %
66.0
56.0
46.0
36.0
26.0
16.0
6.0
56.0


R1234yf
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

446
379
312
245
178
111
44
379


COP ratio
%
99.6
99.5
99.3
99.2
99.4
100.0
100.9
98.9



(relative to











R410A)










Refrigerating
%
113.1
108.4
103.0
96.3
89.9
82.3
73.7
112.9


capacity ratio
(relative to











R410A)










Condensation
° C.
2.6
3.3
4.2
5.5
7.1
9.2
11.2
2.7


glide







Example
Example
Example
Example
Comp. Ex.
Comp. Ex.
Comp. Ex.
Example


Item
Unit
279
280
281
282
155
156
157
283





HFO-1132(E)
mass %
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0


R32
mass %
46.0
36.0
26.0
16.0
6.0
46.0
36.0
26.0


R1234yf
mass %
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

312
245
177
110
43
311
244
177


COP ratio
%
98.7
98.6
98.7
99.0
99.8
98.3
98.1
98.1



(relative to











R410A)










Refrigerating
%
107.7
101.9
95.4
88.0
79.9
112.1
106.6
100.4


capacity ratio
(relative to











R410A)










Condensation
° C.
3.5
4.6
6.0
7.8
9.8
2.8
3.8
5.0


glide







Example
Example
Comp. Ex.
Comp. Ex.
Example
Example
Comp. Ex.
Comp. Ex.


Item
Unit
284
285
158
159
286
287
160
161





HFO-1132(E)
mass %
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0


R32
mass %
16.0
6.0
36.0
26.0
16.0
6.0
26.0
16.0


R1234yf
mass %
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

110
43
244
177
110
43
177
109


COP ratio
%
98.3
98.8
97.7
97.7
97.8
98.2
97.3
97.4



(relative to











R410A)










Refrigerating
%
93.4
85.6
110.9
105.0
98.4
90.9
109.3
103.0


capacity ratio
(relative to











R410A)










Condensation
° C.
6.6
8.4
3.1
4.1
5.5
7.1
3.4
4.6


glide







Example
Comp. Ex.
Comp. Ex.
Comp. Ex.
Example
Example
Example
Example


Item
Unit
288
162
163
164
289
290
291
292





HFO-1132(E)
mass %
60.0
70.0
70.0
80.0
15.0
15.0
15.0
15.0


R32
mass %
6.0
16.0
6.0
6.0
48.5
46.0
43.5
41.0


R1234yf
mass %
30.0
10.0
20.0
10.0
32.5
35.0
37.5
40.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

42
109
42
42
329
312
295
279


COP ratio
%
97.7
97.2
97.4
97.2
99.7
99.6
99.6
99.6



(relative to











R410A)










Refrigerating
%
95.9
107.3
100.5
104.9
101.9
100.4
98.9
97.4


capacity ratio
(relative to











R410A)










Condensation
° C.
6.0
3.8
5.1
4.3
4.3
4.6
4.9
5.2


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
293
294
295
296
297
298
299
300





HFO-1132(E)
mass %
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0


R32
mass %
38.5
36.0
33.5
31.0
28.5
26.0
23.5
21.0


R1234yf
mass %
42.5
45.0
47.5
50.0
52.5
55.0
57.5
60.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

262
245
228
211
195
178
161
144


COP ratio
%
99.6
99.6
99.6
99.7
99.8
99.9
100.0
100.2



(relative to











R410A)










Refrigerating
%
95.8
94.1
92.4
90.7
88.9
87.1
85.2
83.3


capacity ratio
(relative to











R410A)










Condensation
° C.
5.6
5.9
6.3
6.8
7.2
7.7
8.2
8.7


glide

























TABLE 44









Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
301
302
303
304
305
306
307
308





HFO-1132(E)
mass %
15.0
17.5
17.5
17.5
17.5
17.5
17.5
17.5


R32
mass %
18.5
48.5
46.0
43.5
41.0
38.5
36.0
33.5


R1234yf
mass %
62.5
30.0
32.5
35.0
37.5
40.0
42.5
45.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

128
329
312
295
278
262
245
228


COP ratio
%
100.4
99.5
99.5
99.4
99.4
99.4
99.4
99.4



(relative to











R410A)










Refrigerating
%
81.3
103.1
101.7
100.2
98.7
97.1
95.5
93.8


capacity ratio
(relative to











R410A)










Condensation
° C.
9.3
4.1
4.4
4.7
5.0
5.3
5.7
6.1


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
309
310
311
312
313
314
315
316





HFO-1132(E)
mass %
17.5
17.5
17.5
17.5
17.5
17.5
20.0
20.0


R32
mass %
31.0
28.5
26.0
23.5
21.0
18.5
48.5
43.5


R1234yf
mass %
47.5
50.0
52.5
55.0
57.5
60.0
27.5
32.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

211
195
178
161
144
127
329
295


COP ratio
%
99.5
99.5
99.6
99.8
99.9
100.1
99.3
99.3



(relative to











R410A)










Refrigerating
%
92.1
90.3
88.5
86.7
84.8
82.8
104.4
101.5


capacity ratio
(relative to











R410A)










Condensation
° C.
6.5
7.0
7.4
7.9
8.4
9.0
4.0
4.5


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
317
318
319
320
321
322
323
324





HFO-1132(E)
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0


R32
mass %
41.0
38.5
33.5
31.0
28.5
23.5
21.0
18.5


R1234yf
mass %
35.0
37.5
42.5
45.0
47.5
52.5
55.0
57.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

278
262
228
211
195
161
144
127


COP ratio
%
99.3
99.2
99.3
99.3
99.3
99.5
99.6
99.8



(relative to











R410A)










Refrigerating
%
100.0
98.4
95.2
93.5
91.7
88.1
86.2
84.3


capacity ratio
(relative to











R410A)










Condensation
° C.
4.8
5.1
5.8
6.2
6.7
7.6
8.1
8.6


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
325
326
327
328
329
330
331
332





HFO-1132(E)
mass %
22.5
22.5
22.5
22.5
22.5
22.5
22.5
22.5


R32
mass %
48.5
46.0
43.5
41.0
38.5
36.0
33.5
31.0


R1234yf
mass %
25.0
27.5
30.0
32.5
35.0
37.5
40.0
42.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

329
312
295
278
262
245
228
211


COP ratio
%
99.2
99.2
99.1
99.1
99.1
99.1
99.1
99.1



(relative to











R410A)










Refrigerating
%
105.6
104.2
102.7
101.3
99.7
98.1
96.5
94.8


capacity ratio
(relative to











R410A)










Condensation
° C.
3.8
4.0
4.3
4.6
4.3
5.2
5.6
6.0


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
333
334
335
336
337
338
339
340





HFO-1132(E)
mass %
22.5
22.5
22.5
22.5
22.5
22.5
22.5
25.0


R32
mass %
28.5
26.0
23.5
21.0
18.5
16.0
13.5
43.5


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
57.5
60.0
27.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

194
178
161
144
127
111
94
295


COP ratio
%
99.1
99.2
99.3
99.4
99.5
99.7
99.9
99.0



(relative to











R410A)










Refrigerating
%
93.1
91.3
89.5
87.7
85.8
83.8
81.8
104.0


capacity ratio
(relative to











R410A)










Condensation
° C.
6.4
6.8
7.3
7.8
8.3
8.8
9.3
4.1


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
341
342
343
344
345
346
347
348





HFO-1132(E)
mass %
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0


R32
mass %
41.0
38.5
36.0
33.5
31.0
28.5
26.0
23.5


R1234yf
mass %
30.0
32.5
35.0
37.5
40.0
42.5
45.0
47.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

278
261
245
228
211
194
178
161


COP ratio
%
98.9
98.9
98.9
98.9
98.9
99.0
99.0
99.1



(relative to











R410A)










Refrigerating
%
102.5
101.0
99.4
97.8
96.1
94.4
92.7
90.9


capacity ratio
(relative to











R410A)










Condensation
° C.
4.4
4.7
5.0
5.4
5.7
6.1
6.5
7.0


glide

























TABLE 45









Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
349
350
351
352
353
354
355
356





HFO-1132(E)
mass %
25.0
25.0
25.0
25.0
27.5
27.5
27.5
27.5


R32
mass %
21.0
18.5
16.0
13.5
35.0
31.0
28.5
26.0


R1234yf
mass %
50.0
52.5
55.0
57.5
35.0
37.5
40.0
42.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

144
127
110
94
238
211
194
178


COP ratio
%
99.2
99.3
99.5
99.7
98.8
98.8
98.3
98.8



(relative to



R410A)


Refrigerating
%
89.1
87.2
85.2
83.2
99.4
97.4
95.8
94.0


capacity ratio
(relative to



R410A)


Condensation
° C.
7.5
8.0
8.5
9.0
5.0
5.5
5.9
6.3


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
357
358
359
360
361
362
363
364





HFO-1132(E)
mass %
27.5
27.5
27.5
27.5
27.5
27.5
30.0
30.0


R32
mass %
23.5
21.0
18.5
16.0
13.5
11.0
23.5
21.0


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
57.5
42.5
45.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

161
144
127
110
94
77
161
144


COP ratio
%
98.9
99.0
99.1
99.2
99.4
99.6
98.7
98.8



(relative to



R410A)


Refrigerating
%
92.3
90.4
88.6
86.7
84.7
82.6
93.6
91.8


capacity ratio
(relative to



R410A)


Condensation
° C.
6.7
7.2
7.6
8.1
8.7
9.2
6.4
6.9


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
365
366
367
368
369
400
401
402





HFO-1132(E)
mass %
30.0
30.0
30.0
30.0
32.5
32.5
32.5
32.5


R32
mass %
18.5
13.5
11.0
8.5
21.0
18.5
16.0
35.0


R1234yf
mass %
47.5
52.5
55.0
57.5
42.5
45.0
47.5
50.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

127
94
77
60
144
127
110
239


COP ratio
%
98.9
99.2
99.3
99.5
98.6
98.7
98.8
99.1



(relative to



R410A)


Refrigerating
%
89.9
86.1
84.1
82.0
93.1
91.3
89.4
94.0


capacity ratio
(relative to



R410A)


Condensation
° C.
7.3
8.3
8.8
9.3
6.6
7.0
7.5
5.5


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
403
404
405
406
407
408
409
410





HFO-1132(E)
mass %
32.5
32.5
32.5
35.0
35.0
35.0
35.0
35.0


R32
mass %
11.0
8.5
6.0
16.0
13.5
11.0
8.5
6.0


R1234yf
mass %
52.5
55.0
57.5
45.0
47.5
50.0
52.5
55.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

77
60
43
110
93
77
60
43


COP ratio
%
99.1
99.3
99.5
98.6
98.7
98.9
99.1
99.3



(relative to



R410A)


Refrigerating
%
85.5
83.4
81.3
90.8
88.8
86.9
84.8
82.8


capacity ratio
(relative to



R410A)


Condensation
° C.
8.5
9.0
9.5
7.2
7.6
8.1
8.6
9.1


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
411
412
413
414
415
416
417
418





HFO-1132(E)
mass %
37.5
37.5
37.5
37.5
37.5
40.0
40.0
40.0


R32
mass %
13.5
11.0
8.5
6.0
3.5
11.0
8.5
3.5


R1234yf
mass %
45.0
47.5
50.0
52.5
55.0
45.0
47.5
52.5


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

93
77
60
43
26
76
60
26


COP ratio
%
98.6
98.7
98.9
99.0
99.2
98.5
98.7
99.0



(relative to



R410A)


Refrigerating
%
90.2
88.2
86.2
84.2
82.0
89.6
87.6
83.4


capacity ratio
(relative to



R410A)


Condensation
° C.
7.3
7.8
8.3
8.8
9.2
7.5
7.9
8.9


glide







Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
419
420
421
422
423
424
425
426





HFO-1132(E)
mass %
40.0
42.5
42.5
42.5
42.5
45.0
45.0
45.0


R32
mass %
1.0
8.5
35.0
3.5
1.0
6.0
3.5
1.0


R1234yf
mass %
55.0
45.0
47.5
50.0
52.5
45.0
47.5
50.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


GWP

9
60
239
26
9
43
26
9


COP ratio
%
99.2
98.5
98.8
98.8
99.0
98.5
98.6
98.8



(relative to



R410A)


Refrigerating
%
81.2
88.9
95.6
84.8
82.6
88.3
86.2
84.0


capacity ratio
(relative to



R410A)


Condensation
° C.
9.3
7.6
5.0
8.5
9.0
7.8
8.2
8.7


glide























TABLE 46







Example
Example
Example
Example
Example
Example


Item
Unit
427
428
429
430
431
432






















HFO-1132(E)
mass %
47.5
47.5
50.0
50.0
52.5
55.0


R32
mass %
4.5
2.0
3.5
1.0
2.0
1.0


R1234yf
mass %
44.0
46.5
42.5
45.0
41.5
40.0


CO2
mass %
4.0
4.0
4.0
4.0
4.0
4.0


GWP

33
16
26
9
16
9


COP ratio
%
98.4
98.6
98.3
98.5
98.3
98.2



(relative



to R410A)


Refrigerating
%
88.4
86.3
88.9
86.8
88.9
89.4


capacity ratio
(relative



to R410A)


Condensation
° C.
7.7
8.1
7.6
8.0
7.5
7.4


glide









These results indicate that under the condition that the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z, when coordinates (x,y,z) in a ternary composition diagram (FIGS. 2 to 9) in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are on straight line A″B″, the mixed refrigerant has a GWP of 350, and when coordinates (x,y,z) in the ternary composition diagram are positioned on the right side of the line, the mixed refrigerant has a GWP of less than 350. The results also indicate that when coordinates (x,y,z) in the ternary composition diagram of FIGS. 2 to 9 are on straight line A′B′, the mixed refrigerant has a GWP of 250, and that when coordinates (x,y,z) in the ternary composition diagram are positioned on the right side of the line, the mixed refrigerant has a GWP of less than 250. Further, the results also indicate that when coordinates (x,y,z) in the ternary composition diagram of FIGS. 2 to 9 are on straight line AB, the mixed refrigerant has a GWP of 125, and that when coordinates (x,y,z) in the ternary composition diagram are positioned on the right side of the line, the mixed refrigerant has a GWP of less than 125.


It is found that the straight line connecting points D and C is positioned on the slightly left side of the curve connecting points at which the refrigerating capacity ratio relative to R410A is 80%. Accordingly, it is indicated that when the coordinates (x, y, z) are on the left side of the straight line connecting points D and C, the refrigerating capacity ratio of the mixed refrigerant is 80% or more relative to R410A.


Coordinates of points A and B, A′ and B′, and A″ and B″ were determined by obtaining the approximate expression based on each of the points shown in the above tables. Specifically, calculation was performed according to Table 47 (points A and B), Table 48 (points A′ and B′), and Table 49 (points A″ and B″).












TABLE 47





Item
1.2 ≥ CO2 > 0
4.0 ≥ CO2 ≥ 1.2
7.0 ≥ CO2 ≥ 4.0















Point A
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
81.6
81.0
80.4
80.4
79.1
77.6
77.6
76.1
74.6


R32
18.4
18.4
18.4
18.4
18.4
18.4
18.4
18.4
18.4


R1234yf
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0










CO2
W
w
w


Approximate
−w + 81.6
−w + 81.6
−w + 81.6


formula of


HFO-1132 (E)


Approximate
18.4
18.4
18.4


formula of


R32


Approximate
 0.0
 0.0
 0.0


formula of


R1234yf







Point B
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R32
18.1
18.1
18.1
18.1
18.1
18.1
18.1
18.1
18.1


R1234yf
81.9
81.3
80.7
80.7
79.4
77.9
77.9
76.4
74.9










CO2
w
w
W


Approximate
 0.0
 0.0
 0.0


formula of


HFO-1132 (E)


Approximate
18.1
18.1
18.1


formula of


R32


Approximate
−w + 81.9
−w + 81.9
−w + 81.9


formula of


R1234yf



















TABLE 48





Item
1.2 ≥ CO2 > 0
4.0 ≥ CO2 ≥ 1.2
7.0 ≥ CO2 ≥ 4.0















Point A′
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
63.1
62.5
61.9
61.9
60.6
59.1
59.1
57.6
56.1


R32
36.9
36.9
36.9
36.9
36.9
36.9
36.9
36.9
36.9


R1234yf
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0










CO2
w
w
w


Approximate
−w + 63.1
−w + 63.1
−w + 63.1


formula of


HFO-1132 (E)


Approximate
36.9
36.9
36.9


formula of


R32


Approximate
 0.0
 0.0
 0.0


formula of


R1234yf







Point B′
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R32
36.7
36.7
36.6
36.6
36.6
36.6
36.6
36.6
36.6


R1234yf
63.3
62.7
62.2
62.2
60.9
59.4
59.4
57.9
56.4










CO2
w
w
w


Approximate
0 
 0.0
 0.0


formula of


HFO-1132 (E)


Approximate
100-R1234yf-CO2
36.6
36.6


formula of


R32


Approximate
−0.9167w + 63.283
−w + 63.4
−w + 63.4


formula of


R1234yf



















TABLE 49





Item
1.2 ≥ CO2 > 0
4.0 ≥ CO2 ≥ 1.2
7.0 ≥ CO2 ≥ 4.0















Point A″
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
48.2
47.6
47.0
47.0
45.7
44.2
44.2
42.7
41.2


R32
51.8
51.8
51.θ
51.8
51.8
51.8
51.8
51.8
51.8


R1234yf
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0










CO2
W
w
w


Approximate
−w + 48.2
−w + 48.2
−w + 48.2


formula of


HFO-1132 (E)


Approximate
51.8 
51.8
51.8


formula of


R32


Approximate
0.0
 0.0
 0.0


formula of


R1234yf







Point B″
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R32
51.5
51.6
51.6
51.6
51.6
51.6
51.6
51.6
51.6


R1234yf
49.5
47.8
47.2
47.2
45.9
44.4
44.4
42.9
41.4










CO2
W
w
w


Approximate
0.0
 0.0
 0.0


formula of


HFO-1132 (E)


Approximate
100-R1234yf-CO2
51.6
51.6


formula of


R32


Approximate
1.5278W2 − 3.75w + 49.5
−w + 48.4
−w + 48.4


formula of


R1234yf









Coordinates C to G were determined by obtaining the approximate expression based on each of the points shown in the above tables. Specifically, calculation was performed according to Tables 50 and 51.












