JP7492130B2 - Composition containing a refrigerant, method for inhibiting a disproportionation reaction using the composition, method for storing the composition, method for transporting the composition, and refrigeration method, method for operating a refrigeration device, and refrigeration device using the composition - Google Patents

Description

The present disclosure relates to a composition containing a refrigerant, a method for suppressing a disproportionation reaction using the composition, a method for storing the composition, a method for transporting the composition, a refrigeration method using the composition, a method for operating a refrigeration device, and a refrigeration device.

Patent Document 1 discloses a composition containing trans-1,2-difluoroethylene (HFO-1132(E)) and 3,3,3-trifluoropropene (HFO-1243zf).

Patnet No.: U.S. Patent No. 8,961,811

The present disclosure aims to provide a composition containing a refrigerant that has a low global warming potential (GWP), an excellent coefficient of performance (COP) and refrigeration capacity (refrigeration capacity, cooling capacity, or capacity), and suppresses disproportionation reactions.

The present disclosure also aims to provide a method for suppressing a disproportionation reaction using the composition, a method for storing the composition, a method for transporting the composition, a refrigeration method using the composition, a method for operating a refrigeration device, and a refrigeration device.

This disclosure provides the following aspects of the invention:

Item 1.
A composition containing a refrigerant,
The refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)) and 3,3,3-trifluoropropene (HFO-1243zf),
For the total mass of HFO-1132(E) and HFO-1243zf,
The content of HFO-1132(E) is 24% by mass to 60% by mass,
The content of HFO-1243zf is 76% by mass to 40% by mass,
The composition, wherein the refrigerant is a refrigerant used for operating a refrigeration cycle having an evaporation temperature of -50°C to -5°C.

Item 2.
A composition containing a refrigerant,
The refrigerant is
ethylenically fluorinated hydrocarbons having a first double bond;
3,3,3-Trifluoropropene (HFO-1243zf); and Trifluoroiodomethane ( _CF3I ), Difluoromethane (HFC-32), 2,3,3,3-Tetrafluoropropene (HFO-1234yf), Trans-1,3,3,3-Tetrafluoropropene (HFO-1234ze(E)), Hexafluoropropene (FO-1216), Perfluoromethane (PFC-14), Pentafluoroethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane at least one third component selected from the group consisting of HFC-134a, 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane ₍ HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E) ₎ , CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, and an ethylenic fluorinated hydrocarbon having a second double bond (provided that the ethylenic fluorinated hydrocarbon has a double bond different from that having the first double bond);
A composition comprising:

Item 3.
3. The composition according to item 2, wherein the ethylenic fluorinated hydrocarbon having a first and a second double bond is at least one component selected from the group consisting of trifluoroethylene (HFO-1123), trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), and tetrafluoroethylene (FO-1114).

Item 4.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
The third component comprises HFO-1234yf,
When the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A1 (60, 39, 1),
Point B1 (55, 1, 44),
Point C1 (26, 73, 1) and Point D1 (18, 1, 81)
The point is located within a range of a figure enclosed by lines A1-B1, B1-D1, D1-C1, and C1-A1, which respectively connect the four points, or on the lines A1-B1 and D1-C1,
The line segment D1-C1 is
Expressed as (x, ^-1.75x² + 86x - 980, 100-xy),
Item 3. The composition according to item 2.

Item 5.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
comprising HFC-32 as the third component,
Based on the total amount of HFO-1132(E), HFO-1243zf and HFC-32, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A2 (60, 39, 1),
Point B2 (65, 1, 34),
Point C2 (24, 75, 1),
Point D2 (1, 77, 22),
Point E2 (1, 25, 74) and Point F2 (25, 1, 74)
The point is located within a range of a figure enclosed by lines A2-B2, B2-F2, F2-E2, E2-D2, D2-C2, and C2-A2, which respectively connect the above six points, or on said lines A2-B2, F2-E2, and D2-C2,
The line segment D2-C2 is
It is expressed by the coordinates (x, ^-0.0079x² + 0.1107x + 76.897, 100-xy).
Item 3. The composition according to item 2.

Item 6.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
The third component includes CF ₃ I,
Based on the total of HFO-1132(E), HFO-1243zf and CF ₃ I, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for CF ₃ I,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A3 (60, 39, 1),
Point B3 (50, 1, 49),
Point C3 (26, 73, 1), and Point D3 (20, 1, 79)
The point is located within the area of the figure enclosed by the lines A3-B3, B3-D3, D3-C3, and C3-A3, which respectively connect the above four points, or on the lines A3-B3 and D3-C3,
The line segment D3-C3 is
It is expressed by the coordinates (x, 5.1429x ² - 224.57x + 2435.3, 100-xy),
Item 3. The composition according to item 2.

Item 7.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
The third component includes HFO-1234ze(E),
When the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234ze(E) based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A4 (60, 39, 1),
Point B4 (55, 1, 44),
Point C4 (26, 73, 1) and Point D4 (28, 1, 71)
The point is located within the area of the figure enclosed by lines A4-B4, B4-D4, D4-C4, and C4-A4, which respectively connect the four points, or on the lines A4-B4 and D4-C4,
The line segment D4-C4 is
Represented by the coordinates (x, 17x ² - 954x + 13385, 100-xy),
Item 3. The composition according to item 2.

Item 8.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
The third component comprises HFO-1216,
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1216, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1216,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A5 (60, 39, 1),
Point B5 (55, 1, 44),
Point C5 (26, 73, 1) and Point D5 (13, 1, 86)
The point is located within the area of the figure enclosed by the lines A5-B5, B5-D5, D5-C5, and C5-A5, which respectively connect the above four points, or on the lines A5-B5 and D5-C5,
The line segment D5-C5 is
It is expressed by the coordinates (x, ^-0.0531x² + 7.6099x - 88.952, 100-xy).
Item 3. The composition according to item 2.

Item 9.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1132(E),
The third component contains HFO-1123 as the ethylenic fluorinated hydrocarbon having a second double bond,
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1123, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1123, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A6 (59, 40, 1),
Point B6 (1, 40, 59),
Point C6 (25, 74, 1) and Point D6 (1, 75, 24)
The point is located within the area of the figure enclosed by the lines A6-B6, B6-D6, D6-C6, and C6-A6, which respectively connect the four points, or on the lines A6-B6 and D6-C6,
The line segment D6-C6 is
Represented by the coordinates (x, ^-0.0032x² + 0.0417x + 74.962, 100-xy),
3. The composition of claim 2.

Item 10.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1123,
The third component comprises HFO-1234yf,
When the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1123, HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A7 (60, 39, 1),
Point B7 (55, 1, 44),
Point C7 (24, 75, 1) and Point D7 (17, 1, 82)
The point is located within the area of the figure bounded by the lines A7-B7, B7-D7, D7-C7, and C7-A7, which respectively connect the four points above, or on the lines A7-B7 and D7-C7,
The line segment D7-C7 is
It is expressed by the coordinates (x, ^-0.7738x² + 42.298x - 494.43, 100-xy).
Item 3. The composition according to item 2.

Item 11.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1123,
comprising HFC-32 as the third component,
Based on the total amount of HFO-1123, HFO-1243zf and HFC-32, the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A8 (60, 39, 1),
Point B8 (65, 1, 34),
Point C8 (23, 76, 1),
Point D8 (1, 86, 13),
Point E8 (1, 25, 74) and Point F8 (25, 1, 74)
The point lies within the area of the figure bounded by the lines A8-B8, B8-F8, F8-E8, E8-D8, D8-C8, and C8-A8, which respectively connect the above six points, or on the lines A8-B8, F8-E8, and D8-C8,
The line segment D8-C8 is,
Expressed by the coordinates (x, -0.0034x ² - 0.3909x + 86.794, 100-xy),
Item 3. The composition according to item 2.

Item 12.
The ethylenic fluorinated hydrocarbon having a first double bond includes HFO-1123,
The third component includes CF ₃ I,
Based on the total of HFO-1123, HFO-1243zf and CF ₃ I, the mass percentages of each component are x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for CF ₃ I, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A9 (60, 39, 1),
Point B9 (50, 1, 49),
Point C9 (24, 75, 1) and Point D9 (10, 1, 89)
The point is located within the area of the figure bounded by the lines A9-B9, B9-D9, D9-C9, and C9-A9, which respectively connect the above four points, or on the lines A9-B9 and D9-C9,
The line segment D9-C9 is
It is expressed by the coordinates (x, ^-0.254x² + 13.921x - 112.81, 100-xy).
Item 3. The composition according to item 2.

Item 13.
13. The composition according to any one of items 1 to 12, further comprising at least one substance selected from the group consisting of water, a tracer, an ultraviolet fluorescent dye, a stabilizer, and a polymerization inhibitor.

Item 14.
14. The composition according to any one of items 1 to 13, further comprising a refrigerating machine oil and used as a working fluid for a refrigeration system.