TABLE 50







Item
1.2 ≥ CO2 > 0
4.0 ≥ CO2 ≥ 1.2
7.0 ≥ CO2 ≥ 4.0










Point C
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
58.3
55.4
52.4
52.4
46.2
39.5
39.5
33.0
26.8


R32
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234yf
41.7
44.0
46.4
46.4
51.3
56.5
56.5
61.5
66.2










CO2
w
w
w


Approximate
−4.9167w + 58.317
0.1081w2
0.0667w2


formula of

5.169w + 58.447
4.9667w + 58.3


HFO-1132 (E)


Approximate
0.0
0.0
0.0


formula of


R32


Approximate
100-E-HFO-1132-CO2
100-E-HFO-1132-CO2
100-E-HFO-1132-CO2


formula of


R1234yf







Point D
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R32
40.3
38.6
36.8
36.8
33.2
28.9
28.9
24.7
20.5


R1234yf
59.7
60.8
62.0
62.0
64.3
67.1
67.1
69.8
72.5










CO2
w
W
w


Approximate
0.0
0.0
0.0


formula of


HFO-1132 (E)


Approximate
−2.9167w + 40.317
−2.8226w + 40.211
−2.8w + 40.1


formula of


R32


Approximate
100-R32-CO2
100-R32-CO2
100-R32-CO2


formula of


R1234yf







Point E
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
31.9
29.6
26.5
26.5
20.9
14.7
14.7
8.8
3.1


R32
18.2
18.2
18.2
18.2
18.2
18.1
18.1
18.1
18.1


R1234yf
49.9
51.6
54.1
54.1
58.4
63.2
63.2
67.6
71.8










CO2
w
W
W


Approximate
−1.1111w2
0.0623w2
0.0444w2


formula of
3.1667w + 31.9
4.5381w + 31.856
4.3556w + 31.411


HFO-1132 (E)


Approximate
18.2 
−0.0365w + 18.26
18.1 


formula of


R32


Approximate
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2


formula of


R1234yf












Item
1.2 ≥ CO2 > 0
1.3 ≥ CO2 > 1.2







Point F















CO2
0.0
0.6
1.2
1.2
1.3


E-HFO-1132
5.2
2.7
0.3
0.3
0


R32
36.7
36.7
36.6
36.6
36.6


R1234yf
58.1
60.0
61.9
61.9
62.1









CO2
W
w


Approximate
−4.0833w + 5.1833
−3w + 3.9


formula of


HFO-1132 (E)


Approximate
−0.0833w + 36.717
36.6


formula of


R32


Approximate
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2


formula of


R1234yf













Item
1.2 ≥ CO2 ≥ 0







Point G















CO2
0.0
0.6
1.2



E-HFO-1132
26.2
29.6
38.1



R32
22.2
18.2
10.0



R1234yf
51.6
51.6
50.7










CO2
w



Approximate
7.0833w2 + l.4167w + 26.2



formula of



HFO-1132 (E)



Approximate
−5.8333w2



formula of R32
3.1667w + 22.2



Approximate
100-E-HFO-1132-R32-CO2



formula of



R1234yf




















TABLE 51





Item
1.2 ≥ CO2 > 0
4.0 ≥ CO2 ≥ 1.2
7.0 ≥ CO2 ≥ 4.0















Point M
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
52.6
55.4
58.0
58.0
59.7
60.4
0.0
33.0
26.8


R32
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234yf
47.4
44.0
40.8
40.8
37.8
35.6
56.5
61.5
66.2










CO2
w
w
w


Approximate
100-E-HFO-1132-R1234yf-CO2
100-E-HFO-1132-R1234yf-CO2
100-E-HFO-1132-R1234yf-CO2


formula of


HFO-1132 (E)


Approximate
 0.0
 0.0
 0.0


formula of


R32


Approximate
0.2778w2
0.3004w2
0.0667w2


formula of
5.8333w + 47.4
3.419w + 44.47
1.8333w + 41.867


R1234yf







Point W
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
32.4
35.1
38.1
38.1
40.9
42.6
42.6
43.3
43.7


R32
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R1234yf
57.6
54.3
50.7
50.7
46.6
43.4
43.4
41.2
39.3










CO2
W
w
w


Approximate
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2


formula of


HFO-1132 (E)


Approximate
10.0
10.0
10.0


formula of


R32


Approximate
−0.4167w2
0.3645w2
0.0667w2


formula of
5.25w + 57.6
4.5024w + 55.578
2.1w + 50.733


R1234yf







Point N
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
27.7
29.6
31.7
31.7
34.2
35.5
35.5
36.3
36.7


R32
18.2
18.2
18.2
18.2
18.2
18.2
18.2
18.2
18.2


R1234yf
54.1
51.6
48.9
48.9
45.1
42.3
42.3
40.0
38.1










CO2
w
w
w


Approximate
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2


formula of


HFO-1132 (E)


Approximate
18.2
18.2
18.2


formula of


R32


Approximate
−0.2778w2
0.3773w2
0.0889w2


formula of
4w + 54.1
4.319w + 53.54
2.3778w + 50.389


R1234yf







Point O
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
22.6
24.0
25.4
25.4
27.2
28.0
28.0
28.4
28.6


R32
36.8
36.8
36.8
36.8
36.8
36.8
36.8
36.8
36.8


R1234yf
40.6
38.6
36.0
36.0
33.5
31.2
31.2
29.3
27.6










CO2
w
w
w


Approximate
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2


formula of


HFO-1132 (E)


Approximate
36.8
36.8
36.8


formula of


R32


Approximate
−0.8333w2
0.1392w2
0.0444w2


formula of
2.8333w + 40.6
2.4381w + 38.725
1.6889w + 37.244


R1234yf







Point P
















CO2
0.0
0.6
1.2
1.2
2.5
4.0
4.0
5.5
7.0


E-HFO-1132
20.5
20.9
22.1
22.1
23.4
23.9
23.9
24.2
24.2


R32
51.7
51.7
51.7
51.7
51.7
51.7
51.7
51.7
51.7


R1234yf
27.8
26.8
25.0
25.0
22.4
20.4
20.4
18.6
17.1










CO2
W
w
w


Approximate
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2
100-R32-R1234yf-CO2


formula of


HFO-1132 (E)


Approximate
51.7
51.7
51.7


formula of


R32


Approximate
−1.1111w2
0.2381w2
0.0667w2


formula of
w + 27.8
2.881w + 28.114
1.8333w + 26.667


R1234yf









Coordinates of the points on the curves IJ, JK, and KL were determined by obtaining the approximate expression based on each of the points shown in the above tables. Specifically, calculation was performed according to Table 52.









TABLE 52







E-HFO-1132 approximate expression when x = R32
















Refrigerant type
I
Example
J
J
Example
K
K
Example
L




















CO2
R32
0.0
10.0
18.3
18.3
27.6
36.8
36.8
44.2
51.7


0.0
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
28.0
32.8
33.2
33.2
31.2
27.6
27.6
23.8
19.4


0.6
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
27.4
32.2
32.6
32.6
30.6
27.0
27.0
23.2
18.8


1.2
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
26.8
31.6
32.0
32.0
30.0
26.4
26.4
22.6
18.2


2.5
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
25.5
30.3
30.7
30.7
28.7
25.1
25.1
21.3
16.9


4.0
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
24.0
28.8
29.2
29.2
27.2
23.6
23.6
19.8
15.4


5.5
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
22.5
27.3
27.7
27.7
25.7
22.1
22..1
18.3
13.9


7.0
E-HFO-1132
72.0
57.2
48.5
48.5
41.2
35.6
35.6
32.0
28.9



R1234yf
21.0
25.8
26.2
26.2
24.2
20.6
20.6
16.8
12.4











w =
Approximate
0.0236x2
0.0095x2
0.0049x2


CO2
formula of
1.716x + 72
1.2222x + 67.676
0.8842x + 61.488



E-HFO-1132



when x = R32



R1234yf
100-E-HFO-1132-x-w
100-E-HFO-1132-x-w
100-E-HFO-1132-x-w









Coordinates of the points on the curves MW and WM were determined by obtaining the approximate expression based on each of the points shown in the above tables. Specifically, calculation was performed according to Table 53 (when 0 mass %<CO2 concentration≤1.2 mass %), Table 54 (when 1.2 mass %<CO2 concentration≤4.0 mass %), and Table 55 (when 4.0 mass %<CO2 concentration≤7.0 mass %).









TABLE 53







1.2 ≥ CO2 > 0














M
Example
W
W
Example
N


Item
0.0
5.0
10.0
10.0
14.5
18.2
















CO2 = 0 mass %
52.6
39.2
32.4
32.4
29.3
27.7









Approximate
0.132x2
0.0313x2


formula of
3.34x + 52.6
1.4551x + 43.824


E-HFO-1132


when x = R32













CO2 = 0.6 mass %
55.4
42.4
35.1
35.1
31.6
29.6









Approximate
0.114x2
0.0289x2


formula of
3.17x + 55.4
1.4866x + 47.073


E-HFO-1132


when x = R32













CO2 = 1.2 mass %
58.0
45.2
38.1
38.1
34.0
31.7









Approximate
0.114x2
0.0353x2


formula of
3.13x + 58.0
1.776x + 52.330


E-HFO-1132


when x = R32







In ax2 + bx + c, which is the approximate formula of E-HFO-1132,


approximate formulas of coefficients a, b, and c when w = CO2


concentration









Approximate
0.025w2
0.0122w2


formula of
0.045w + 0.132
0.0113w + 0.0313


coefficient a


Approximate
−0.1806w2 +
−0.3582w2 +


formula of
0.3917w − 3.34
0.1624w − 1.4551


coefficient b


Approximate
−0.2778w2 +
2.7889w2 +


formula of
4.8333w + 52.6
3.7417w + 43.824


coefficient c


Approximate
(0.025w2 − 0.045w +
(0.0122w2 − 0.0113w +


formula of
0.132)x2 + (−0.1806w2 +
0.0313)x2 + (−0.3582w2 +


E-HFO-1132
0.3917w − 3.34)x + (−0.2778w2 +
0.1624w − 1.4551)x + (2.7889w2 +


when x = R32,
4.8333w + 52.6)
3.7417w + 43.824)


w = CO2, and


1.2 ≥ w > 0


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2
















TABLE 54







4.0 ≥ CO2 ≥ 1.2














M
Example
W
W
Example
N


Item
0.0
5.0
10.0
10.0
14.5
18.2
















CO2 = 1.2 mass %
58
45.2
38.1
38.1
34
31.7









Approximate
0.114x2
0.0353x2


formula of
3.13x + 58.0
1.776x + 52.330


E-HFO-1132


when x = R32













CO2 = 2.5 mass %
59.7
48.1
40.9
40.9
36.9
34.2









Approximate
0.088x2
0.0194x2


formula of
2.76x + 59.7
1.3644x + 52.603


E-HFO-1132


when x = R32













CO2 = 4.0 mass %
60.4
49.6
42.6
42.6
38.3
35.5









Approximate
0.076x2
0.0242x2


formula of
2.54x + 60.4
1.5495x + 55.671


E-HFO-1132


when x = R32







In the approximate formula of E-HFO-1132 ax2 + bx + c, approximate


formulas of coefficients a, b, and c when w = CO2 concentration









Approximate
0.0043w2
0.0055w2


formula of
0.0359w + 0.1509
0.0326w + 0.0665


coefficient a


Approximate
−0.0493w2 +
−0.1571w2 +


formula of
0.4669w − 3.6193
0.8981w − 2.6274


coefficient b


Approximate
−0.3004w2 +
0.6555w2


formula of
2.419w + 55.53
2.2153w + 54.044


coefficient c


Approximate
(0.0043w2 − 0.0359w +
(0.0055w2 − 0.0326w +


formula of
0.1509)x2 + (−0.0493w2 +
0.0665)x2 + (−0.1571w2 +


E-HFO-1132
0.4669w − 3.6193)x + (−0.3004w2 +
0.8981w − 2.6274)x + (0.6555w2 −


when x = R32,
2.419w + 55.53)
2.2153w + 54.044)


w = CO2, and


4.0 ≥ w ≥ 1.2


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2
















TABLE 55







7.0 ≥ CO2 ≥ 4.0














M
Example
W
W
Example
N


Item
0.0
5.0
10.0
10.0
14.5
18.2
















CO2 = 4.0 mass %
60.4
49.6
42.6
42.6
38.3
35.5









Approximate
0.076x2
0.0242x2


formula of
2.54x + 60.4
1.5495x + 55.671


E-HFO-1132


when x = R32













CO2 = 5.5 mass %
60.7
50.3
43.3
43.3
39
36.3









Approximate
0.068x2
0.0275x2


formula of
2.42x + 60.7
1.6303x + 56.849


E-HFO-1132


when x = R32













CO2 = 7.0 mass %
60.7
50.3
43.7
43.7
39.5
36.7









Approximate
0.076x2
0.0215x2


formula of
2.46x + 60.7
1.4609x + 56.156


E-HFO-1132


when x = R32







In ax2 + bx + c, which is the approximate formula of E-HFO-1132, approximate


formulas of coefficients a, b, and c when w = CO2 concentration









Approximate
0.00357w2
−0.002061w2 +


formula of
0.0391w + 0.1756
0.0218w − 0.0301


coefficient a


Approximate
−0.0356w2 +
0.0556w2


formula of
0.4178w − 3.6422
0.5821w − 0.1108


coefficient b


Approximate
−0.0667w2 +
− 0.4158w2 +


formula of
0.8333w + 58.103
4.7352w + 43.383


coefficient c


Approximate
(0.00357w2 − 0.0391w +
(−0.002061w2 + 0.0218w −


formula of
0.1756)x2 + (−0.0356w2 +
0.0301)x2 + (0.0556w2


E-HFO-1132
0.4178w − 3.6422)x +
0.5821w − 0.1108)x +


when x = R32,
(−0.0667w2 + 0.8333w + 58.103)
(−0.4158w2 + 4.7352w + 43.383)


w = CO2, and


7.0 ≥ w ≥ 4.0


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2









Coordinates of the points on the curves NO and OP were determined by obtaining the approximate expression based on each of the points shown in the above tables. Specifically, calculation was performed according to Table 56 (when 0 mass %<CO2 concentration≤1.2 mass %), Table 57 (when 1.2 mass %<CO2 concentration≤4.0 mass %), and Table 58 (when 4.0 mass %<CO2 concentration≤7.0 mass %).









TABLE 56







1.2 ≥ CO2 > 0














N
Example
O
O
Example
P


Item
18.2
27.6
36.8
36.8
44.2
51.7
















CO2 = 0 mass %
27.7
24.5
22.6
22.6
21.2
20.5









Approximate
0.0072x2
0.0064x2


formula of
0.6701x + 37.512
0.7103x + 40.07


E-HFO-1132


when x = R32













CO2 = 0.6 mass %
29.6
26.3
24
24
22.4
20.9









Approximate
0.0054x2
0.0011x2


formula of
0.5999x + 38.719
0.3044x + 33.727


E-HFO-1132


when x = R32













CO2 = 1.2 mass %
31.7
27.9
25.4
25.4
23.7
22.1









Approximate
0.0071x2
0.0011x2


formula of
0.7306x + 42.636
0.3189x + 35.644


E-HFO-1132


when x = R32







In ax2 + bx + c, which is the approximate formula of E-HFO-1132, approximate


formulas of coefficients a, b, and c when w = CO2 concentration









Approximate
0.00487w2
0.0074w2


formula of
0.0059w + 0.0072
0.0133w + 0.0064


coefficient a


Approximate
−0.279w2 +
−0.5839w2 +


formula of
0.2844w − 0.6701
1.0268w − 0.7103


coefficient b


Approximate
3.7639w2
11.472w2


formula of
0.2467w + 37.512
17.455w + 40.07


coefficient c


Approximate
(0.00487w2 − 0.0059w +
(0.0074w2 − 0.0133w +


formula of
0.0072)x2 + (−0.279w2 +
0.0064)x2 + (−0.5839w2 +


E-HFO-1132
0.2844w − 0.6701)x + (3.7639w2
1.0268w − 0.7103)x + (11.472w2


when x = R32,
0.2467w + 37.512)
17.455w + 40.07)


w = CO2, and


1.2 ≥ w > 0


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2
















TABLE 57







4.0 ≥ CO2 ≥ 1.2














N
Example
O
O
Example
P


Item
18.2
27.6
36.8
36.8
44.2
51.7
















CO2 = 1.2 mass %
31.7
27.9
25.4
25.4
23.7
22.1









Approximate
0.0071x2 − 0.7306x + 42.636
0.0011x2 − 0.3189x + 35.644


formula of


E-HFO-1132


when x = R32













CO2 = 2.5 mass %
34.2
29.9
27.2
27.2
25.2
23.4









Approximate
0.0088x2 − 0.8612x + 46.954
0.002x2 − 0.4348x + 40.5 


formula of


E-HFO-1132


when x = R32













CO2 = 4.0 mass %
35.5
31
28
28
25.9
23.9









Approximate
0.0082x2 − 0.8546x + 48.335
0.0011x2 − 0.3768x + 40.412


formula of


E-HFO-1132


when x = R32







In ax2 + bx + c, which is the approximate formula of E-HFO-1132,


approximate formulas of coefficients a, b, and c when w = CO2


concentration









Approximate
−0.00062w2 + 0.0036w + 0.0037
−0.000463w2 + 0.0024w − 0.0011


formula of


coefficient a


Approximate
0.0375w2 − 0.239w − 0.4977
0.0457w2 − 0.2581w − 0.075


formula of


coefficient b


Approximate
−0.8575w2 + 6.4941w + 36.078
−1.355w2 + 8.749w + 27.096


formula of


coefficient c


Approximate
(−0.00062w2 + 0.0036w + 0.0037)x2 +
(−0.000463w2 + 0.0024w −


formula of
(0.0375w2 − 0.239w −
0.0011)x2 + (0.0457w2 − 0.2581w −


E-HFO-1132
0.4977)x + (−0.8575w2 + 6.4941w +
0.075)x + (−1.355w2 + 8.749w +


when x = R32,
36.078)
27.096)


w = CO2, and


4.0 ≥ w ≥ 1.2


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2
















TABLE 58







7.0 ≥ CO2 ≥ 4.0














N
Example
O
O
Example
P


Item
18.2
27.6
36.8
36.8
44.2
51.7
















CO2 = 4.0 mass %
35.5
31.0
28.0
28.0
25.9
23.9









Approximate
0.0082x2 − 0.8546x + 48.335
0.0011x2 − 0.3768x + 40.412


formula of


E-HFO-1132 when


x = R32













CO2 = 5.5 mass %
36.3
31.6
28.4
28.4
26.2
24.2









Approximate
0.0082x2 − 0.8747x + 49.51 
0.0021x2 − 0.4638x + 42.584


formula of


E-HFO-1132 when


x = R32













CO2 = 7.0 mass %
36.7
31.9
28.6
28.6
26.4
24.2









Approximate
0.0082x2 − 0.8848x + 50.097
0.0003x2 − 0.3188x + 39.923


formula of


E-HFO-1132 when


x = R32







In ax2 + bx + c, which is the approximate formula of E-HFO-1132,


approximate formulas of coefficients a, b, and c when w = CO2


concentration









Approximate
0.0082
−0.0006258w2 + 0.0066w −


formula of

0.0153


coefficient a


Approximate
0.0022w2 − 0.0345w − 0.7521
0.0516w2 − 0.5478w + 0.9894


formula of


coefficient b


Approximate
−0.1307w2 + 2.0247w + 42.327
−1.074w2 + 11.651w + 10.992


formula of


coefficient c


Approximate
0.0082x2 + (0.0022w2
(−0.0006258w2 + 0.0066w −


formula of
0.0345w − 0.7521)x +
0.0153)x2 + (0.0516w2 −


E-HFO-1132 when
(−0.1307w2 + 2.0247w + 42.327)
0.5478w + 0.9894)x +


x = R32, w = CO2,

(−1.074w2 + 11.651w + 10.992)


and 7.0 ≥ w ≥ 4.0


R1234yf
100-E-HFO-1132-R32-CO2
100-E-HFO-1132-R32-CO2









5. Refrigerants 1 to 5

Refrigerants 1 to 5 used in the present disclosure are described in detail below.


The disclosures of Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, and Refrigerant 5 are independent from each other. Thus, the alphabetical letters used for points and line segments, as well as the numbers used for Examples and Comparative Examples, are all independent in each of Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, and Refrigerant 5. For example, Example 1 of Refrigerant 1 and Example 1 of Refrigerant 2 each represent an example according to a different embodiment.


5.1. Refrigerant 1

In an embodiment, the refrigerant according to the present disclosure comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of 35.0 to 65.0 mass %, and HFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as “Refrigerant 1.”


In the present disclosure, Refrigerant 1 is for use in operating a refrigeration cycle in which the evaporating temperature is −75 to −5° C.


Refrigerant 1 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP equivalent to or higher than that of R404A; and (3) it has a refrigerating capacity equivalent to or higher than that of R404A.


Since Refrigerant 1 comprises HFO-1132 (E) in an amount of 35.0 mass % or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 1 has a refrigerating capacity equivalent to or higher than that of R404A.


Moreover, since Refrigerant 1 comprises HFO-1132 (E) in an amount of 65.0 mass % or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of Refrigerant 1 at a saturation temperature of 40° C. in the refrigeration cycle can be maintained within a suitable range (in particular 2.10 Mpa or less).


Refrigerant 1 may have a refrigerating capacity of 95% or more, preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more, relative to that of R404A.


Since the GWP is 100 or less, Refrigerant 1 can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants.


In Refrigerant 1, the ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) relative to that of R404A is preferably high, from the viewpoint of energy consumption efficiency. Specifically, the COP relative to that of R404A is preferably 98% or more, more preferably 100% or more, and particularly preferably 102% or more.


In Refrigerant 1, it is preferred that HFO-1132 (E) be present in an amount of 40.5 to 59.0 mass %, and HFO-1234yf be present in an amount of 59.5 to 41.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, it is more preferred that HFO-1132 (E) be present in an amount of 41.3 to 59.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 41.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, it is further preferred that HFO-1132 (E) be present in an amount of 41.3 to 55.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 45.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, it is particularly preferred that HFO-1132 (E) be present in an amount of 41.3 to 53.5 mass %, and HFO-1234yf be present in an amount of 58.7 to 46.5 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, it is particularly preferred that HFO-1132 (E) be present in an amount of 41.3 to 51.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 49.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, it is most preferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, the saturation pressure at a saturation temperature of 40° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40° C. is within the above range, Refrigerant 1 is applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 1, the saturation pressure at a saturation temperature of 40° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40° C. is within the above range, Refrigerant 1 is applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In the present disclosure, when Refrigerant 1 is used for operating a refrigeration cycle, the discharge temperature is preferably 150° C. or lower, more preferably 140° C. or lower, even more preferably 130° C. or lower, and particularly preferably 120° C. or lower, from the viewpoint of extending the life of the components of a commercially available refrigeration apparatus for R404A.


The use of Refrigerant 1 for operating a refrigeration cycle in which the evaporating temperature is −75 to −5° C. is advantageous in terms of ensuring a refrigerating capacity equivalent to or higher than that of R404A.


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, when the evaporating temperature exceeds −5° C., the compression ratio becomes less than 2.5, which reduces the efficiency of the refrigeration cycle. In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, when the evaporating temperature is less than −75° C., the evaporation pressure becomes less than 0.02 MPa, which makes suction of the refrigerant into a compressor difficult. The compression ratio is calculated with the following equation.





Compression ratio=condensation pressure (Mpa)/evaporation pressure (Mpa).


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the evaporating temperature is preferably −7.5° C. or lower, more preferably −10° C. or lower, and even more preferably −35° C. or lower.


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more and −5° C. or lower, more preferably −60° C. or more and −5° C. or lower, even more preferably −55° C. or more and −7.5° C. or lower, and particularly preferably −50° C. or more and −10° C. or lower.


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more, from the viewpoint of improving the suction of the refrigerant into a compressor.


In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more, from the viewpoint of improving the efficiency of the refrigeration cycle. In a refrigeration cycle in which Refrigerant 1 according to the present disclosure is used, the compression ratio is preferably 200 or less, more preferably 150 or less, even more preferably 100 or less, and particularly preferably 50 or less, from the viewpoint of improving the efficiency of the refrigeration cycle.


Refrigerant 1 may comprise HFO-1132 (E) and HFO-1234yf in such amounts that the sum of their concentrations is usually 99.5 mass % or more. In the present disclosure, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7 mass % or more, more preferably 99.8 mass % or more, and even more preferably 99.9 mass % or more, of entire Refrigerant 1.


Refrigerant 1 may further comprise an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf as long as the above characteristics are not impaired. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less, of entire Refrigerant 1. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants widely used in the field. Refrigerant 1 may comprise one additional refrigerant or two or more additional refrigerants.


It is particularly preferred that Refrigerant 1 consist of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 1 is particularly preferably 100 mass % of entire Refrigerant 1.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 35.0 to 65.0 mass %, and HFO-1234yf is usually present in an amount of 65.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 1 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP equivalent to or higher than that of R404A; and (3) it has a refrigerating capacity equivalent to or higher than that of R404A.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 40.5 to 59.0 mass %, and HFO-1234yf be present in an amount of 59.5 to 41.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 41.3 to 59.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 41.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is further preferred that HFO-1132 (E) be present in an amount of 41.3 to 55.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 45.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 41.3 to 53.5 mass %, and HFO-1234yf be present in an amount of 58.7 to 46.5 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 41.3 to 51.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 49.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


5.2 Refrigerant 2

In an embodiment, the refrigerant according to the present disclosure comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of 40.5 to 49.2 mass %, and HFO-1234yf is present in an amount of 59.5 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as “Refrigerant 2.”


Refrigerant 2 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP equivalent to or higher than that of R404A; (3) it has a refrigerating capacity equivalent to or higher than that of R404A; and (4) it is slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


Since Refrigerant 2 comprises HFO-1132 (E) in an amount of 40.5 mass % or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 2 has a refrigerating capacity equivalent to or higher than that of R404A. Moreover, since Refrigerant 2 comprises HFO-1132 (E) in an amount of 49.2 mass % or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of Refrigerant 2 at a saturation temperature of 40° C. in the refrigeration cycle can be maintained within a suitable range (in particular 2.10 Mpa or less).


Refrigerant 2 may have a refrigerating capacity of 99% or more, preferably 100% or more, more preferably 101% or more, even more preferably 102% or more, and particularly preferably 103% or more, relative to that of R404A.


Since the GWP is 100 or less, Refrigerant 2 can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants.


In Refrigerant 2, the ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) relative to that of R404A is preferably high, from the viewpoint of energy consumption efficiency. Specifically, the COP relative to that of R404A is preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more.


In Refrigerant 2, it is preferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, it is preferred that HFO-1132 (E) be present in an amount of 43.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 57.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 101% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, it is further preferred that HFO-1132 (E) be present in an amount of 44.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 56.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 101% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, it is particularly preferred that HFO-1132 (E) be present in an amount of 45.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 55.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 102% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, it is particularly preferred that HFO-1132 (E) be present in an amount of 45.0 to 48.0 mass %, and HFO-1234yf be present in an amount of 55.0 to 52.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102.5% or more relative to that of R404A, and a refrigerating capacity of 102.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, it is most preferred that HFO-1132 (E) be present in an amount of 45.0 to 47.0 mass %, and HFO-1234yf be present in an amount of 55.0 to 53.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102.5% or more relative to that of R404A, and a refrigerating capacity of 102.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.85 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, the saturation pressure at a saturation temperature of 40° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40° C. is within the above range, Refrigerant 2 is applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In Refrigerant 2, the saturation pressure at a saturation temperature of 40° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40° C. is within the above range, Refrigerant 2 is applicable to commercially available refrigeration apparatuses for R404A without significant design change.


In the present disclosure, when Refrigerant 2 is used for operating a refrigeration cycle, the discharge temperature is preferably 150° C. or lower, more preferably 140° C. or lower, even more preferably 130° C. or lower, and particularly preferably 120° C. or lower, from the viewpoint of extending the life of the components of a commercially available refrigeration apparatus for R404A.


In the present disclosure, Refrigerant 2 is preferably used for operating a refrigeration cycle in which the evaporating temperature is −75 to 15° C. from the viewpoint of obtaining a refrigerating capacity equivalent to or higher than that of R404A.


In a refrigeration cycle in which Refrigerant 2 according to the present disclosure is used, the evaporating temperature is preferably 15° C. or lower, more preferably 5° C. or lower, even more preferably 0° C. or lower, and particularly preferably −5° C. or lower.


In a refrigeration cycle in which Refrigerant 2 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


In a refrigeration cycle in which Refrigerant 2 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more and 15° C. or lower, more preferably −60° C. or more and 5° C. or lower, even more preferably −55° C. or more and OC or lower, and particularly preferably −50° C. or more and −5° C. or lower.


In a refrigeration cycle in which Refrigerant 2 according to the present disclosure is used, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more, from the viewpoint of improving the suction of the refrigerant into a compressor.


In a refrigeration cycle in which Refrigerant 2 according to the present disclosure is used, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more, from the viewpoint of improving the efficiency of the refrigeration cycle.


Refrigerant 2 may comprise HFO-1132 (E) and HFO-1234yf in such amounts that the sum of their concentrations is usually 99.5 mass % or more. In the present disclosure, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7 mass % or more, more preferably 99.8 mass % or more, and even more preferably 99.9 mass % or more, of entire Refrigerant 2.


Refrigerant 2 may further comprise an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf as long as the above characteristics are not impaired. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less, of entire Refrigerant 2. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants widely used in the field. Refrigerant 2 may comprise one additional refrigerant or two or more additional refrigerants.


It is particularly preferred that Refrigerant 2 consist of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 2 is particularly preferably 100 mass % of entire Refrigerant 2.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 40.5 to 49.2 mass %, and HFO-1234yf is usually present in an amount of 59.5 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 2 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP equivalent to or higher than that of R404A; (3) it has a refrigerating capacity equivalent to or higher than that of R404A; and (4) it is slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 99.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 43.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 57.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 101% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it is further preferred that HFO-1132 (E) be present in an amount of 44.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 56.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 101% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 45.0 to 49.2 mass %, and HFO-1234yf be present in an amount of 55.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102% or more relative to that of R404A, and a refrigerating capacity of 102% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 45.0 to 48.0 mass %, and HFO-1234yf be present in an amount of 55.0 to 52.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics of having a GWP of 100 or less, a COP of 102.5% or more relative to that of R404A, and a refrigerating capacity of 102.5% or more relative to that of R404A, as well as being slightly flammable according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40° C., and is thus applicable to commercially available refrigeration apparatuses for R404A without significant design change.


5.3 Refrigerant 3

In an embodiment, the refrigerant according to the present disclosure comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of 31.1 to 39.8 mass %, and HFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as “Refrigerant 3.”


Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R134a; (3) it has a refrigerating capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90° C. or less.


Since Refrigerant 3 comprises HFO-1132 (E) in an amount of 31.1 mass % or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 3 has a refrigerating capacity of 150% or more relative to that of R134a. Moreover, since Refrigerant 3 comprises HFO-1132 (E) in an amount of 39.8 mass % or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the discharge temperature of Refrigerant 3 in a refrigeration cycle can be maintained at 90° C. or less, and long life of the components of a refrigeration apparatus for R134a can be ensured.


Refrigerant 3 may have a refrigerating capacity of 150% or more, preferably 151% or more, more preferably 152% or more, even more preferably 153% or more, and particularly preferably 154% or more, relative to that of R134a.


Refrigerant 3 has a discharge temperature of preferably 90.0° C. or less, more preferably 89.7° C. or less, even more preferably 89.4° C. or less, and particularly preferably 89.0° C. or less, in a refrigeration cycle.


Since the GWP is 100 or less, Refrigerant 3 can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants.


In Refrigerant 3, the ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) relative to that of R134a is preferably high, from the viewpoint of energy consumption efficiency. Specifically, the COP relative to that of R134a is preferably 90% or more, more preferably 91% or more, even more preferably 91.5% or more, and particularly preferably 92% or more.


In Refrigerant 3, HFO-1132 (E) is usually present in an amount of 31.1 to 39.8 mass %, and HFO-1234yf is usually present in an amount of 68.9 to 60.2 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R134a; (3) it has a refrigerating capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90.0° C. or less.


In Refrigerant 3, it is preferred that HFO-1132 (E) be present in an amount of 31.1 to 37.9 mass %, and HFO-1234yf be present in an amount of 68.9 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has an COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 150% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


In Refrigerant 3, it is more preferred that HFO-1132 (E) be present in an amount of 32.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 68.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 151% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less, and (5) the critical temperature is 81° C. or more.


In Refrigerant 3, it is further preferred that HFO-1132 (E) be present in an amount of 33.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 67.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 152% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


In Refrigerant 3, it is even more preferred that HFO-1132 (E) be present in an amount of 34.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 66.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 153% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


In Refrigerant 3, it is particularly preferred that HFO-1132 (E) be present in an amount of 35.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 65.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 155% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


In the present disclosure, when Refrigerant 3 is used for operating a refrigeration cycle, the discharge temperature is preferably 90.0° C. or less, more preferably 89.7° C. or less, even more preferably 89.4° C. or less, and particularly preferably 89.0° C. or less, from the viewpoint of extending the life of the components of a commercially available refrigeration apparatus for R134a.


In the present disclosure, when Refrigerant 3 is used for operating a refrigeration cycle, the refrigeration cycle requires the process of liquefying (condensing) the refrigerant; thus, the critical temperature needs to be notably higher than the temperature of cooling water or cooling air for liquefying the refrigerant. From this viewpoint, in a refrigeration cycle in which Refrigerant 3 according to the present disclosure is used, the critical temperature is preferably 80° C. or more, more preferably 81° C. or more, even more preferably 81.5° C. or more, and particularly preferably 82° C. or more.


In the present disclosure, Refrigerant 3 is usually used for operating a refrigeration cycle in which the evaporating temperature is −75 to 15° C., from the viewpoint of obtaining a refrigerating capacity of 150% or more relative to that of R134a.


In a refrigeration cycle in which Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably 15° C. or less, more preferably 5° C. or less, even more preferably 0° C. or less, and particularly preferably −5° C. or less.


In a refrigeration cycle in which Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


In a refrigeration cycle in which Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more and 15° C. or less, more preferably −60° C. or more and 5° C. or less, even more preferably −55° C. or more and 0° C. or less, and particularly preferably −50° C. or more and −5° C. or less.


In a refrigeration cycle in which Refrigerant 3 according to the present disclosure is used, the critical temperature of the refrigerant is preferably 80° C. or more, more preferably 81° C. or more, even more preferably 81.5° C. or more, and particularly preferably 82° C. or more, from the viewpoint of improving the performance.


Refrigerant 3 may comprise HFO-1132 (E) and HFO-1234yf in such amounts that the sum of their concentrations is usually 99.5 mass % or more. In the present disclosure, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7 mass % or more, more preferably 99.8 mass % or more, and even more preferably 99.9 mass % or more, of entire Refrigerant 3.


Refrigerant 3 may further comprise an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf as long as the above characteristics are not impaired. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less, of entire Refrigerant 3. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants widely used in the field. Refrigerant 3 may comprise one additional refrigerant or two or more additional refrigerants.


It is particularly preferred that Refrigerant 3 consist of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 3 is particularly preferably 100 mass % of entire Refrigerant 3.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 31.1 to 39.8 mass %, and HFO-1234yf is usually present in an amount of 68.9 to 60.2 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R134a; (3) it has a refrigerating capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90° C. or less.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 31.1 to 37.9 mass %, and HFO-1234yf be present in an amount of 68.9 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 150% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is more preferred that HFO-1132 (E) be present in an amount of 32.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 68.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 151% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) be present in an amount of 33.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 67.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 152% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is further preferred that HFO-1132 (E) be present in an amount of 34.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 66.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 153% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is further preferred that HFO-1132(E) be present in an amount of 35.0 to 37.9 mass %, and HFO-1234yf be present in an amount of 65.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP of 92% or more relative to that of R134a; (3) it has a refrigerating capacity of 155% or more relative to that of R134a; (4) the discharge temperature is 90.0° C. or less; and (5) the critical temperature is 81° C. or more.


5.4 Refrigerant 4

In an embodiment, the refrigerant according to the present disclosure comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of 21.0 to 28.4 mass %, and HFO-1234yf is present in an amount of 79.0 to 71.6 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as “Refrigerant 4.”