Item 15.
Item 15. The composition according to item 14, wherein the refrigerating machine oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

Item 16.
16. A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of items 1 to 15.

Item 17.
16. A method for operating a refrigeration system, comprising operating a refrigeration cycle using the composition according to any one of items 1 to 15.

Item 18.
16. A refrigeration device comprising the composition according to any one of items 1 to 15 as a working fluid.

Item 19.
20. The refrigeration apparatus according to item 18, which is an air conditioner, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a freezing and refrigeration unit, a refrigeration machine for a refrigerated and freezer warehouse, an in-vehicle air conditioner, a turbo refrigeration machine, or a screw refrigeration machine.

Item 20.
A method for suppressing a disproportionation reaction of an ethylenically fluorinated hydrocarbon having a double bond by using a disproportionation inhibitor, comprising the steps of:
The method wherein the disproportionation inhibitor comprises 3,3,3-trifluoropropene (HFO-1243zf).

Item 21.
1. A method for storing an ethylenically fluorinated hydrocarbon having a double bond, comprising the steps of:
storing in the presence of 3,3,3-trifluoropropene (HFO-1243zf).

Item 22.
1. A method for transporting an ethylenically fluorinated hydrocarbon having a double bond, comprising the steps of:
The method comprises transporting the compound in the presence of 3,3,3-trifluoropropene (HFO-1243zf).

The composition is preferably used as a replacement 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.

Compositions containing the refrigerants disclosed herein have the following characteristics: low GWP, excellent COP and refrigeration capacity, and suppression of disproportionation reactions.

In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1132(E), HFO-1243zf, and HFO-1234yf, and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234yf, is 100 mass%, and the diagram shows points (A1 to D1) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. Of the compositions containing the refrigerants disclosed herein, the refrigerants are HFO-1132(E), HFO-1243zf, and HFO-HFC-32, and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFC-32, is 100 mass%, and this diagram shows points (A2 to F2) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In the composition containing the refrigerant disclosed herein, the refrigerants are HFO-1132(E), HFO-1243zf, and CF ₃ I, and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and CF ₃ I, is 100 mass%, and the diagram shows points (A3 to D3) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In the composition containing the refrigerant of the present disclosure, the refrigerants are HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), is 100 mass%, and the diagram shows points (A4 to D4) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1132(E), HFO-1243zf, and FO-1216, and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and FO-1216, is 100 mass%, and this diagram shows points (A5 to D5) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1132(E), HFO-1243zf, and HFO-1123, and the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1123, is 100 mass%, and this diagram shows points (A6 to D6) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1123, HFO-1243zf, and HFO-1234yf, and the total concentration of the three components, HFO-1123, HFO-1243zf, and HFO-1234yf, is 100 mass%, and the diagram shows points (A7 to D7) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1123, HFO-1243zf, and HFO-HFC-32, and the total concentration of the three components, HFO-1123, HFO-1243zf, and HFC-32, is 100 mass%, and this diagram shows points (A8 to F8) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points. In a composition containing a refrigerant according to the present disclosure, the refrigerants are HFO-1123, HFO-1243zf, and CF ₃ I, and the total concentration of the three components, HFO-1123, HFO-1243zf, and CF ₃ I, is 100% by mass. This diagram shows points (A9 to D9) that define the mass ratios of these three refrigerant components in a triangular component composition diagram with the three components as the vertices, and the area surrounded by these points.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that a refrigerant composition containing, for example, trans-1,2-difluoroethylene (HFO-1132(E)) and 3,3,3-trifluoropropene (HFO-1243zf) has the above characteristics.

This disclosure was completed as a result of further research based on these findings. The present invention includes the following embodiments.

<Definition of terms>
In this specification, the numerical range indicated using "to" indicates a range that includes the numerical values before and after "to" as the minimum and maximum values, respectively.

In this specification, the terms "contain" and "include" encompass the concepts of the terms "consist essentially of" and "consist only of."

In this specification, the term "refrigerant" includes at least compounds that have a refrigerant number (ASHRAE number) beginning with the letter R, which indicates the type of refrigerant, as defined by ISO817 (International Organization for Standardization), and also includes compounds that have equivalent refrigerant properties even if they have not yet been assigned a refrigerant number.

Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" based on the chemical structure.

"Fluorocarbon compounds" include hydrofluoroolefins (HFOs), hydrofluorocarbons (HFCs), fluoroolefins (FOs), perfluorocarbons (PFCs), etc.

"Non-fluorocarbon compounds" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744) and ammonia (R717), etc.