Refrigerant 4 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R1234yf; (3) it has a refrigerating capacity of 140% or more relative to that of R1234yf; and (4) it is slightly flammable according to ASHRAE standards (Class 2L). Further, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


Since Refrigerant 4 comprises HFO-1132 (E) in an amount of 21.0 mass % or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 4 has a refrigerating capacity of 140% or more relative to that of R1234yf. Moreover, Refrigerant 4 comprises HFO-1132 (E) in an amount of 28.4 mass % or less based on the total mass of HFO-1132 (E) and HFO-1234yf. This makes it easy to ensure a critical temperature of 83.5° C. or more.


Refrigerant 4 may have a refrigerating capacity of 140% or more, preferably 142% or more, more preferably 143% or more, even more preferably 145% or more, and particularly preferably 146% or more, relative to that of R1234yf.


Since the GWP is 100 or less, Refrigerant 4 can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants.


In Refrigerant 4, the ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) relative to that of R1234yf is preferably high from the viewpoint of energy consumption efficiency. Specifically, the COP relative to that of R1234yf is preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, and particularly preferably 98% or more.


In Refrigerant 4, it is preferred that HFO-1132 (E) be present in an amount of 21.5 to 28.0 mass %, and HFO-1234yf be present in an amount of 78.5 to 72.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0° C. or less; and the critical temperature is 83.5° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, it is more preferred that HFO-1132 (E) be present in an amount of 22.0 to 27.7 mass %, and HFO-1234yf be present in an amount of 78.0 to 72.3 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0° C. or less; and the critical temperature is 83.5° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, it is even more preferred that HFO-1132 (E) be present in an amount of 22.5 to 27.5 mass %, and HFO-1234yf be present in an amount of 77.5 to 72.5 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, it is particularly preferred that HFO-1132 (E) be present in an amount of 23.0 to 27.2 mass %, and HFO-1234yf be present in an amount of 77.0 to 72.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 141% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, it is further particularly preferred that HFO-1132 (E) be present in an amount of 23.5 to 27.0 mass %, and HFO-1234yf be present in an amount of 76.5 to 73.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 142% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, it is most preferred that HFO-1132 (E) be present in an amount of 24.0 to 26.7 mass %, and HFO-1234yf be present in an amount of 76.0 to 73.3 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 144% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.6° C. or less; and the critical temperature is 84.0° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, the saturation pressure at a saturation temperature of −10° C. is usually 0.420 MPa or less, preferably 0.418 MPa or less, more preferably 0.417 MPa or less, even more preferably 0.415 MPa or less, and particularly preferably 0.413 MPa or less. When the saturation pressure is within this range, Refrigerant 4 is applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In Refrigerant 4, the saturation pressure at a saturation temperature of −10° C. is usually 0.380 MPa or more, preferably 0.385 MPa or more, more preferably 0.390 MPa or more, even more preferably 0.400 MPa or more, and particularly preferably 0.410 MPa or more. In these cases, Refrigerant 4 is applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


In the present disclosure, when Refrigerant 4 is used for operating a refrigeration cycle, the discharge temperature is preferably 65° C. or less, more preferably 64.8° C. or less, even more preferably 64.7° C. or less, and particularly preferably 64.5° C. or less, from the viewpoint of extending the life of the components of a commercially available refrigeration apparatus for R1234yf.


In the present disclosure, Refrigerant 4 is preferably used for operating a refrigeration cycle in which the evaporating temperature is −75 to 5° C., from the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf.


In a refrigeration cycle in which Refrigerant 4 according to the present disclosure is used, the evaporating temperature is preferably 5° C. or less, more preferably 0° C. or less, even more preferably −5° C. or less, and particularly preferably −10° C. or less, from the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf.


In a refrigeration cycle in which Refrigerant 4 according to the present disclosure is used, the evaporating temperature is preferably −75° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more, from the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf.


In a refrigeration cycle in which Refrigerant 4 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more and 0° C. or less, more preferably −60° C. or more and −5° C. or less, even more preferably −55° C. or more and −7.5° C. or less, and particularly preferably −50° C. or more and −10° C. or less, from the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf.


In a refrigeration cycle in which Refrigerant 4 according to the present disclosure is used, the discharge temperature is preferably 65.0° C. or less, more preferably 64.9° C. or less, even more preferably 64.8° C. or less, and particularly preferably 64.7° C. or less, from the viewpoint of extending the life of the components of a commercially available refrigeration apparatus for R1234yf.


In the present disclosure, when Refrigerant 4 is used for operating a refrigeration cycle, the refrigeration cycle requires the process of liquefying (condensing) the refrigerant; thus, the critical temperature needs to be notably higher than the temperature of cooling water or cooling air for liquefying the refrigerant. From this viewpoint, in a refrigeration cycle in which Refrigerant 4 according to the present disclosure is used, the critical temperature is preferably 83.5° C. or more, more preferably 83.8° C. or more, even more preferably 84.0° C. or more, and particularly preferably 84.5° C. or more.


Refrigerant 4 may further comprise an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf as long as the above characteristics are not impaired. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less, of entire Refrigerant 4. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants widely used in the field. Refrigerant 4 may comprise one additional refrigerant or two or more additional refrigerants.


It is particularly preferred that Refrigerant 4 consist of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 4 is particularly preferably 100 mass % of entire Refrigerant 4.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 21.0 to 28.4 mass %, and HFO-1234yf is usually present in an amount of 79.0 to 71.6 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 4 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R1234yf; (3) it has a refrigerating capacity of 140% or more relative to that of R1234yf; and (4) it is slightly flammable according to ASHRAE standards (Class 2L). Further, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of −10° C. and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 21.5 to 28.0 mass %, and HFO-1234yf be present in an amount of 78.5 to 72.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0° C. or less; and the critical temperature is 83.5° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of −10° C. and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is more preferred that HFO-1132 (E) be present in an amount of 22.0 to 27.7 mass %, and HFO-1234yf be present in an amount of 78.0 to 72.3 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0° C. or less; and the critical temperature is 83.5° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) be present in an amount of 22.5 to 27.5 mass %, and HFO-1234yf be present in an amount of 77.5 to 72.5 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 140% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 23.0 to 27.2 mass %, and HFO-1234yf be present in an amount of 77.0 to 72.8 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 141% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is further particularly preferred that HFO-1132 (E) be present in an amount of 23.5 to 27.0 mass %, and HFO-1234yf be present in an amount of 76.5 to 73.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 142% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8° C. or less; and the critical temperature is 83.8° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) be present in an amount of 24.0 to 26.7 mass %, and HFO-1234yf be present in an amount of 76.0 to 73.3 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: the GWP is 100 or less; it has a COP of 98% or more relative to that of R1234yf; it has a refrigerating capacity of 144% or more relative to that of R1234yf; it is slightly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.6° C. or less; and the critical temperature is 84.0° C. or more. Further, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of −10° C., and is thus applicable to commercially available refrigeration apparatuses for R1234yf without significant design change.


5.5 Refrigerant 5

In an embodiment, the refrigerant according to the present disclosure comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of 12.1 to 72.0 mass %, and HFO-1234yf is present in an amount of 87.9 to 28.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as “Refrigerant 5.”


In the present disclosure, Refrigerant 5 is used for an air-conditioning system for vehicles.


Refrigerant 5 has the above feature and thus has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a COP almost equivalent to that of R1234yf; (3) it has a refrigerating capacity of 128% or more relative to that of R1234yf; and (4) the burning velocity is less than 10.0 cm/s.


Refrigerant 5 comprises HFO-1132 (E) in an amount of 12.1 mass % or more based on the total mass of HFO-1132 (E) and HFO-1234yf. This makes it possible to ensure a boiling point of −40° C. or less, which is advantageous when an electric vehicle is heated using a heat pump. A boiling point of −40° C. or less means that the saturation pressure is equal to or higher than atmospheric pressure at −40° C. For the above application, a lower boiling point that is not higher than −40° C. is preferred. Further, Refrigerant 5 comprises HFO-1132 (E) in an amount of 72.0 mass % or less based on the total mass of HFO-1132 (E) and HFO-1234yf. This makes it possible to ensure a burning velocity of less than 10.0 cm/s, which contributes to safety when used for an air-conditioning system for vehicles.


Refrigerant 5 may have a refrigerating capacity of 128% or more, preferably 130% or more, more preferably 140% or more, even more preferably 150% or more, and particularly preferably 160% or more, relative to that of R1234yf.


Since the GWP is 5 or more and 100 or less, Refrigerant 5 can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants.


In Refrigerant 5, the ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) relative to that of R1234yf may be 100% or more from the viewpoint of energy consumption efficiency.


The use of Refrigerant 5 for an air-conditioning system for vehicles enables heating with a heat pump, which consumes less power than electrical heaters.


The air-conditioning system for which Refrigerant 5 is used is preferably for gasoline vehicles, hybrid vehicles, electric vehicles, or hydrogen vehicles. From the viewpoint of improving the travel distance of a vehicle while the interior of the vehicle is heated with a heat pump, the air-conditioning system for which Refrigerant 5 is used is particularly preferably for electric vehicles among these. Specifically, in the present disclosure, Refrigerant 5 is particularly preferably used for electric vehicles.


In the present disclosure, Refrigerant 5 is used for air-conditioning systems for vehicles. In the present disclosure, Refrigerant 5 is preferably used for air-conditioning systems for gasoline vehicles, air-conditioning systems for hybrid vehicles, air-conditioning systems for electric vehicles, or air-conditioning systems for hydrogen vehicles. In the present disclosure, Refrigerant 5 is particularly preferably used for air-conditioning systems for electric vehicles.


In the present disclosure, Refrigerant 5 has a boiling point of preferably −51.2 to −40.0° C., more preferably −50.0 to −42.0° C., and even more preferably −48.0 to −44.0° C., since a pressure equal to or higher than atmospheric pressure at −40° C. is required when the interior of a vehicle is heated using a heat pump.


In Refrigerant 5, it is preferred that HFO-1132 (E) be present in an amount of 15.0 to 65.0 mass %, and HFO-1234yf be present in an amount of 85.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


In Refrigerant 5, it is more preferred that HFO-1132 (E) be present in an amount of 20.0 to 55.0 mass %, and HFO-1234yf be present in an amount of 80.0 to 45.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


In Refrigerant 5, it is even more preferred that HFO-1132 (E) be present in an amount of 25.0 to 50.0 mass %, and HFO-1234yf be present in an amount of 75.0 to 50.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


In Refrigerant 5, it is particularly preferred that HFO-1132 (E) be present in an amount of 30.0 to 45.0 mass %, and HFO-1234yf be present in an amount of 70.0 to 55.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


In Refrigerant 5, it is most preferred that HFO-1132 (E) be present in an amount of 35.0 to 40.0 mass %, and HFO-1234yf be present in an amount of 65.0 to 60.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


In the present disclosure, the burning velocity of Refrigerant 5 is preferably less than 10.0 cm/s, more preferably less than 5.0 cm/s, even more preferably less than 3.0 cm/s, and particularly preferably 2.0 cm/s.


In the present disclosure, Refrigerant 5 is preferably used for operating a refrigeration cycle in which the evaporating temperature is −40 to 10° C. from the viewpoint of obtaining a refrigerating capacity equivalent to or higher than that of R1234yf.


In the present disclosure, when Refrigerant 5 is used for operating a refrigeration cycle, the discharge temperature is preferably 79° C. or less, more preferably 75° C. or less, even more preferably 70° C. or less, and particularly preferably 67° C. or less.


Refrigerant 5 may comprise HFO-1132 (E) and HFO-1234yf in such amounts that the sum of their concentrations is usually 99.5 mass % or more. In the present disclosure, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7 mass % or more, more preferably 99.8 mass % or more, and even more preferably 99.9 mass % or more, of entire Refrigerant 5.


Refrigerant 5 may further comprise an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf as long as the above characteristics are not impaired. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less, of entire Refrigerant 5. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants widely used in the field. Refrigerant 5 may comprise one additional refrigerant or two or more additional refrigerants.


It is particularly preferred that Refrigerant 5 consist of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 5 is particularly preferably 100 mass % of entire Refrigerant 5.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 12.1 to 72.0 mass %, and HFO-1234yf is usually present in an amount of 87.9 to 28.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is preferred that HFO-1132 (E) be present in an amount of 15.0 to 65.0 mass %, and HFO-1234yf be present in an amount of 85.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is more preferred that HFO-1132 (E) be present in an amount of 20.0 to 55.0 mass %, and HFO-1234yf be present in an amount of 80.0 to 45.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) be present in an amount of 25.0 to 50.0 mass %, and HFO-1234yf be present in an amount of 75.0 to 50.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) be present in an amount of 30.0 to 45.0 mass %, and HFO-1234yf be present in an amount of 70.0 to 55.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) be present in an amount of 35.0 to 40.0 mass %, and HFO-1234yf be present in an amount of 65.0 to 60.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.


1.6 Application

The composition containing the refrigerant according to the present disclosure can be widely used as a working fluid for known refrigerant applications in 1) a refrigeration method comprising operating a refrigeration cycle and 2) a method for operating a refrigeration apparatus that operates a refrigeration cycle.


The refrigeration cycle herein means performing energy conversion by circulating in the refrigeration apparatus the refrigerant (Refrigerant 1, 2, 3, 4, or 5 according to the present disclosure) in the state of the single refrigerant, or in the state of a refrigerant composition or a refrigerant oil-containing working fluid explained below, through a compressor.


The composition containing the refrigerant according to the present disclosure is not limited; however, it is suitably used in a vapor-compression refrigeration cycle. A vapor-compression refrigeration cycle comprises a series of cycles of (1) compressing a refrigerant in a gaseous state in a compressor, (2) cooling the refrigerant to convert it into a high-pressure liquid state in a condenser, (3) reducing the pressure with an expansion valve, and (4) evaporating the liquid refrigerant at a low temperature in an evaporator and removing heat by the heat of evaporation. Depending on the system of compressing gaseous refrigerants, vapor-compression refrigeration cycles can be classified into a turbo (centrifugal) cycle, a reciprocating cycle, a twin-screw cycle, a single-screw cycle, a scroll compressor cycle, etc., and can be selected according to heat capacity, compression ratio, and size.


The composition containing the refrigerant according to the present disclosure is not limited, and is suitable as a refrigerant used for large chiller refrigerating machines, and particularly turbo (centrifugal) compressors.


The present disclosure includes use of the refrigerant (or composition comprising the refrigerant) according to the present disclosure in a refrigeration method, use of the refrigerant (or composition comprising the refrigerant) according to the present disclosure in a method of operating a refrigeration apparatus etc., and a refrigeration apparatus or the like comprising the refrigerant (or composition comprising the refrigerant) according to the present disclosure.


The composition comprising Refrigerant 1 according to the present disclosure is used for operating a refrigeration cycle in which the evaporating temperature is −75 to −5° C.


By using the composition comprising Refrigerant 1 according to the present disclosure for operating a refrigeration cycle in which the evaporating temperature is −75 to −5° C., there is an advantage that a refrigerating capacity that is equivalent to or higher than that of R404A can be obtained.


In the refrigeration cycle in which the composition comprising Refrigerant 1 according to the present disclosure is used, the evaporating temperature is preferably −7.5° C. or less, more preferably −10° C. or less, even more preferably −35° C. or less.


In the refrigeration cycle in which the composition comprising Refrigerant 1 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


From the viewpoint of obtaining a refrigerating capacity that is equivalent to or higher than R404A, the composition comprising Refrigerant 2 according to the present disclosure is preferably used for operating a refrigeration cycle in which the evaporating temperature is −75 to 5° C.


In the refrigeration cycle in which the composition comprising Refrigerant 2 according to the present disclosure is used, the evaporating temperature is preferably 0° C. or less, more preferably −5° C. or less, even more preferably −7.5° C. or less, and particularly preferably −10° C. or less.


In the refrigeration cycle in which the composition comprising Refrigerant 2 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


From the viewpoint of obtaining a refrigerating capacity that is equivalent to or higher than R134a, the composition comprising Refrigerant 3 according to the present disclosure is preferably used for operating a refrigeration cycle in which the evaporating temperature is −75 to 15° C.


In the refrigeration cycle in which the composition comprising Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably 15° C. or less, more preferably 5° C. or less, even more preferably 0° C. or less, and particularly preferably −5° C. or less.


In the refrigeration cycle in which the composition comprising Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


In the refrigeration cycle in which the composition comprising Refrigerant 3 according to the present disclosure is used, the evaporating temperature is preferably −65° C. or more to 15° C. or less, more preferably −60° C. or more to 5° C. or less, even more preferably −55° C. or more to 0° C. or less, and particularly preferably −50° C. or more to −5° C. or less.


From the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf, the composition comprising Refrigerant 4 according to the present disclosure is preferably used for operating a refrigeration cycle in which the evaporating temperature is −75 to 20° C.


From the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf, in the refrigeration cycle in which the composition comprising Refrigerant 4 according to the present disclosure is used, the evaporating temperature is preferably 20° C. or less, more preferably 10° C. or less, even more preferably 0° C. or less, and particularly preferably −10° C. or less.


From the viewpoint of obtaining a refrigerating capacity of 140% or more relative to that of R1234yf, in the refrigeration cycle in which he composition comprising Refrigerant 4 according to the present disclosure is used, the evaporating temperature is preferably −75° C. or more, more preferably −60° C. or more, even more preferably −55° C. or more, and particularly preferably −50° C. or more.


Preferable examples of refrigeration apparatuses in which Refrigerant 1, 2, 3, or 4 (or a composition containing the refrigerant) according to the present disclosure can be used include air-conditioning systems, refrigerators, freezers, water coolers, ice makers, refrigerated showcases, freezing showcases, freezing and refrigerating units, refrigerating machines for freezing and refrigerating warehouses, air-conditioning systems for vehicles, turbo refrigerating machines, or screw refrigerating machines. Of these, air-conditioning systems for vehicles are preferred. Of the air-conditioning systems for vehicles, air-conditioning systems for gas vehicles, air-conditioning systems for hybrid vehicles, air-conditioning systems for electric vehicles, and air-conditioning systems for hydrogen vehicles are more preferred. Of the air-conditioning systems for vehicles, air-conditioning systems for electric vehicles are particularly preferred.


The composition comprising Refrigerant 1 or 2 according to the present disclosure is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, or R513A. The composition comprising Refrigerant 1 or 2 according to the present disclosure is suitably used as an alternative refrigerant for R22, R404A, R407F, R407H, R448A, R449A, R454C, R455A, or R465A. Additionally, since the composition comprising Refrigerant 1 or 2 according to the present disclosure has a refrigerating capacity equivalent to R404A, which has been widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R404A.


The composition comprising Refrigerant 3 according to the present disclosure is suitably used as an alternative refrigerant for R134a, R1234yf, or CO2. The composition comprising Refrigerant 3 according to the present disclosure is suitably used as an alternative refrigerant for R134a. Additionally, since the composition comprising Refrigerant 3 according to the present disclosure has a refrigerating capacity of 150% or more relative to that of R134a, which has been widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R134a.


The composition comprising Refrigerant 4 according to the present disclosure is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. The composition comprising Refrigerant 4 according to the present disclosure is suitably used as an alternative refrigerant for R12, R134a, R404A, R407C, R449C, R454C, R1234yf, or R1234ze. Additionally, since the composition comprising Refrigerant 4 according to the present disclosure has a refrigerating capacity of 140% or more relative to that of R1234yf, which has been widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.


The composition comprising Refrigerant 5 according to the present disclosure is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. The composition comprising Refrigerant 5 according to the present disclosure is suitably used as an alternative refrigerant for R12, R134a, or R1234yf. Additionally, since the composition comprising Refrigerant 5 according to the present disclosure has a refrigerating capacity of 140% or more relative to that of R1234yf, which has been widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.


The composition comprising Refrigerant 5 according to the present disclosure is preferably used in air-conditioning systems for vehicles. The air-conditioning systems for vehicles are preferably air-conditioning systems for gas vehicles, air-conditioning systems for hybrid vehicles, air-conditioning systems for electric vehicles, or air-conditioning systems for hydrogen vehicles. Of these, the air-conditioning systems for vehicles are particularly preferably air-conditioning systems for electric vehicles. That is, in the present disclosure, the composition comprising Refrigerant 5 is particularly preferably used for electric vehicles.


Examples of Refrigerants 1 to 5

The present disclosure is described in more detail below with reference to Examples of Refrigerants 1 to 5. However, Refrigerants 1 to 5 according to the present disclosure are not limited to the Examples.


Test Example 1-1

The GWP of each of the mixed refrigerants shown in Examples 1-1 to 1-13, Comparative Examples 1-1 to 1-2, and Reference Example 1-1 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


Evaporating temperature: −50° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The “evaporating temperature of −50° C.” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration apparatus is −50° C. Further, the “condensation temperature of 40° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigeration apparatus is 40° C.


Table 59 shows the results of Test Example 1-1. Table 59 shows Examples and Comparative Examples with regard to Refrigerant 1 according to the present disclosure. In Table 59, the “COP ratio” and the “refrigerating capacity ratio” refer to a ratio (%) relative to R404A.


In Table 59, the “saturation pressure (40° C.)” refers to a saturation pressure at a saturation temperature of 40° C. In Table 1, the “discharge temperature (° C.)” refers to a temperature at which the mixed refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations of the mixed refrigerant.


The coefficient of performance (COP) was calculated according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


The compression ratio was calculated according to the following formula.





Compression ratio=condensation pressure (Mpa)/evaporation pressure (Mpa)


The flammability of the mixed refrigerants were determined by adjusting the mixed formulations of the mixed refrigerants to WCF concentrations and measuring the burning velocity according to ANSI/ASHRAE Standard 34-2013. The mixed refrigerant with a burning velocity of 0 cm/s to 10 cm/s was classified as Class 2L (slight flammability), the mixed refrigerant with a burning velocity of more than 10 cm/s was classified as Class 2 (weak flammability), and the mixed refrigerant with no flame propagation was classified as Class 1 (non-flammability). In Table 59, the ASHRAE flammability classification shows the results based on these criteria.


The burning velocity test was performed as follows. 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 in a PC.


The flammable range of each of the mixed refrigerants was measured using a measurement device according to ASTM E681-09 (see FIG. 20).


More specifically, a 12-L spherical glass flask was used so that the combustion state could be visually observed and photographically recorded. When excessive pressure was generated by combustion in the glass flask, gas was allowed to escape from the upper lid. Ignition was achieved by electric discharge from electrodes disposed at one-third the distance from the bottom.


Test Conditions

Test vessel: 280-mm φ spherical (internal volume: 12 liters)


Test temperature: 60° C.±3° C.


Pressure: 101.3 kPa±0.7 kPa


Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at 23° C.) per gram of dry air


Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2 vol. %


Mixture of refrigerant composition: ±0.1 mass %


Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA, neon transformer


Electrode spacing: 6.4 mm (¼ inch)


Spark: 0.4 seconds±0.05 seconds


Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignition point, it was evaluated that flame propagation was present (flammable).


When the flame spread at an angle of 90° or less from the ignition point, it was evaluated that flame propagation was absent (non-flammable).


















TABLE 59









Reference











Example
Comparative




1-1
Example
Example
Example
Example
Example
Example
Example


Item
Unit
(R404A)
1-1
1-1
1-2
1-3
1-4
1-5
1-6




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-
mass %
44.0
0
0
0
0
0
0
0



125
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
100.6
106.6
114.7
115.0
115.5
116.5
117.6
118.8


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.082
0.063
0.072
0.073
0.074
0.075
0.077
0.079


Compression ratio

22.2
25.3
24.1
24.0
23.9
23.8
23.6
23.4


COP ratio (relative to
%
100
106.2
106.2
106.2
106.2
106.2
106.2
106.2


R404A)


Refrigerating capacity
%
100
86.2
98.5
99.1
100
102.1
104.5
106.9


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification




























Comparative




Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
1-7
1-8
1-9
1-10
1-11
1-12
1-13
1-2




















Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0


ratio
1132 (E)



HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0



1234yf



HFC-
mass %
0
0
0
0
0
0
0
0



134a



HFC-
mass %
0
0
0
0
0
0
0
0



143a



HFC-
mass %
0
0
0
0
0
0
0
0



125
















GWP (AR4)

7
7
7
7
7
8
8
8


Discharge temperature
° C.
120.0
121.0
122.4
123.3
124.4
125.5
126.0
131.7


Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128


(40° C.)


Evaporation pressure
MPa
0.081
0.083
0.085
0.086
0.088
0.090
0.091
0.099


Compression ratio

23.1
23.0
22.8
22.6
22.5
22.3
22.2
21.6


COP ratio (relative to
%
106.2
106.3
106.3
106.3
106.3
106.4
106.4
106.7


R404A)


Refrigerating capacity
%
109.5
111.7
114.6
116.4
118.7
121
122.2
133.3


ratio (relative to R404A)


ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2


classification









Test Example 1-2

The GWP of each of the mixed refrigerants shown in Examples 1-14 to 1-26, Comparative Examples 1-3 to 1-4, and Reference Example 1-2 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −35° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 1-1.


Table 60 shows the results of Test Example 1-2. Table 60 shows Examples and Comparative Examples with regard to Refrigerant 1 according to the present disclosure. In Table 60, the definitions of the terms are the same as those in Test Example 1-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 1-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 1-1. The burning velocity test was performed as in Test Example 1-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 1-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 60









Reference











Example
Comparative




1-2
Example
Example
Example
Example
Example
Example
Example


Item
Unit
(R404A)
1-3
1-14
1-15
1-16
1-17
1-18
1-19




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-
mass %
44.0
0
0
0
0
0
0
0



12S
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
89.1
99.8
100.6
100.8
101.2
102.0
102.9
103.8


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.165
0.131
0.148
0.149
0.151
0.154
0.157
0.160


Compression ratio

11.0
12.2
11.8
11.7
11.7
11.6
11.6
11.5


COP ratio (relative to
%
100
105.1
104.8
104.7
104.7
104.7
104.6
104.5


R404A)


Refrigerating capacity
%
100
87.7
98.5
99.0
99.8
101.6
103.7
105.7


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification




























Comparative




Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
1-20
1-21
1-22
1-23
1-24
1-25
1-26
1-4




















Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0


ratio
1132 (E)



HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0



1234yf



HFC-
mass %
0
0
0
0
0
0
0
0



134a



HFC-
mass %
0
0
0
0
0
0
0
0



143a



HFC-
mass %
0
0
0
0
0
0
0
0



12S
















GWP (AR4)

7
7
7
7
7
8
8
8


Discharge temperature
° C.
104.7
105.5
106.6
107.3
108.1
109.0
109.5
113.9


Saturation pressure
MPa
1.874
1.898
1.831
1.950
1.975
2.000
2.012
2.128


(40° C.)


Evaporation pressure
MPa
0.164
0.167
0.171
0.174
0.177
0.180
0.181
0.196


Compression ratio

11.4
11.4
11.3
11.2
11.2
11.1
11.1
10.8


COP ratio (relative to
%
104.5
104.4
104.4
104.4
104.3
104.3
104.3
1043


R404A)


Refrigerating capacity
%
108.0
109.8
112.3
113.8
115.7
117.7
118.6
128.0


ratio (relative to R404A)


ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2


classification









Test Example 1-3

The GWP of each of the mixed refrigerants shown in Examples 1-27 to 1-39, Comparative Examples 1-5 to 1-6, and Reference Example 1-3 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −10° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 1-1.


Table 61 shows the results of Test Example 1-3. Table 61 shows Examples and Comparative Examples with regard to Refrigerant 1 according to the present disclosure. In Table 61, the definitions of the terms are the same as those in Test Example 1-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 1-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 1-1. The burning velocity test was performed as in Test Example 1-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 1-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 61









Reference











Example
Comparative




1-3
Example
Example
Example
Example
Example
Example
Example


Item
Unit
(R404A)
1-5
1-27
1-28
1-29
1-30
1-31
1-32




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
75.8
80.8
83.7
83.9
84.1
84.5
85.1
85.6


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporator pressure
MPa
0.434
0.357
0.399
0.401
0.404
0.411
0.419
0.427


Compression ratio

4.2
4.5
4.4
4.4
4.4
4.3
4.3
4.3


COP ratio (relative to
%
100
103.8
102.9
102.9
102.8
102.7
102.5
102.4


R404A)


Refrigerating capacity
%
100
89.8
98.7
99.1
99.8
101.2
102.8
104.5


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification




























Comparative




Example
Example
Example
Example
Example
Example
Example
Example


Item
Unit
1-33
1-34
1-35
1-36
1-37
1-38
1-39
1-6




















Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0


ratio
1132 (E)



HFO-
mass %
50.8
49.0
46.5
45.0
43.0
4.10
40.0
30.0



1234yf



HFC-
mass %
0
0
0
0
0
0
0
0



134a



HFC-
mass %
0
0
0
0
0
0
0
0



143a



HFC-125
mass %
0
0
0
0
0
0
0
0
















GWP (AR4)

7
7
7
7
7
8
8
8


Discharge temperature
° C.
86.2
86.6
87.3
87.7
88.2
88.7
88.9
91.5


Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128


(40° C.)


Evaporator pressure
MPa
0.436
0.443
0.452
0.457
0.465
0.472
0.475
0.509


Compression ratio

4.3
4.3
4.3
4.3
4.3
4.2
4.2
4.2


COP ratio (relative to
%
102.2
102.1
102.0
101.9
101.8
101.7
101.6
101.3


R404A)


Refrigerating capacity
%
106.2
107.7
109.6
110.8
112.3
113.8
114.5
121.7


ratio (relative to R404A)


ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2


classification









Test Example 1-4

The GWP of each of the mixed refrigerants shown in Comparative Examples 1-7 to 1-21 and Reference Example 1-4 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −80° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 1-1.


Table 62 shows the results of Test Example 1-4. Table 62 shows Comparative Examples with regard to Refrigerant 1 according to the present disclosure. In Table 62, the definitions of the terms are the same as those in Test Example 1-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 1-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 1-1. The burning velocity test was performed as in Test Example 1-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 1-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 62









Reference











Example
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




1-4
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.


Item
Unit
(R404A)
1-7
1-8
1-9
1-10
1-11
1-12
1-13




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-
mass %
44.0
0
0
0
0
0
0
0



125
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
136.7
146.0
157.7
158.1
158.8
160.4
162.1
163.9


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.014
0.011
0.012
0.012
0.012
0.012
0.013
0.013


Compression ratio

134.6
149.1
150.8
150.2
149.3
147.2
145.0
142.8


COP ratio (relative to
%
100
112.6
110.3
110.3
110.4
110.6
110.8
111.0


R404A)


Refrigerating capacity
%
100
91.7
99.3
100.2
101.5
104.4
107.8
111.3


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
1-14
1-15
1-16
1-17
1-18
1-19
1-20
1-21























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-
mass %
0
0
0
0
0
0
0
0




134a




HFC-
mass %
0
0
0
0
0
0
0
0




143a




HFC-
mass %
0
0
0
0
0
0
0
0




125


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
165.8
167.4
169.6
170.9
172.6
174.3
175.2
184.0



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.013
0.014
0.014
0.014
0.015
0.015
0.015
0.017



Compression ratio

140.5
138.7
136.3
134.9
133.2
131.5
130.7
123.8



COP ratio (relative to
%
111.3
111.4
111.7
111.9
112.1
112.3
112.4
113.5



R404A)



Refrigerating capacity
%
115.1
118.2
122.5
125.2
128.6
132.1
133.8
151.0



ratio (relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 1-5

The GWP of each of the mixed refrigerants shown in Comparative Examples 1-22 to 1-36 and Reference Example 1-5 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: 10° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 1-1.


Table 63 shows the results of Test Example 1-5. Table 63 shows Comparative Examples with regard to Refrigerant 1 according to the present disclosure. In Table 63, the definitions of the terms are the same as those in Test Example 1-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 1-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 1-1. The burning velocity test was performed as in Test Example 1-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 1-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 63









Reference











Example
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




1-5
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.


Item
Unit
(R404A)
1-22
1-23
1-24
1-25
1-26
1-27
1-28




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-134a
mass %
4.0
0
0
0
0
0
0
0



HFC-143a
mass %
52.0
0
0
0
0
0
0
0



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
68.5
72.4
74.0
74.1
74.2
74.4
74.7
74.9


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.820
0.694
0.768
0.772
0.777
0.789
0.803
0.817


Compression ratio

2.2
2.3
2.3
2.3
2.3
2.3
2.3
2.3


COP ratio (relative to
%
100.0
103.1
101.9
101.8
101.7
101.5
101.3
101.1


R404A)


Refrigerating capacity ratio
%
100.0
91.2
98.9
99.8
99.3
101.0
102.5
103.8


(relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
1-29
1-30
1-31
1-32
1-33
1-34
1-35
1-36























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-134a
mass %
0
0
0
0
0
0
0
0




HFC-143a
mass %
0
0
0
0
0
0
0
0




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
75.2
75.5
75.8
76.0
76.2
76.5
76.6
77.9



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.832
0.844
0.860
0.870
0.882
0.895
0.901
0.959



Compression ratio

2.3
2.2
2.2
2.2
2.2
2.2
2.2
2.2



COP ratio (relative to
%
100.9
100.8
100.6
100.4
100.3
100.1
100.1
99.5



R404A)



Refrigerating capacity ratio
%
105.3
106.5
108.2
109.1
110.4
111.6
112.3
118.2



(relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 2-1

The GWP of each of the mixed refrigerants shown in Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-9, and Reference Example 2-1 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


Evaporating temperature: −50° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The “evaporating temperature of −50° C.” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration apparatus is −50° C. Further, the “condensation temperature of 40° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigeration apparatus is 40° C.


Table 64 shows the results of Test Example 2-1. Table 64 shows Examples and Comparative Examples with regard to Refrigerant 2 according to the present disclosure. In Table 64, the “COP ratio” and the “refrigerating capacity ratio” refer to a ratio (%) relative to R404A.


In Table 64, the “saturation pressure (40° C.)” refers to a saturation pressure at a saturation temperature of 40° C. In Table 64, the “discharge temperature (° C.)” refers to a temperature at which the mixed refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations of the mixed refrigerant.


The coefficient of performance (COP) was calculated according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


The compression ratio was calculated according to the following formula.





Compression ratio=condensation pressure (Mpa)/evaporation pressure (Mpa)


The flammability of the mixed refrigerants was determined by adjusting the mixed formulations of the mixed refrigerants to WCF concentrations and measuring the burning velocity according to ANSI/ASHRAE Standard 34-2013. The mixed refrigerant with a burning velocity of 0 cm/s to 10 cm/s was classified as Class 2L (slight flammability), the mixed refrigerant with a burning velocity of more than 10 cm/s was classified as Class 2 (weak flammability), and the mixed refrigerant with no flame propagation was classified as Class 1 (non-flammability). In Table 64, the ASHRAE flammability classification shows the results based on these criteria.


The burning velocity test was performed as follows. 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 by 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 in a PC.


The flammable range of each of the mixed refrigerants was measured using a measurement device according to ASTM E681-09 (see FIG. 20).


More specifically, a 12-L spherical glass flask was used so that the combustion state could be visually observed and photographically recorded. When excessive pressure was generated by combustion in the glass flask, gas was allowed to escape from the upper lid. Ignition was achieved by electric discharge from electrodes disposed at one-third the distance from the bottom.


Test Conditions

Test vessel: 280-mm φ spherical (internal volume: 12 liters)


Test temperature: 60° C.±3° C.


Pressure: 101.3 kPa±0.7 kPa


Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at 23° C.) per gram of dry air


Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2 vol. %


Mixture of refrigerant composition: ±0.1 mass %


Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA, neon transformer


Electrode spacing: 6.4 mm (¼ inch)


Spark: 0.4 seconds±0.05 seconds


Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignition point, it was evaluated that flame propagation was present (flammable).


When the flame spread at an angle of 90° or less from the ignition point, it was evaluated that flame propagation was absent (non-flammable).


















TABLE 64









Reference











Example
Comp.
Comp.