As used herein, the term "refrigerant-containing composition" includes
(1) Refrigerants themselves (including mixtures of refrigerants, i.e. "mixed refrigerants") and
(2) A composition which further contains other components and can be used to obtain a working fluid for a refrigeration system by mixing with at least a refrigerating machine oil;
(3) A working fluid for a refrigeration system containing a refrigeration oil.

In this specification, of these three aspects, the composition (2) is also referred to as the "refrigerant composition" to distinguish it from the refrigerant itself (including mixed refrigerants).

In this specification, of these three aspects, the working fluid for refrigeration equipment (3) is also referred to as a "refrigerant oil-containing working fluid" to distinguish it from a "refrigerant composition."

In this specification, the term "substitution," when used in the context of "substituting" a first refrigerant with a second refrigerant, means that, as the first type, equipment designed to operate using a first refrigerant can be operated under optimal conditions using a second refrigerant by simply changing a few parts (at least one of refrigeration oil, gaskets, packing, expansion valves, dryers, and other parts) and adjusting the equipment as necessary. In other words, this type refers to operating the same equipment by "substituting" a refrigerant.

This type of "substitution" can be categorized into "drop-in substitution," "nearly drop-in substitution," and "retrofit," in order of decreasing degree of change or adjustment required when replacing with the second refrigerant.

The second category, where equipment designed to operate with a second refrigerant is installed and used for the same application as an existing application of the first refrigerant, is also included in the term "substitution." This category refers to "substituting" a refrigerant to serve the same application.

In this specification, the term "refrigeration system" refers to any device that removes heat from an object or space to lower the temperature of the object or space below the surrounding air temperature and maintains this low temperature. In other words, in a broad sense, a refrigeration system is a conversion device that obtains energy from the outside, performs work, and converts the energy in order to transfer heat from a low temperature to a high temperature. In this disclosure, a refrigeration system is synonymous with a heat pump.

In this specification, the evaporation temperature in the refrigeration cycle means the temperature at which the refrigerant liquid absorbs heat and turns into vapor during the evaporation process of the refrigeration cycle. The evaporation temperature in the refrigeration cycle can be determined by measuring the temperature at the evaporator inlet and/or outlet. For simple refrigerants and azeotropic refrigerants, the evaporation temperature is constant, but for non-azeotropic refrigerants, the evaporation temperature is the average of the evaporator inlet temperature and the dew point temperature. That is, for non-azeotropic refrigerants, the evaporation temperature can be calculated as "evaporation temperature = (evaporator inlet temperature + dew point temperature) / 2".

1. Composition
(1) Binary Composition In one embodiment, the composition containing the refrigerant of the present disclosure contains trans-1,2-difluoroethylene (HFO-1132(E)) and 3,3,3 - containing trifluoropropene (HFO-1243zf), the content of HFO-1132(E) being 24% by mass to 60% by mass based on the total mass of HFO-1132(E) and HFO-1243zf, The content of HFO-1243zf is 76% by mass to 40% by mass, and the refrigerant is a refrigerant used for operating a refrigeration cycle having an evaporation temperature of -50°C to -5°C.

In the composition containing the refrigerant disclosed herein, the content of HFO-1132(E) is 24% to 60% by mass, and the content of HFO-1243zf is 76% to 40% by mass, based on the total mass of HFO-1132(E) and HFO-1243zf, so that the refrigeration capacity can achieve 70% or more of the refrigeration capacity of propane, and disproportionation reactions are suppressed at a saturation pressure of 3 MPa (absolute pressure).

The composition containing the refrigerant disclosed herein, in particular, has a HFO-1132(E) content of 24 mass% or more and a HFO-1243zf content of 76 mass% or less relative to the total mass of HFO-1132(E) and HFO-1243zf, and thus can achieve a refrigeration capacity of 70% or more of that of propane.

In particular, the composition containing the refrigerant disclosed herein has a content of HFO-1132(E) of 60 mass% or less and a content of HFO-1243zf of 40 mass% or more relative to the total mass of HFO-1132(E) and HFO-1243zf, and thus the disproportionation reaction is suppressed at a saturation pressure of 3 MPa (absolute pressure).

In a composition containing the refrigerant of the present disclosure, the content of HFO-1132(E) is preferably 45% by mass to 60% by mass and the content of HFO-1243zf is preferably 55% by mass to 40% by mass, and more preferably the content of HFO-1132(E) is 56% by mass to 60% by mass and the content of HFO-1243zf is 44% by mass to 40% by mass, based on the total mass of HFO-1132(E) and HFO-1243zf.