2-1
Ex.
Ex.
Example
Example
Example
Example
Example


Item
Unit
(R404A)
2-1
2-2
2-1
2-2
2-3
2-4
2-5




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-134a
mass %
4.0
0
0
0
0
0
0
0



HFC-143a
mass %
52.0
0
0
0
0
0
0
0



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
100.6
108.6
114.7
115.0
115.5
116.5
117.6
118.8


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.082
0.063
0.072
0.073
0.074
0.075
0.077
0.079


Compression ratio

22.2
25.3
24.1
24.0
23.9
23.8
23.6
23.4


COP ratio (relative to
%
100
106.2
106.2
106.2
106.2
106.2
106.2
106.2


R404A)


Refrigerating capacity ratio
%
100
86.2
98.5
99.1
100
102.1
104.5
106.9


(relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Example
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
2-6
2-3
2-4
2-5
2-6
2-7
2-8
2-9























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-134a
mass %
0
0
0
0
0
0
0
0




HFC-143a
mass %
0
0
0
0
0
0
0
0




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
120.0
121.0
122.4
123.3
124.4
125.5
126.0
131.7



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.081
0.083
0.085
0.086
0.088
0.090
0.091
0.099



Compression ratio

23.1
23.0
22.8
22.6
22.5
22.3
22.2
21.6



COP ratio (relative to
%
106.2
106.3
106.3
106.3
106.3
106.4
106.4
106.7



R404A)



Refrigerating capacity ratio
%
109.5
111.7
114.6
116.4
118.7
121
122.2
133.3



(relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 2-2

The GWP of each of the mixed refrigerants shown in Examples 2-7 to 2-12, Comparative Examples 2-10 to 2-18, and Reference Example 2-2 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −35° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 2-1.


Table 65 shows the results of Test Example 2-2. Table 65 shows Examples and Comparative Examples with regard to Refrigerant 2 according to the present disclosure. In Table 65, the definitions of the terms are the same as those in Test Example 2-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 2-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 2-1. The burning velocity test was performed as in Test Example 2-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 2-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 65









Reference











Example
Comp.
Comp.




2-2
Ex.
Ex.
Example
Example
Example
Example
Example


Item
Unit
(R404A)
2-10
2-11
2-7
2-8
2-9
2-10
2-11




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-134a
mass %
4.0
0
0
0
0
0
0
0



HFC-143a
mass %
52.0
0
0
0
0
0
0
0



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
89.1
95.8
100.6
100.8
101.2
102.0
102.9
103.8


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.165
0.131
0.148
0.149
0.151
0.154
0.157
0.160


Compression ratio

11.0
12.2
11.8
11.7
11.7
11.6
11.6
11.5


COP ratio (relative to
%
100
105.1
104.8
104.7
104.7
104.7
104.6
104.5


R404A)


Refrigerating capacity ratio
%
100
87.7
98.5
99.0
99.8
101.6
103.7
105.7


(relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Example
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
2-12
2-12
2-13
2-14
2-15
2-16
2-17
2-18























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
466
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-134a
mass %
0
0
0
0
0
0
0
0




HFC-143a
mass %
0
0
0
0
0
0
0
0




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
104.7
105.5
106.6
107.3
108.1
109.0
109.5
113.9



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.164
0.167
0.171
0.174
0.177
0.180
0.181
0.196



Compression ratio

11.4
11.4
11.3
11.2
11.2
11.1
11.1
10.8



COP ratio (relative to
%
104.5
104.4
104.4
104.4
104.3
104.3
104.3
104.3



R404A)



Refrigerating capacity ratio
%
108.0
109.8
112.3
113.8
115.7
117.7
118.6
128.0



(relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 2-3

The GWP of each of the mixed refrigerants shown in Examples 2-13 to 2-18, Comparative Examples 2-19 to 2-27, and Reference Example 2-3 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −10° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 2-1.


Table 66 shows the results of Test Example 2-3. Table 66 shows Examples and Comparative Examples with regard to Refrigerant 2 according to the present disclosure. In Table 66, the definitions of the terms are the same as those in Test Example 2-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 2-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 2-1. The burning velocity test was performed as in Test Example 2-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 2-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 66









Reference











Example
Comp.
Comp.




2-3
Ex.
Ex.
Example
Example
Example
Example
Example


Item
Unit
(R404A)
2-19
2-20
2-13
2-14
2-15
2-16
2-17




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
75.8
80.8
83.7
83.9
84.1
84.5
85.1
85.6


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.434
0.357
0.399
0.401
0.404
0.411
0.419
0.427


Compression ratio

4.2
4.5
4.4
4.4
4.4
4.3
4.3
4.3


COP ratio (relative to
%
100
103.8
102.9
102.9
102.8
102.7
102.5
102.4


R404A)


Refrigerating capacity
%
100
89.8
98.7
99.1
99.8
101.2
102.8
104.5


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Example
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
2-18
2-21
2-22
2-23
2-24
2-25
2-26
2-27























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-
mass %
0
0
0
0
0
0
0
0




134a




HFC-
mass %
0
0
0
0
0
0
0
0




143a




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
86.2
86.6
87.3
87.7
88.2
88.7
88.9
91.5



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.436
0.443
0.452
0.457
0.465
0.472
0.475
0.509



Compression ratio

4.3
4.3
4.3
4.3
4.3
4.2
4.2
4.2



COP ratio (relative to
%
102.2
102.1
102.0
101.9
101.8
101.7
101.6
101.3



R404A)



Refrigerating capacity
%
106.2
107.7
109.6
110.8
112.3
113.8
114.5
121.7



ratio (relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 2-4

The GWP of each of the mixed refrigerants shown in Examples 2-19 to 2-24, Comparative Examples 2-28 to 2-36, and Reference Example 2-4 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: −80° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 2-1.


Table 67 shows the results of Test Example 2-4. Table 67 shows Examples and Comparative Examples with regard to Refrigerant 2 according to the present disclosure. In Table 67, the definitions of the terms are the same as those in Test Example 2-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 2-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 2-1. The burning velocity test was performed as in Test Example 2-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 2-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 67









Reference











Example
Comp.
Comp.




2-4
Ex.
Ex.
Example
Example
Example
Example
Example


Item
Unit
(R404A)
2-26
2-29
2-19
2-20
2-21
2-22
2-23




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
136.7
146.0
157.7
158.1
158.8
160.4
162.1
163.9


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.014
0.011
0.012
0.012
0.012
0.012
0.013
0.013


Compression ratio

134.6
149.1
150.8
150.2
149.3
147.2
145.0
142.8


COP ratio (relative to
%
100
112.6
110.3
110.3
110.4
110.6
110.8
111.0


R404A)


Refrigerating capacity
%
100
91.7
99.3
100.2
101.5
104.4
107.8
111.3


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Example
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
2-24
2-30
2-31
2-32
2-33
2-34
2-35
2-36























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-
mass %
0
0
0
0
0
0
0
0




134a




HFC-
mass %
0
0
0
0
0
0
0
0




143a




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
165.8
167.4
169.6
170.9
172.6
174.3
175.2
184.0



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.013
0.014
0.014
0.014
0.015
0.015
0.015
0.017



Compression ratio

140.5
138.7
136.3
134.9
133.2
131.5
130.7
123.8



COP ratio (relative to
%
111.3
111.4
111.7
111.9
112.1
112.3
112.4
113.5



R404A)



Refrigerating capacity
%
115.1
118.2
122.5
125.2
128.6
132.1
133.8
151.0



ratio (relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 2-5

The GWP of each of the mixed refrigerants shown in Examples 2-25 to 2-30, Comparative Examples 2-37 to 2-45, and Reference Example 2-5 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 40° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using NIST and Refprop 9.0 under the following conditions.


Evaporating temperature: 10° C.


Condensation temperature: 40° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The definitions of the terms are the same as those in Test Example 2-1.


Table 68 shows the results of Test Example 2-5. Table 68 shows Examples and Comparative Examples with regard to Refrigerant 2 according to the present disclosure. In Table 68, the definitions of the terms are the same as those in Test Example 2-1.


The coefficient of performance (COP) and the compression ratio were determined as in Test Example 2-1.


The flammability of each of the mixed refrigerants was evaluated as in Test Example 2-1. The burning velocity test was performed as in Test Example 2-1.


The flammable range of each of the mixed refrigerants was measured in the same manner and under the same test conditions as in Test Example 2-1 by using a measurement device according to ASTM E681-09 (see FIG. 20).


















TABLE 68









Reference











Example
Comp.
Comp.




2-5
Ex.
Ex.
Example
Example
Example
Example
Example


Item
Unit
(R404A)
2-37
2-38
2-25
2-26
2-27
2-28
2-29




















Composition
HFO-
mass %
0
30.0
40.0
40.5
41.3
43.0
45.0
47.0


ratio
1132 (E)



HFO-
mass %
0
70.0
60.0
59.5
58.7
57.0
55.0
53.0



1234yf



HFC-
mass %
4.0
0
0
0
0
0
0
0



134a



HFC-
mass %
52.0
0
0
0
0
0
0
0



143a



HFC-125
mass %
44.0
0
0
0
0
0
0
0
















GWP (AR4)

3922
6
6
6
6
7
7
7


Discharge temperature
° C.
68.5
72.4
74.0
74.1
74.2
74.4
74.7
74.9


Saturation pressure
MPa
1.822
1.592
1.745
1.752
1.764
1.788
1.817
1.844


(40° C.)


Evaporation pressure
MPa
0.820
0.694
0.768
0.772
0.777
0.789
0.803
0.817


Compression ratio

2.2
2.3
2.3
2.3
2..3
2.3
2.3
2.3


COP ratio (relative to
%
100.0
103.1
101.9
101.8
101.7
101.5
101.3
101.1


R404A)


Refrigerating capacity
%
100.0
91.2
98.9
99.3
99.8
101.0
102.5
103.8


ratio (relative to R404A)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.





Example
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.



Item
Unit
2-30
2-39
2-40
2-41
2-42
2-43
2-44
2-45























Composition
HFO-
mass %
49.2
51.0
53.5
55.0
57.0
59.0
60.0
70.0



ratio
1132 (E)




HFO-
mass %
50.8
49.0
46.5
45.0
43.0
41.0
40.0
30.0




1234yf




HFC-
mass %
0
0
0
0
0
0
0
0




134a




HFC-
mass %
0
0
0
0
0
0
0
0




143a




HFC-125
mass %
0
0
0
0
0
0
0
0


















GWP (AR4)

7
7
7
7
7
8
8
8



Discharge temperature
° C.
75.2
75.5
75.8
76.0
76.2
76.5
76.6
77.9



Saturation pressure
MPa
1.874
1.898
1.931
1.950
1.975
2.000
2.012
2.128



(40° C.)



Evaporation pressure
MPa
0.832
0.844
0.860
0.870
0.882
0.895
0.901
0.959



Compression ratio

2.3
2.2
2.2
2.2
2.2
2.2
2.2
2.2



COP ratio (relative to
%
100.9
100.8
100.6
100.4
100.3
100.1
100.1
99.5



R404A)



Refrigerating capacity
%
105.3
106.5
108.2
109.1
110.4
111.6
112.3
118.2



ratio (relative to R404A)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2
Class 2
Class 2
Class 2
Class 2



classification










Test Example 3

The GWP of each of the mixed refrigerants shown in Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-5, Reference Example 3-1 (R134a), and Reference Example 3-2 (R404A) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, saturation pressure at a saturation temperature of 45° C., condensation pressure, and evaporation pressure of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


Evaporating temperature: −10° C.


Condensation temperature: 45° C.


Superheating temperature: 20 K


Subcooling temperature: 0 K


Compressor efficiency: 70%


The “evaporating temperature of −10° C.” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration apparatus is −10° C. Further, the “condensation temperature of 45° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigeration apparatus is 45° C.


Table 69 shows the results of Test Example 3. Table 69 shows Examples and Comparative Examples with regard to Refrigerant 3 according to the present disclosure. In Table 69, the “COP ratio” and the “refrigerating capacity ratio” refer to a ratio (%) relative to R134a. In Table 69, the “saturation pressure (45° C.)” refers to a saturation pressure at a saturation temperature of 45° C. In Table 69, the “discharge temperature (° C.)” refers to a temperature at which the mixed refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations of the mixed refrigerant.


The coefficient of performance (COP) was calculated according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


The critical temperature was determined by performing calculations using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).


The flammability of the mixed refrigerants was determined by adjusting the mixed formulations of the mixed refrigerants to WCF concentrations and measuring the burning velocity according to ANSI/ASHRAE Standard 34-2013. The mixed refrigerant with a burning velocity of 0 cm/s to 10 cm/s was classified as Class 2L (slight flammability), the mixed refrigerant with a burning velocity of more than 10 cm/s was classified as Class 2 (weak flammability), and the mixed refrigerant with no flame propagation was classified as Class 1 (non-flammability). In Table 69, the ASHRAE flammability classification shows the results based on these criteria.


The burning velocity test was performed as follows. 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 in a PC.


The flammable range of each of the mixed refrigerants was measured using a measurement device according to ASTM E681-09 (see FIG. 20).


More specifically, a 12-L spherical glass flask was used so that the combustion state could be visually observed and photographically recorded. When excessive pressure was generated by combustion in the glass flask, gas was allowed to escape from the upper lid. Ignition was achieved by electric discharge from electrodes disposed at one-third the distance from the bottom.


Test Conditions

Test vessel: 280-mm φ spherical (internal volume: 12 liters) Test temperature: 60° C.±3° C.


Pressure: 101.3 kPa±0.7 kPa


Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at 23° C.) per gram of dry air


Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2 vol. %


Mixture of refrigerant composition: ±0.1 mass %


Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA, neon transformer


Electrode spacing: 6.4 mm (¼ inch)


Spark: 0.4 seconds±0.05 seconds


Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignition point, it was evaluated that flame propagation was present (flammable).


When the flame spread at an angle of 90° or less from the ignition point, it was evaluated that flame propagation was absent (non-flammable).

















TABLE 69









Reference










Example
Comp.
Comp.




3-1
Ex.
Ex.
Example
Example
Example
Example


Item
Unit
(R134a)
3-1
3-2
3-1
3-2
3-3
3-4



















Composition
HFO-1132 (E)
mass %
0
20.0
30.0
31.1
33.0
35.0
37.9


ratio



HFO-1234yf
mass %
0
80.0
70.0
68.9
67.0
65.0
62.1



HFC-134a
mass %
100.0
0
0
0
0
0
0



HFC-143a
mass %
0
0
0
0
0
0
0



HFC-125
mass %
0
0
0
0
0
0
0















GWP (AR4)

1430
5
6
6
6
6
6


Discharge temperature
° C.
86.9
86.3
86.9
87.2
87.9
88.5
89.4


Situration pressure
MPa
1.160
1.607
1.795
1.814
1.848
1.883
1.930


(45° C.)


Evaporation pressure
MPa
0.201
0.311
0.355
0.360
0.368
0.376
0.388


Critical temperature
° C.
101.1
84.6
83.0
82.7
82.2
81.7
81.0


COP ratio (relative to R134a)
%
100.0
93.8
92.7
92.6
92.4
92.2
92.0


Refrigerating capacity ratio
%
100.0
132.3
148.3
150.0
152.8
155.8
159.8


(relative to R134a)


ASHRAE flammability

Class 1
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification
























Reference






Comp.
Comp.
Comp.
Example





Example
Ex.
Ex.
Ex.
3-2



Item
Unit
3-5
3-3
3-4
3-5
(R404A)




















Composition
HFO-1132 (E)
mass %
39.8
40.0
50.0
0.0
0



ratio




HFO-1234yf
mass %
60.2
60.0
50.0
100.0
0




HFC-134a
mass %
0
0
0
0
4.0




HFC-143a
mass %
0
0
0
0
52.0




HFC-125
mass %
0
0
0
0
44.0















GWP (AR4)

6
6
7
4
3922



Discharge temperature
° C.
90.0
90.1
93.0
72.2
81.7



Situration pressure
MPa
1.963
1.966
2.123
1.154
2.052



(45° C.)



Evaporation pressure
MPa
0.397
0.397
0.437
0.222
0.434



Critical temperature
° C.
80.5
80.5
78.7
94.7
72.0



COP ratio (relative to R134a)
%
91.8
91.8
91.0
95.7
88.6



Refrigerating capacity ratio
%
162.7
162.9
176.6
96.2
164.4



(relative to R134a)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2L
Class 1



classification










Test Example 4

The GWP of each of the mixed refrigerants shown in Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-5 was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, discharge temperature, and saturation pressure at a saturation temperature of −10° C. of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


Evaporating temperature: 5° C.


Condensation temperature: 45° C.


Superheating temperature: 5 K


Subcooling temperature: 5 K


Compressor efficiency: 70%


The “evaporating temperature of 5° C.” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration apparatus is 5° C. Further, the “condensation temperature of 45° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigeration apparatus is 45° C.


Table 70 shows the results of Test Example 4. Table 70 shows Examples and Comparative Examples with regard to Refrigerant 4 according to the present disclosure. In Table 70, the “COP ratio” and the “refrigerating capacity ratio” refer to a ratio (%) relative to R1234yf. In Table 70, the “saturation pressure (−10° C.)” refers to a saturation pressure at a saturation temperature of −10° C., which is a typical value of the evaporating temperature in the refrigeration condition. In Table 70, the “discharge temperature (° C.)” refers to a temperature at which the mixed refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations of the mixed refrigerant.


The coefficient of performance (COP) was calculated according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


The critical temperature was determined by performing calculations using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).


The flammability of the mixed refrigerants was determined by adjusting the mixed formulations of the mixed refrigerants to WCF concentrations and measuring the burning velocity according to ANSI/ASHRAE Standard 34-2013. The mixed refrigerant with a burning velocity of 0 cm/s to 10 cm/s was classified as Class 2L (slight flammability), the mixed refrigerant with a burning velocity of more than 10 cm/s was classified as Class 2 (weak flammability), and the mixed refrigerant with no flame propagation was classified as Class 1 (non-flammability). In Table 70, the ASHRAE flammability classification shows the results based on these criteria.


The burning velocity test was performed as follows. 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 in a PC.


The flammable range of each of the mixed refrigerants was measured using a measurement device according to ASTM E681-09 (see FIG. 20).


More specifically, a 12-L spherical glass flask was used so that the combustion state could be visually observed and photographically recorded. When excessive pressure was generated by combustion in the glass flask, gas was allowed to escape from the upper lid. Ignition was achieved by electric discharge from electrodes disposed at one-third the distance from the bottom.


Test Conditions

Test vessel: 280-mm φ spherical (internal volume: 12 liters)


Test temperature: 60° C.±3° C.


Pressure: 101.3 kPa±0.7 kPa


Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at 23° C.) per gram of dry air


Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2 vol. %


Mixture of refrigerant composition: ±0.1 mass %


Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA, neon transformer


Electrode spacing: 6.4 mm (¼ inch)


Spark: 0.4 seconds±0.05 seconds


Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignition point, it was evaluated that flame propagation was present (flammable).


When the flame spread at an angle of 90° or less from the ignition point, it was evaluated that flame propagation was absent (non-flammable).

