The refrigerant-containing composition of the present disclosure may contain, in addition to HFO-1132(E) and HFO-1243zf, other additional refrigerants, provided that the properties of the composition are not impaired.

The composition containing the refrigerant disclosed herein preferably contains HFO-1132(E) and HFO-1243zf in a total concentration of 99.5% by mass or more, more preferably 99.7% by mass or more, even more preferably 99.8% by mass or more, and even more preferably 99.9% by mass or more, based on the total composition.

The content of other additional refrigerants in the entire composition containing the refrigerant of the present disclosure is preferably 0.5 mass% or less, more preferably 0.3 mass% or less, even more preferably 0.2 mass% or less, and even more preferably 0.1 mass% or less, based on the entire composition.

The additional refrigerant is not particularly limited and can be selected from a wide range of known refrigerants that are widely used in this field. The composition containing the refrigerant of the present disclosure may contain the other refrigerant alone or may contain two or more types of other refrigerants.

In compositions containing the refrigerants of the present disclosure, other additional refrigerants include, for example, trace amounts of by-products generated during synthesis processes, etc., contained in HFO-1132(E), HFO-1243zf, etc. Compositions containing the refrigerants of the present disclosure do not exclude these other additional refrigerants.

In the composition containing the refrigerant of the present disclosure, the refrigerant preferably consists only of HFO-1132(E) and HFO-1243zf. In other words, it is particularly preferable that the total concentration of HFO-1132(E) and HFO-1243zf in the entire composition is 100% by mass. Even when the composition containing the refrigerant of the present disclosure "consists only of HFO-1132(E) and HFO-1243zf," it does not exclude, for example, ultratrace amounts of by-products generated in the synthesis process of HFO-1132(E), HFO-1243zf, etc.

The composition containing the refrigerant disclosed herein has the above-mentioned configuration, and as a result, has the following characteristics: low GWP, excellent COP and refrigeration capacity, and suppression of disproportionation reactions.

The composition containing the refrigerant of the present disclosure, particularly by containing HFO-1132(E), has a low GWP and excellent COP and refrigeration capacity; for example, the refrigeration capacity can achieve 70% or more, preferably 90% or more, of the refrigeration capacity of propane. The composition containing the refrigerant of the present disclosure has excellent energy consumption efficiency, since the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle for propane (coefficient of performance (COP)) is 70% or more, preferably 90% or more. The composition containing the refrigerant of the present disclosure has a GWP of 100 or less, and therefore can significantly reduce the environmental load from the perspective of global warming compared to other general-purpose refrigerants.

The composition containing the refrigerant of the present disclosure contains HFO-1243zf, which suppresses the disproportionation reaction of HFO-1132(E). The composition containing the refrigerant of the present disclosure suppresses the disproportionation reaction, for example, at a saturation temperature of 150°C and a saturation pressure in the range of 1 MPa to 7 MPa (also referred to as "1 MPa to 7 MPa", e.g., 3 MPa).

In this disclosure, the pressure conditions that suppress the disproportionation reaction refer to absolute pressure.

Disproportionation is a chemical reaction in which two or more of the same chemical species (HFO-1132(E)) react with each other to give two or more different products.

In the present disclosure, the composition containing the refrigerant is used to operate a refrigeration cycle with an evaporation temperature of -50°C to -5°C. The composition containing the refrigerant of the present disclosure exhibits excellent refrigeration capacity when used to operate a refrigeration cycle with an evaporation temperature of -50°C to -5°C.

In a refrigeration cycle using a composition containing the refrigerant of the present disclosure, when the evaporation temperature is -5°C or lower, the compression ratio is 4 or higher, improving the efficiency of the refrigeration cycle. In a refrigeration cycle using a composition containing the refrigerant of the present disclosure, when the evaporation temperature is -50°C or higher, the evaporation pressure is 0.04MPa or higher, reducing the load on the compressor related to the intake of the refrigerant. The compression ratio can be calculated using the following formula.
Compression ratio = condensation pressure (Mpa) / evaporation pressure (Mpa)

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, the evaporation temperature is preferably -7.5°C or lower, more preferably -10°C or lower, and even more preferably -15°C or lower. In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, the evaporation temperature is preferably -45°C or higher, more preferably -40°C or higher, and even more preferably -35°C or higher.

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, from the viewpoint of reducing the load associated with the intake of the refrigerant into the compressor, the evaporation pressure is preferably 0.04 MPa or more, more preferably 0.05 MPa or more, even more preferably 0.06 MPa or more, and particularly preferably 0.07 MPa or more.