TABLE 70









Comparative
Comparative









Example
Example
Example
Example
Example
Example
Example


Item
Unit
4-1
4-2
4-1
4-2
4-3
4-4
4-5



















Composition
HFO-1132 (E)
mass %
0
15.0
21.0
23.6
24.3
25.1
26.7


ratio
HFO-1234yf
mass %
100.0
85.0
79.0
76.4
75.7
74.9
73.3















GWP (AR4)

4
5
5
5
5
6
6


Discharge temperature
° C.
54.4
61.3
63.1
63.8
64.0
64.2
64.6


Situration pressure
MPa
0.222
0.350
0.383
0.396
0.400
0.403
0.411


(−10° C.)


Critical temperature
° C.
94.7
88.1
85.9
85.0
84.8
84.5
84.0


COP ratio (relative to R1234yf)
%
100.0
99.1
98.8
98.6
98.5
98.4
98.3


Refrigerating capacity ratio
%
100.0
129.8
140.0
144.2
145.4
146.6
149.1


(relative to R1234yf)


ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L
Class 2L


classification






















Comparative
Comparative
Comparative





Example
Example
Example
Example
Example



Item
Unit
46
4-7
4-3
4-4
4-5




















Composition
HFO-1132 (E)
mass %
27.5
28.4
30.0
40.0
50.0



ratio
HFO-1234yf
mass %
72.5
71.6
70.0
60.0
50.0















GWP (AR4)

6
6
6
6
7



Discharge temperature
° C.
64.8
65.0
65.4
67.5
69.4



Situration pressure
MPa
0.414
0.418
0.425
0.461
0.492



(−10° C.)



Critical temperature
° C.
83.8
83.5
83.0
80.5
78.7



COP ratio (relative to R1234yf)
%
98.2
98.2
98.0
97.2
96.6



Refrigerating capacity ratio
%
150.3
151.7
154.1
168.2
181.3



(relative to R1234yf)



ASHRAE flammability

Class 2L
Class 2L
Class 2L
Class 2L
Class 2L



classification










Test Example 5

The GWP of each of the mixed refrigerants shown in Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-3, and Reference Example 5-1 (R134a) was evaluated based on the values stated in the IPCC, fourth report.


The COP, refrigerating capacity, boiling point, and discharge temperature of each of the mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


Evaporating temperature: −30° C.


Condensation temperature: 30° C.


Superheating temperature: 5 K


Subcooling temperature: 5 K


Compressor efficiency: 70%


The “evaporating temperature of −30° C.” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration apparatus is −30° C. Further, the “condensation temperature of 30° C.” means that the condensation temperature of the mixed refrigerant in the condenser provided in the refrigeration apparatus is 30° C.


Table 71 shows the results of Test Example 5. Table 71 shows Examples and Comparative Examples with regard to Refrigerant 5 according to the present disclosure. In Table 71, the “COP ratio” and the “refrigerating capacity ratio” refer to a ratio (%) relative to R1234yf. In Table 71, the “discharge temperature (° C.)” refers to a temperature at which the mixed refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations of the mixed refrigerant. In Table 71, the “boiling point (° C.)” means a temperature at which the liquid phase of the mixed refrigerant has atmospheric pressure (101.33 kPa). In Table 71, the “motor power consumption (%)” refers to electrical energy used to enable an electric vehicle to run, and is expressed as a ratio with respect to power consumption when the refrigerant is HFO-1234yf. In Table 71, the “heater power consumption (%)” refers to electrical energy used to operate a heater by an electric vehicle, and is expressed as a ratio with respect to power consumption when the refrigerant is HFO-1234yf. In Table 71, the “drivable distance” refers to a distance drivable by an electric vehicle equipped with a rechargeable battery having a constant electric capacity while having a heater turned on, and is expressed as a ratio (%) relative to a drivable distance (100%) when the electric vehicle is driven without a heater turned on (i.e., heater power consumption is 0).


The coefficient of performance (COP) was calculated according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


The flammability of the mixed refrigerants was determined by adjusting the mixed formulations of the mixed refrigerants to WCF concentrations and measuring the burning velocity according to ANSI/ASHRAE Standard 34-2013. The burning velocity was measured as follows. 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 in a PC.


Heating was performed by using an electrical heater in the case of a refrigerant having a boiling point of more than −40° C., and using a heat pump in the case of a refrigerant having a boiling point of −40° C. or less.


The power consumption when the heater was used was calculated according to the following formula.





Power consumption when the heater was used=heating capacity/COP of heater


The COP of the heater refers to heating efficiency.


With regard to the heating efficiency, the COP of the heater is 1 in an electric heater, and the heater consumes an electrode equivalent to the motor power. That is, the power consumption of the heater is E=E/(1+COP). In the case of a heat pump, the COP of the heater 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.


Evaporating temperature: −30° C.


Condensation temperature: 30° C.


Superheating temperature: 5 K


Subcooling temperature: 5 K


Compressor efficiency: 70%


The drivable distance was calculated according to the following formula.





Drivable distance=(battery capacity)/(motor power consumption+heater power consumption)



















TABLE 71









Reference
Comp.
Comp.










Example
Ex.
Ex.
Example
Example
Example
Example
Example
Example


Item
Unit
5-1
5-1
5-2
5-1
5-2
5-3
54
5-5
5-6





















Composition
HFO-
mass %
0.0
0
10.0
12.1
15.0
20.0
25.0
30.0
35.0


ratio
1132 (E)



HFO-
mass %
0.0
100.0
90.0
87.9
85.0
80.0
75.0
70.0
65.0



1234yf



HFC-
mass %
100.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0



134a

















GWP (AR4)

1430
4
5
5
5
5
6
6
6


COP ratio (relative to
%
105
100
100
100
100
100
100
100
100


R1234yf)


Refrigerating capacity
%
99
100
123
128
134
145
155
165
175


ratio (relative to 1234yf)


Motor power
%
100
100
100
100
100
100
100
100
100


consumption amount


Heater power
%
95
100
100
33
33
33
33
33
33


consumption amount


Drivable distance
%
100
100
100
100
100
100
100
100
100


(without heater)


Drivable distance
%
50
50
50
84
84
84
84
84
84


(with heater)


Discharge temperature
° C.
66.0
48.0
54.8
56.0
57.5
59.8
61.9
63.9
65.8


Combustion rate
cm/s
0.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.0


Boiling point
° C.
−26.1
−29.5
−38.8
−40.0
−41.4
−43.3
−44.7
−45.9
−46.9


Saturation pressure at −40° C.
kPaG
−50.1
−39
−4.4
0.9
7.5
17.2
25.3
32.3
38.4


Heating method
System
Electric
Electric
Electric
Heat
Heat
Heat
Heat
Heat
Heat




heater
heater
heater
pump
pump
pump
pump
pump
pump






























Comp.





Example
Example
Example
Example
Example
Example
Example
Ex.



Item
Unit
5-7
5-8
5-9
5-10
5-11
5-12
5-13
5-3























Composition
HFO-
mass %
40.0
45.0
50.0
55.0
60.0
65.0
72.0
75.0



ratio
1132 (E)




HFO-
mass %
60.0
55.0
50.0
45.0
40.0
35.0
28.0
25.0




1234yf




HFC-
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0




134a


















GWP (AR4)

6
7
7
7
8
8
8
9



COP ratio (relative to
%
100
100
100
100
100
100
100
100



R1234yf)



Refrigerating capacity
%
185
194
203
212
220
229
240
245



ratio (relative to 1234yf)



Motor power
%
100
100
100
100
100
100
100
100



consumption amount



Heater power
%
33
33
33
33
33
33
33
33



consumption amount



Drivable distance
%
100
100
100
100
100
100
100
100



(without heater)



Drivable distance
%
84
84
84
84
84
84
84
84



(with heater)



Discharge temperature
° C.
67.6
69.3
70.9
72.6
74.2
75.9
78.2
79.2



Combustion rate
cm/s
2.6
3.4
4.3
5.3
6.5
7.3
9.9
10.9



Boiling point
° C.
−47.7
−48.4
−49.1
−49.6
−50.2
−50.5
−51.2
−51.4



Saturation pressure at −40° C.
kPaG
43.9
48.8
53.4
57.5
61.4
65.0
69.6
71.5



Heating method
System
Heat
Heat
Heat
Heat
Heat
Heat
Heat
Heat





pump
pump
pump
pump
pump
pump
Pump
pump










4. Refrigerating Machine

The refrigerating machine according to the present disclosure comprises, as a working fluid, a gas phase containing a refrigerant comprising HFO-1132 and oxygen, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


As mentioned above, the stability of HFO-1132 is improved in the 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.


EXAMPLES

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


Stability Test 1
Examples 1 to 7

The inside of a pressure-resistant container made of SUS316 (internal volume: 30 cc) was evacuated, and a predetermined amount of oxygen was enclosed in the pressure-resistant container. Thereafter, 15 g of liquefied trans-1,2-difluoroethylene having a purity of 99.5% or more was placed therein, and the oxygen concentration in the gas phase was adjusted to the value shown in Table 72 at 25° C. Subsequently, the pressure-resistant container, in which trans-1,2-difluoroethylene was enclosed together with the predetermined concentration of oxygen, was placed in a hot-air-circulating constant-temperature chamber and allowed to stand at a constant temperature of 60° C. for 20 days.


After 20 days, the pressure-resistant container was removed from the constant-temperature chamber, and trans-1,2-difluoroethylene was released. The presence or absence of production of solid substance was examined with the naked eye. Moreover, the inside of the container was washed with dichloropentafluoropropane and perfluorohexane, and the solution was dried at 100° C. to determine the amount of solid substance produced. Table 72 shows the results. In Table 72, A indicates that the amount of solid substance produced is less than 3 mg; B indicates that the amount of solid substance produced is 3 to 10 mg, but that there is no practical problem; C indicates that the amount of solid substance produced is 11 to 50 mg, but that there is no practical problem; and D indicates that the amount of solid substance produced is 50 mg or more.


Subsequently, with respect to Examples 1 to 7, in which a solid substance was observed with the naked eye, the solid substance after drying was dissolved in deuterated acetone, and 1H-NMR, 13C-NMR, and 19F-NMR spectra were measured. Identification of the solid substance by peak assignment of the measured NMR spectra revealed that it was a homopolymer of trans-1,2-difluoroethylene. It is presumed that this was produced by polymerization of trans-1,2-difluoroethylene.













TABLE 72









Amount of



Oxygen
Presence or
solid



concentration
absence of
substance



in gas
solid
produced



(volume ppm)
substance
(mg)





















Example 1
4
A
<3



Example 2
10
A
<3



Example 3
200
B
4



Example 4
400
B
10



Example 5
500
C
15



Example 6
1000
C
20



Example 7
4000
D
60










Stability Test 2
Examples 8 and 9

The inside of a pressure-resistant container made of SUS316 (internal volume: 30 cc) was evacuated, and a predetermined amount of oxygen was enclosed in the pressure-resistant container. Thereafter, 10 g of liquefied trans-1,2-difluoroethylene having a purity of 99.5% or more was placed therein, and the oxygen concentration in the gas phase was adjusted to the value shown in Table 73 at 25° C. Subsequently, the pressure-resistant container, in which trans-1,2-difluoroethylene was enclosed together with the predetermined concentration of oxygen, was placed in a hot-air-circulating constant-temperature chamber and allowed to stand at a constant temperature of 80° C. for 5 days.


After 5 days, the pressure-resistant container was removed from the constant-temperature chamber, and trans-1,2-difluoroethylene was released. The presence or absence of production of solid substance was examined with the naked eye. Moreover, the inside of the container was washed with dichloropentafluoropropane and perfluorohexane, and the solution was dried at 100° C. to determine the amount of solid substance produced. Table 73 shows the results. In Table 73, A indicates that the amount of solid substance produced is less than 3 mg; B indicates that the amount of solid substance produced is 0 to 3 mg, but that there is no practical problem; C indicates that the amount of solid substance produced is 4 to 50 mg, but that there is no practical problem; and D indicates that the amount of solid substance produced is 50 mg or more.


Subsequently, with respect to Examples 8 and 9, in which a solid substance was observed with the naked eye, the solid substance after drying was dissolved in deuterated acetone, and 1H-NMR, 13C-NMR, and 19F-NMR spectra were measured. Identification of the solid substance by peak assignment of the measured NMR spectra revealed that it was a homopolymer of trans-1,2-difluoroethylene. It is presumed that this was produced by polymerization of trans-1,2-difluoroethylene.













TABLE 73









Amount of



Oxygen
Presence or
solid



concentration
absence of
substance



in gas
solid
produced



(volume ppm)
substance
(mg)





















Example 8
4
A
<3



Example 9
300
D
60










Stability Test 2
Examples 10 to 15

Trans-1,2-difluoroethylene with a purity of 99.5% or more was placed in a glass tube (8 mm ID×12 mm OD×300 mm L) sealed on one side. Subsequently, oxygen was enclosed in the tube so that the oxygen concentration in the gas phase was adjusted to the value shown in Table 74 at 25° C. The tube was allowed to stand in a constant-temperature chamber in an atmosphere at 150° C. and kept in this state for 1 week. Thereafter, the tube was removed from the constant-temperature chamber and cooled. The acid in the gas inside the tube was analyzed to evaluate the stability of trans-1, 2-difluoroethylene.


The acid in the gas was analyzed by the following method. Gas remaining in the above tube after cooling was completely solidified using liquid nitrogen. The tube was then opened and gradually thawed to collect gas into a Tedlar bag. 5 g of pure water was injected into the Tedlar bag to extract the acid into the pure water while efficiently bringing the pure water into contact with the collected gas. The extract was detected by ion chromatography to determine the content (weight ppm) of fluoride ions (F). Table 74 shows the test results. In Table 74, A indicates that the acid content is less than 1 weight ppm; B indicates that the acid content is 1 to 3 weight ppm, but that there is no practical problem; C indicates that the acid content is 4 to 10 weight ppm, but that there is no practical problem; and D indicates that the acid content is 100 weight ppm or more.













TABLE 74







Oxygen





concentration
Presence or



in gas
absence of
Acid content



(volume ppm)
acid
(weight ppm)



















Example 10
4
A
<1


Example 11
200
A
<1


Example 12
400
B
3


Example 13
1000
C
10


Example 14
4000
D
100









Item 1. A method for allowing a refrigerant comprising 1,2-difluoroethylene (HFO-1132) and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


Item 2. A method for storing a refrigerant comprising HFO-1132 by allowing the refrigerant and oxygen to coexist in a gas phase in a closed container, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


Item 3. The method according to Item 1 or 2, wherein the temperature of the gas phase is less than 80° C.


Item 4. The method according to any one of Items 1 to 3, wherein the gas phase coexists with a liquid phase containing the refrigerant.


Item 5. The method according to Item 1 or 2, wherein a refrigerating machine is operated using the refrigerant as a working fluid, the method comprises performing the coexistence in the refrigerating machine, and the concentration of oxygen in the gas phase at a temperature of 25° C. is 1000 volume ppm or less.


Item 6. The method according to Item 5, wherein the gas phase coexists with a liquid phase containing the refrigerant in at least part of the refrigerating machine.


Item 7. A method for stabilizing a refrigerant comprising HFO-1132, the method comprising, in a state that allows the refrigerant and oxygen to coexist in a gas phase, maintaining the concentration of oxygen in the gas phase at a temperature of 25° C. to 1000 volume ppm or less to thereby stabilize the refrigerant.


Item 7. A storage container of a refrigerant comprising HFO-1132, in which the refrigerant and oxygen coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


Item 8. A refrigerating machine comprising, as a working fluid, a gas phase containing a refrigerant comprising HFO-1132 and oxygen, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.


Item 9. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and 2,3,3, 3-tetrafluoro-1-propene (R1234yf).


Item 10. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein in the refrigerant, 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, 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment GH is represented by coordinates (−0.0134z2−1.0825z+56.692, 0.0134z2+0.0825z+43.308, z), and


the lines HO and OD are straight lines.


Item 11. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein in the refrigerant, 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 (0.0047y2−1.5177y+87.598, y, −0.0047y2+0.5177y+12.402),


the line segment GH is represented by coordinates (−0.0134z2−1.0825z+56.692, 0.0134z2+0.0825z+43.308, z), and


the line segments HI and IL are straight lines.


Item 12. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant further comprises difluoromethane (R32).


Item 13. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein in the refrigerant, when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32 based on their sum is respectively represented by x, y, z, and a,


if 0<a≤10.0, 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 straight lines that connect the following 4 points:


point A (0.02a2−2.46a+93.4, 0, −0.02a2+2.46a+6.6),


point B′ (−0.008a2−1.38a+56, 0.018a2−0.53a+26.3, −0.01a2+1.91a+17.7),


point C (−0.016a2+1.02a+77.6, 0.016a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C);


if 10.0<a≤16.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0244a2−2.5695a+94.056, 0, −0.0244a2+2.5695a+5.944),


point B′ (0.1161a2−1.9959a+59.749, 0.014a2−0.3399a+24.8, −0.1301a2+2.3358a+15.451),


point C (−0.0161a2+1.02a+77.6, 0.0161a2−1.02a+22.4, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C); or


if 16.5<a≤21.8, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines that connect the following 4 points:


point A (0.0161a2−2.3535a+92.742, 0, −0.0161a2+2.3535a+7.258),


point B′ (−0.0435a2−0.0435a+50.406, −0.0304a2+1.8991a−0.0661, 0.0739a2−1.8556a+49.6601),


point C (−0.0161a2+0.9959a+77.851, 0.0161a2−0.9959a+22.149, 0), and


point O (100.0, 0.0, 0.0),


or on the straight lines OA, AB′, and B′C (excluding the points O and C).


Item 14. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1123 in a total amount of 99.5 mass % or more based on the entire refrigerant, and the refrigerant comprises HFO-1132(E) in an amount of 62.5 mass % to 72.5 mass % based on the entire refrigerant.


Item 15. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), R32, and R1234yf, and


in the refrigerant, when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AC, CF, FD, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point C (36.5, 18.2, 45.3),


point F (47.6, 18.3, 34.1), and


point D (72.0, 0.0, 28.0),


or on the line segments AC, CF, FD, and DA;


the line segment AC is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904),


the line segment FD is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28), and


the line segments CF and DA are straight lines.


Item 16. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), R32, and R1234yf, and


in the refrigerant, when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments AB, BE, ED, and DA that connect the following 4 points:


point A (71.1, 0.0, 28.9),


point B (42.6, 14.5, 42.9),


point E (51.4, 14.6, 34.0), and


point D (72.0, 0.0, 28.0),


or on the line segments AB, BE, ED, and DA;


the line segment AB is represented by coordinates (0.0181y2−2.2288y+71.096, y, −0.0181y2+1.2288y+28.904),


the line segment ED is represented by coordinates (0.02y2−1.7y+72, y, −0.02y2+0.7y+28), and


Item 17. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), R32, and R1234yf, and


in the refrigerant, when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments GI, IJ, and JK that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point I (55.1, 18.3, 26.6), and


point J (77.5. 18.4, 4.1),


or on the line segments GI, IJ, and JK;


the line segment GI is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604), and


the line segments IJ and JK are straight lines.


Item 18. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), R32, and R1234yf, and


in the refrigerant, when the mass % of HFO-1132(E), R32, 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), R32, and R1234yf is 100 mass % are within the range of a figure surrounded by line segments GH, HK, and KG that connect the following 3 points:


point G (77.5, 6.9, 15.6),


point H (61.8, 14.6, 23.6), and


point K (77.5, 14.6, 7.9),


or on the line segments GH, HK, and KG;


the line segment GH is represented by coordinates (0.02y2−2.4583y+93.396, y, −0.02y2+1.4583y+6.604), and


the line segments HK and KG are straight lines.


Item 19. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), HFO-1123, and R32, and


in the refrigerant, when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC′, C′D′, D′E′, E′A′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5),


point E′ (41.8, 39.8, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments C′D′, D′E′, and E′A′ (excluding the points C′ and A′);


the line segment C′D′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2+1.1915z+43.3, z),


the line segment D′E′ is represented by coordinates (−0.0535z2+0.3229z+53.957, 0.0535z2+0.6771z+46.043, z), and


the line segments OC′, E′A′, and A′O are straight lines.


Item 20. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), HFO-1123, and R32, and


in the refrigerant, when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC, CD, DE, EA′, and A′O that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5),


point E (72.2, 9.4, 18.4), and


point A′ (81.6, 0.0, 18.4),


or on the line segments CD, DE, and EA′ (excluding the points C and A′);


the line segment CDE is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2+0.9852z+22.316, z), and


the line segments OC, EA′ and A′0 are straight lines.


Item 21. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), HFO-1123, and R32, and


in the refrigerant, when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC′, C′D′, D′A, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C′ (56.7, 43.3, 0.0),


point D′ (52.2, 38.3, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments C′D′ and D′A (excluding the points C′ and A);


the line segment C′D′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2+1.1915z+43.3, z), and


the line segments OC′, D′A, and AO are straight lines.


Item 22. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E), HFO-1123, and R32, and


in the refrigerant, when the mass % of HFO-1132(E), HFO-1123, and R32 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 R32 is 100 mass % are within the range of a figure surrounded by line segments OC, CD, DA, and AO that connect the following 5 points:


point O (100.0, 0.0, 0.0),


point C (77.7, 22.3, 0.0),


point D (76.3, 14.2, 9.5), and


point A (90.5, 0.0, 9.5),


or on the line segments CD and DA (excluding the points C and A);


the line segment CD is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2+0.9852z+22.316, z), and


the line segments OC, DA, and AO are straight lines.


Item 23. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf), and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤1.2, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5),


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight lines B″D and CI);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (51.6, 0.0, 48.4-w),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight lines B″D and CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ, JK, and KL, as well as straight lines LB″, B″D, DC, and CI that connect the following 7 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point L (51.7, 28.9, 19.4-w),


point B″ (51.6, 0.0, 48.4-w),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight lines B″D and CI);


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w),


the curve JK is represented by coordinates (x, 0.0095x2−1.2222x+67.676, −0.0095x2+0.2222x+32.324-w), and


the curve KL is represented by coordinates (x, 0.0049x2−0.8842x+61.488, −0.0049x2−0.1158x+38.512).


Item 24. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 2,3,3,3-tetrafluoro-1-propene (R1234yf), and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤1.2, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 5 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight line CI);


if 1.2<w≤1.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 5 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point F (36.6, −3w+3.9, 2w+59.5), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI);


if 1.3<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KB′, B′D, DC, and CI that connect the following 6 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KB′, B′D, DC, and CI that connect the following 6 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point K (36.8, 35.6, 27.6-w),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CI);


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w), and


the curve JK is represented by coordinates (x, 0.0095x2−1.2222x+67.676, −0.0095x2+0.2222x+32.324-w).


Item 25. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, R32, HFO-1132(E), and R1234yf, and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤1.2, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (18.2, −1.1111w2−3.1667w+31.9, 1.1111w2+2.1667w+49.9), and


point C (0.0, −4.9167w+58.317, 3.9167w+41.683),


or on the above line segments (excluding the points on the straight line CI);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (−0.0365w+18.26, 0.0623w2−4.5381w+31.856, −0.0623w2+3.5746w+49.884), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CI); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves IJ and JK, as well as straight lines KF, FC, and CI that connect the following 4 points:


point I (0.0, 72.0, 28.0-w),


point J (18.3, 48.5, 33.2-w),


point E (18.1, 0.0444w2−4.3556w+31.411, −0.0444w2+3.3556w+50.489), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CI); and


the curve IJ is represented by coordinates (x, 0.0236x2−1.716x+72, −0.0236x2+0.716x+28-w).


Item 26. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, R32, HFO-1132(E), and R1234yf, and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤0.6, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a FIG. surrounded by curves GO and OP, as well as straight lines PB″, B″D, and DG that connect the following 5 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2+1.4167w+26.2, −1.25w2+0.75w+51.6),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6),


point P (51.7, 1.1111w2+20.5, −1.1111w2−w+27.8),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5), and


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683),


or on the above line segments (excluding the points on the straight line B″D);


if 0.6<w≤1.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves GN, NO, and OP, as well as straight lines PB″, B″D, and DG that connect the following 6 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2+1.4167w+26.2, −1.25w2+0.75w+51.6),


point N (18.2, 0.2778w2+3w+27.7, −0.2778w2−4w+54.1),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6),


point P (51.7, 1.1111w2+20.5, −1.1111w2−w+27.8),


point B″ (−1.5278w2+2.75w+50.5, 0.0, 1.5278w2−3.75w+49.5), and


point D (−2.9167w+40.317, 0.0, 1.9167w+59.683),


or on the above line segments (excluding the points on the straight line B″D),


if 0<w≤0.6, the curve GO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y),


if 0.6<w≤1.2, the curve GN is represented by coordinates (x, (0.0122w2−0.0113w+0.0313)x2+(−0.3582w2+0.1624w−1.4551)x+2.7889w2+3.7417w+43.824, 100-w-x-y),


if 0.6<w≤1.2, the curve NO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y), and


if 0<w≤1.2, the curve OP is represented by coordinates (x, (0.0074w2−0.0133w+0.0064)x2+(−0.5839w2+1.0268w−0.7103)x+11.472w2−17.455w+40.07, 100-w-x-y);


if 1.2<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, NO, and OP, as well as straight lines PB″, B″D, DC, and CM that connect the following 8 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+44.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point P (51.7, −0.2381w2+1.881w+20.186, 0.2381w2−2.881w+28.114),


point B″ (51.6, 0.0, −w+48.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight lines B″D and CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y),


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0375w2−0.239w−0.4977)x−0.8575w2+6.4941w+36.078, 100-w-x-y), and


the curve OP is represented by coordinates (x, (−0.000463w2+0.0024w−0.0011)x2+(0.0457w2−0.2581w−0.075)x−1.355w2+8.749w+27.096, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, NO, and OP, as well as straight lines PB″, B″D, DC, and CM that connect the following 8 points:


point M (0.0, −0.0667w2+0.8333w+58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point O (36.8, −0.0444w2+0.6889w+25.956, 0.0444w2−1.6889w+37.244),


point P (51.7, −0.0667w2+0.8333w+21.633, 0.0667w2−1.8333w+26.667),


point B″ (51.6, 0.0, −w+48.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight lines B″D and CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y),


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y),


the curve NO is represented by coordinates (x, 0.0082x2+(0.0022w2−0.0345w−0.7521)x−0.1307w2+2.0247w+42.327, 100-w-x-y), and


the curve OP is represented by coordinates (x, (−0.0006258w2+0.0066w−0.0153)x2+(0.0516w2−0.5478w+0.9894)x−1.074w2+11.651w+10.992, 100-w-x-y).


Item 27. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, R32, HFO-1132(E), and R1234yf, and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 0<w≤0.6, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curve GO and straight lines OF and FG that connect the following 3 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2−1.4167w+26.2, −1.25w2+3.5834w+51.6),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6), and


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997), or on the above line segments, and


the curve GO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072) x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y);


if 0.6<w≤1.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves GN and NO, as well as straight lines OF and FG that connect the following 4 points:


point G (−5.8333w2−3.1667w+22.2, 7.0833w2−1.4167w+26.2, −1.25w2+3.5834w+51.6),


point N (18.2, 0.2778w2+3.0w+27.7, −0.2.778w2−4.0w+54.1),


point O (36.8, 0.8333w2+1.8333w+22.6, −0.8333w2−2.8333w+40.6), and


point F (−0.0833w+36.717, −4.0833w+5.1833, 3.1666w+58.0997),


or on the above line segments,


if 0.6<w≤1.2, the curve GN is represented by coordinates (x, (0.0122w2−0.0113w+0.0313)x2+(−0.3582w2+0.1624w−1.4551)x+2.7889w2+3.7417w+43.824, 100-w-x-y), and


if 0.6<w≤1.2, the curve NO is represented by coordinates (x, (0.00487w2−0.0059w+0.0072)x2+(−0.279w2+0.2844w−0.6701)x+3.7639w2−0.2467w+37.512, 100-w-x-y);


if 1.2<w≤1.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OF, FC, and CM that connect the following 6 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point F (36.6, −3w+3.9, 2w+59.5), and


point C (0.1081w2−5.169w+58.447, 0.0, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y), and


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0375w2−0.239w−0.4977)x−0.8575w2+6.4941w+36.078, 100-w-x-y);


if 1.3<w≤4.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OB′, B′D, DC, and CM that connect the following 7 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point O (36.8, −0.1392w2+1.4381w+24.475, 0.1392w2−2.4381w+38.725),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8226w+40.211, 0.0, 1.8226w+59.789), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553),


or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y),


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y), and


the curve NO is represented by coordinates (x, (−0.00062w2+0.0036w+0.0037)x2+(0.0457w2−0.2581w−0.075)x−1.355w2+8.749w+27.096, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW, WN, and NO, as well as straight lines OB′, B′D, DC, and CM that connect the following 7 points:


point M (0.0, −0.0667w2+0.8333w58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point O (36.8, −0.0444w2+0.6889w+25.956, 0.0444w2−1.6889w+37.244),


point B′ (36.6, 0.0, −w+63.4),


point D (−2.8w+40.1, 0.0, 1.8w+59.9), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7),


or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y),


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y), and


the curve NO is represented by coordinates (x, (0.0082x2+(0.0022w2−0.0345w−0.7521)x−0.1307w2+2.0247w+42.327, 100-w-x-y).


Item 28. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises CO2, R32, HFO-1132(E), and R1234yf, and


when the mass % of CO2, R32, HFO-1132(E), and R1234yf based on their sum is respectively represented by w, x, y, and z,


if 1.2<w≤4.0, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, HFO-1132(E), and R1234yf is (100-w) mass % are within the range of a figure surrounded by curves MW and WN, as well as straight lines NE, EC, and CM that connect the following 5 points:


point M (0.0, −0.3004w2+2.419w+55.53, 0.3004w2−3.419w+44.47),


point W (10.0, −0.3645w2+3.5024w+34.422, 0.3645w2−4.5024w+55.578),


point N (18.2, −0.3773w2+3.319w+28.26, 0.3773w2−4.319w+53.54),


point E (−0.0365w+18.26, 0.0623w2−4.5381w+31.856, −0.0623w2+3.5746w+49.884), and


point C (0.0, 0.1081w2−5.169w+58.447, −0.1081w2+4.169w+41.553), or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.0043w2−0.0359w+0.1509)x2+(−0.0493w2+0.4669w−3.6193)x−0.3004w2+2.419w+55.53, 100-w-x-y), and


the curve WN is represented by coordinates (x, (0.0055w2−0.0326w+0.0665)x2+(−0.1571w2+0.8981w−2.6274)x+0.6555w2−2.2153w+54.044, 100-w-x-y); or


if 4.0<w≤7.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by curves MW and WN, as well as straight lines NE, EC, and CM that connect the following 5 points:


point M (0.0, −0.0667w2+0.8333w+58.133, 0.0667w2−1.8333w+41.867),


point W (10.0, −0.0667w2+1.1w+39.267, 0.0667w2−2.1w+50.733),


point N (18.2, −0.0889w2+1.3778w+31.411, 0.0889w2−2.3778w+50.389),


point E (18.1, 0.0444w2−4.3556w+31.411, −0.0444w2+3.3556w+50.489), and


point C (0.0, 0.0667w2−4.9667w+58.3, −0.0667w2+3.9667w+41.7), or on the above line segments (excluding the points on the straight line CM),


the curve MW is represented by coordinates (x, (0.00357w2−0.0391w+0.1756)x2+(−0.0356w2+0.4178w−3.6422)x−0.0667w2+0.8333w+58.103, 100-w-x-y), and


the curve WN is represented by coordinates (x, (−0.002061w2+0.0218w−0.0301)x2+(0.0556w2−0.5821w−0.1108)x−0.4158w2+4.7352w+43.383, 100-w-x-y).


Item 29. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1234yf, and


HFO-1132(E) is present in an amount of 35.0 to 65.0 mass %, and HFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 30. The method, storage container, or refrigerating machine according to Item 29, wherein in the refrigerant, HFO-1132(E) is present in an amount of 41.3 to 53.5 mass %, and HFO-1234yf is present in an amount of 58.7 to 46.5 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 31. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1234yf, and


HFO-1132(E) is present in an amount of 40.5 to 49.2 mass %, and HFO-1234yf is present in an amount of 59.5 to 50.8 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 32. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1234yf, and


HFO-1132(E) is present in an amount of 31.1 to 39.8 mass %, and HFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 33. The method, storage container, or refrigerating machine according to Item 32, wherein in the refrigerant, HFO-1132(E) is present in an amount of 31.1 to 37.9 mass %, and HFO-1234yf is present in an amount of 68.9 to 62.1 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 34. The method, storage container, or refrigerating machine according to any one of Items 29 to 33, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.


Item 35. The refrigerating machine according to any one of Items 29 to 34, which has a refrigeration cycle in which the evaporating temperature is −75 to −5° C.


Item 36. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1234yf, and


HFO-1132(E) is present in an amount of 21.0 to 28.4 mass %, and HFO-1234yf is present in an amount of 79.0 to 71.6 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 37. The method, storage container, or refrigerating machine according to Item 36, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.


Item 38. The method, storage container, or refrigerating machine according to Items 1 to 8, wherein the refrigerant comprises HFO-1132(E) and HFO-1234yf, and


HFO-1132(E) is present in an amount of 12.1 to 72.0 mass %, and HFO-1234yf is present in an amount of 87.9 to 28.0 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.


Item 39. The method, storage container, or refrigerating machine according to Item 38, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.


Item 40. The refrigerating machine according to Item 38 or 39, which is an air-conditioning system for vehicles.


Item 41. The air-conditioning system for vehicles according to Item 40, wherein the air-conditioning system for vehicles is for gasoline vehicles, hybrid vehicles, electric vehicles, or hydrogen vehicles.


DESCRIPTION OF THE REFERENCE NUMERALS




  • 1: Supply line


  • 2: Sampling line


  • 3: Thermometer


  • 4: Pressure gauge


  • 5: Electrode


  • 6: Stirring blade (made of PTFE)


Claims
  • 1. A method for allowing a refrigerant comprising 1,2-difluoroethylene (HFO-1132) and oxygen to coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.
  • 2. A method for storing a refrigerant comprising HFO-1132 by allowing the refrigerant and oxygen to coexist in a closed container, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.
  • 3. The method according to claim 1, wherein the temperature of the gas phase is less than 80° C.
  • 4. The method according to claim 1, wherein the gas phase coexists with a liquid phase containing the refrigerant.
  • 5. The method according to claim 1, wherein a refrigerating machine is operated using the refrigerant as a working fluid, the method comprises performing the coexistence in the refrigerating machine, and the concentration of oxygen in the gas phase at a temperature of 25° C. is 1000 volume ppm or less.
  • 6. The method according to claim 5, wherein the gas phase coexists with a liquid phase containing the refrigerant in at least part of the refrigerating machine.
  • 7. A method for stabilizing a refrigerant comprising HFO-1132, the method comprising, in a state that allows the refrigerant and oxygen to coexist in a gas phase, maintaining the concentration of oxygen in the gas phase at a temperature of 25° C. to 1000 volume ppm or less to thereby stabilize the refrigerant.
  • 8. A storage container of a refrigerant comprising HFO-1132, in which the refrigerant and oxygen coexist in a gas phase, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.
  • 9. A refrigerating machine comprising, as a working fluid, a gas phase containing a refrigerant comprising HFO-1132 and oxygen, the concentration of oxygen in the gas phase at a temperature of 25° C. being 1000 volume ppm or less.
  • 10-22. (canceled)
  • 23. The method according to claim 2, wherein the temperature of the gas phase is less than 80° C.
  • 24. The method according to claim 2, wherein the gas phase coexists with a liquid phase containing the refrigerant.
  • 25. The method according to claim 3, wherein the gas phase coexists with a liquid phase containing the refrigerant.
  • 26. The method according to claim 23, wherein the gas phase coexists with a liquid phase containing the refrigerant.
  • 27. The method according to claim 2, wherein a refrigerating machine is operated using the refrigerant as a working fluid, the method comprises performing the coexistence in the refrigerating machine, and the concentration of oxygen in the gas phase at a temperature of 25° C. is 1000 volume ppm or less.
  • 28. The method according to claim 27, wherein the gas phase coexists with a liquid phase containing the refrigerant in at least part of the refrigerating machine.
Priority Claims (2)
Number Date Country Kind
2019-114154 Jun 2019 JP national
2019-115584 Jun 2019 JP national
Continuations (1)
Number Date Country
Parent PCT/JP2020/024198 Jun 2020 US
Child 17554637 US