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, from the viewpoint of improving the efficiency of the refrigeration cycle, the evaporation pressure is preferably 1 MPa or less, more preferably 0.8 MPa or less, even more preferably 0.6 MPa or less, and particularly preferably 0.4 MPa or less.

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, the condensation pressure is preferably 1 MPa or more, more preferably 1.2 MPa or more, even more preferably 1.4 MPa or more, and particularly preferably 1.6 MPa or more, from the viewpoint of improving the efficiency of the refrigeration cycle.

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, from the viewpoint of ensuring a necessary and sufficient latent heat of condensation for the refrigeration cycle, the condensation pressure is preferably 4.5 MPa or less, more preferably 4 MPa or less, even more preferably 3.5 MPa or less, and particularly preferably 3 MPa or less.

In a refrigeration cycle in which a composition containing the refrigerant of the present disclosure is used, the compression ratio is preferably 4.0 or more, more preferably 4.5 or more, even more preferably 5.0 or more, and particularly preferably 5.5 or more, from the viewpoint of improving the efficiency of the refrigeration cycle.

In a refrigeration cycle in which a composition containing the refrigerant of 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.

(2) Ternary Composition In one embodiment, the composition containing the refrigerant of the present disclosure comprises, as the refrigerant,
an ethylenic fluorinated hydrocarbon having a first double bond;
3,3,3-Trifluoropropene (HFO-1243zf); and Trifluoroiodomethane ( _CF3I ), Difluoromethane (HFC-32), 2,3,3,3-Tetrafluoropropene (HFO-1234yf), Trans-1,3,3,3-Tetrafluoropropene (HFO-1234ze(E)), Hexafluoropropene (FO-1216), Perfluoromethane (PFC-14), Pentafluoroethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane and at least one third component selected from the group consisting of HFC-134a, 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane ₍ HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E) ₎ , CF3SCF3, propane, cyclopropane, propylene, isobutene, isobutane, and an ethylenic fluorinated hydrocarbon having a second double bond (provided that the ethylenic fluorinated hydrocarbon has a double bond different from the ethylenic fluorinated hydrocarbon having the first double bond).

In the composition containing the refrigerant of the present disclosure, the ethylenic fluorinated hydrocarbon having the first and second double bonds is preferably at least one component selected from the group consisting of trifluoroethylene (HFO-1123), trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), and tetrafluoroethylene (FO-1114).

In the composition containing the refrigerant of the present disclosure, the content of the ethylenic fluorinated hydrocarbon having the first double bond is preferably 1% by mass or more, the content of the HFO-1243zf is preferably 1% by mass or more, and the content of the third component is preferably 1% by mass or more, based on the total mass of the ethylenic fluorinated hydrocarbon having the first double bond, the HFO-1243zf, and the third component.

The composition containing the refrigerant of the present disclosure includes HFO-1243zf, and preferably, the ethylenic fluorinated hydrocarbon having the first double bond is HFO-1132(E), and the content of the HFO-1132(E) is 30% by mass to 60% by mass, the content of the HFO-1243zf is 10% by mass to 39% by mass, and the content of the third component is 1% by mass or more, based on the total mass of the HFO-1132(E), the HFO-1243zf, and the third component (a component different from HFO-1132(E)).

The composition containing the refrigerant of the present disclosure includes HFO-1243zf, and preferably, the ethylenic fluorinated hydrocarbon having the first double bond is HFO-1123, and the content of the HFO-1123 is 30% by mass to 60% by mass, the content of the HFO-1243zf is 10% by mass to 39% by mass, and the content of the third component is 1% by mass or more, based on the total mass of the HFO-1123, the HFO-1243zf, and the third component (a component different from HFO-1123).

(2-1) HFO-1132(E) / HFO-1243zf / HFO-1234yf (Figure 1)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1132(E) as the ethylenic fluorinated hydrocarbon having the first double bond, and contains HFO-1234yf as the third component,
When the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A1 (60, 39, 1),
Point B1 (55, 1, 44),
Point C1 (26, 73, 1) and Point D1 (18, 1, 81)
The point is located within a range of a figure enclosed by lines A1-B1, B1-D1, D1-C1, and C1-A1, which respectively connect the four points, or on the lines A1-B1 and D1-C1,
The line segment D1-C1 is represented as (x, ^-1.75x2 + 86x-980, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234yf, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A1 and B1, which are lines connecting points A1 and B1, are on line a1. In other words, line A1-B1 is a part of line a1. Line a1 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1132(E) of the triangular composition diagram than line a1, the disproportionation reaction can occur.

In Figure 1, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1234yf is z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a1 connecting points A1 and B1 (line A1-B1 in Figure 1)
y=8x-440
z=100-xy
55≦x≦60

Both points B1 and D1, which are lines connecting points B1 and D1, lie on line b1. In other words, line B1-D1 is part of line b1. Line b1 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of the triangular composition diagram from line b1, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 1, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of HFO-1234yf = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
A part of the line b1 connecting points B1 and D1 (line B1-D1 in Figure 1)
y=1
z=100-xy
18≦x≦55

Both points C1 and D1 on the line connecting points C1 and D1 are on curve c1. Curve c1 is a curve showing the mass ratio where the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side of the triangular composition diagram from curve c1, the refrigeration capacity of the ternary refrigerant mixture exceeds 90% of that of propane.

Curve c1 can be found as follows:

Table 1 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) is 18, 20, or 26 mass%. Curve c1 is shown by the line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of HFO-1234yf = z, curve c1 is approximated by the formula in Table 1 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf, and HFO-1234yf as the base, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1234yf is z, the line segment D1-C1 (curve c1) is the locus of coordinates (x, ^-1.75x2 + 86x - 980, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 18 mass% or more and 26 mass% or less, i.e., 18≦x≦26.

Both points A1 and C1 on the lines connecting points A1 and C1 are on line d1. In other words, line A1-C1 is part of line d1. Line d1 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1234yf is 1 mass%. In the region on the apex HFO-1234yf side of line d1 in the triangular composition diagram, the concentration of HFO-1234yf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 1, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1234yf = y, and the mass percentage of HFO-1234yf = z, the line segment showing the mass ratio where the concentration of HFO-1234yf is 1 mass% is approximated by the line segment expressed by the following formula.

A line segment showing the mass ratio where HFO-1234yf is 1% by mass :
A part of the line d1 connecting points A1 and C1 (line A1-C1 in Figure 1)
y=1.0
z=100-xy
26≦x≦60

(2-2) HFO-1132(E) /HFO-1243zf / HFC-32 (Figure 2)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1132(E) as the ethylenic fluorinated hydrocarbon having the first double bond, and contains HFC-32 as the third component;
Based on the total of HFO-1132(E), HFO-1243zf and HFC-32, the mass% of each component is x for HFO-1132(E), y for HFO-1243zf and z for HFC-32, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A2 (60, 39, 1),
Point B2 (65, 1, 34),
Point C2 (24, 75, 1),
Point D2 (1, 77, 22),
Point E2 (1, 25, 74) and Point F2 (25, 1, 74)
The point is located within a range of a figure enclosed by lines A2-B2, B2-F2, F2-E2, E2-D2, D2-C2, and C2-A2, which respectively connect the above six points, or on said lines A2-B2, F2-E2, and D2-C2,
The line segment D2-C2 is
It is expressed as coordinates (x, ^-0.0079x² + 0.1107x + 76.897, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFC-32, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A2 and B2, which are lines connecting points A2 and B2, are on the line a2. In other words, the line A2-B2 is a part of the line a2. The line a2 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1132(E) of the triangular composition diagram than the line a2, the disproportionation reaction can occur.

In Figure 2, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFC-32 is z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a2 connecting points A2 and B2 (line A2-B2 in Figure 2)
y=-8x-520
z=100-xy
60≦x≦65

Both points B2 and F2, which are lines connecting points B2 and F2, are on line b2. In other words, line B2-F2 is part of line b2. Line b2 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b2 in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 2, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
A part of the line b2 connecting points B2 and F2 (line B2-F2 in Figure 2)
y=1
z=100-xy
25≦x≦65

Both points E2 and F2, which are lines connecting points E2 and F2, are on line c2. In other words, line E2-F2 is a part of line c2. Line c2 is a line indicating GWP=500. In the region on the apex HFO-1132(E) side and the apex HFO-1243zf side of the line c in the triangular composition diagram, the GWP is smaller than 500.

In Figure 2, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFC-32 is z, the line indicating GWP=500 is approximated by the line expressed by the following formula.

Line showing GWP=500 :
A part of the line c2 connecting points E2 and F2 (line E2-F2 in Figure 2)
y=-x-26
z=100-xy
1≦x≦25

Both points D2 and E2, which are lines connecting points D2 and E2, are on line d2. In other words, line D2-E2 is part of line d2. Line d2 is a line that indicates the mass ratio where the concentration (mass%) of HFO-1132(E) is 1 mass%. In the region on the apex HFO-1132(E) side of the triangular composition diagram from line d2, the concentration of HFO-1132(E) in the three-component mixed refrigerant exceeds 1 mass%.

In Figure 2, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFO-1132(E) is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1132(E) is 1% by mass :
A part of the line d2 connecting points D2 and E2 (line D2-E2 in Figure 2)
x=1
z=100-xy
25≦y≦78

Both points C2 and D2, which are lines connecting points C2 and D2, lie on curve c2. Curve c2 is a curve that indicates the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side and the apex HFC-32 side of the triangular composition diagram from curve c2, the refrigeration capacity of the ternary refrigerant mixture exceeds 90% of that of propane.

Curve c2 can be found as follows:

Table 2 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) = 1, 13, or 24 mass%. Curve c2 is shown as a line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of HFC-32 = z, curve c2 is approximated by the formula in Table 2 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf, and HFC-32 as the basis, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFC-32 is z, the line segment D2-C2 (curve c2) is the locus of coordinates (x, ^-0.0079x2 + 0.1107x + 76.897, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 1 mass% or more and 24 mass% or less, i.e., 1≦x≦24.

Both points A2 and C2, which are lines connecting points A2 and C2, are on line f2. In other words, line A2-C2 is part of line f2. Line f2 is a line that indicates a mass ratio where the concentration (mass%) of HFC-32 is 1 mass%. In the region on the HFC-32 apex side of the triangular composition diagram from line f2, the concentration of HFC-32 in the ternary refrigerant mixture exceeds 1 mass%.

In Figure 2, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1234yf = y, and the mass percentage of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFC-32 is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFC-32 is 1% by mass :
A part of the line f2 connecting points A2 and C2 (line A2-C2 in Figure 2)
y=100-xz
z=1
24≦x≦60

(2-3) HFO-1132(E) / HFO-1243zf / CF3I ₍ Figure 3)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1132(E) as the ethylenic fluorinated hydrocarbon having the first double bond, and contains CF ₃ I as the third component,
Based on the total of HFO-1132(E), HFO-1243zf and CF ₃ I, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for CF ₃ I,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A3 (60, 39, 1),
Point B3 (50, 1, 49),
Point C3 (26, 73, 1), and Point D3 (20, 1, 79)
The point is located within the area of the figure enclosed by the lines A3-B3, B3-D3, D3-C3, and C3-A3, which respectively connect the above four points, or on the lines A3-B3 and D3-C3,
The line segment D3-C3 is
It is expressed by coordinates (x, ^5.1429x² - 224.57x + 2435.3, 100-xy).

In a composition containing a refrigerant according to the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and CF ₃ I, relative to the entire refrigerant is preferably 99.5 mass % or more.

Both points A3 and B3, which are lines connecting points A3 and B3, are on line a3. In other words, line A3-B3 is a part of line a3. Line a3 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1132(E) of the triangular composition diagram than line a3, the disproportionation reaction can occur.

In Figure 3, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1243zf = y, and the mass percentage of _CF3I = z, the line showing that the disproportionation reaction is suppressed at 3 MPa is approximated to the line represented by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a3 connecting points A3 and B3 (line A3-B3 in Figure 3)
y=4x-200
z=100-xy
50≦x≦60

Both points B3 and D3, which are lines connecting points B3 and D3, are on line b3. In other words, line B3-D3 is part of line b3. Line b3 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b3 in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 3, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of _CF3I = z, the line showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated to a line represented by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
A part of the line b3 connecting points B3 and D3 (line B3-D3 in Figure 3)
y=1
z=100-xy
20≦x≦50

Both points C3 and D3, which are lines connecting points C3 and D3, are on curve c3. Curve c3 is a curve that indicates the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side of the triangular composition diagram from curve c3, the refrigeration capacity of the three-component mixed refrigerant exceeds 90% of that of propane.

Curve c3 can be found as follows:

Table 3 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) is 19, 20, or 26 mass%. Curve c3 is shown by a line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of _CF3I = z, curve c3 is approximated by the formula in Table 3 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf and CF ₃ I as the basis, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of CF ₃ I is z, the line segment D3-C3 (curve c3) is the locus of coordinates (x, 5.1429x ² - 224.57x + 2435.3, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 19 mass% or more and 26 mass% or less, i.e., 19≦x≦26.

Both points A3 and C3, which are lines connecting points A3 and C3, are on line d3. In other words, line A3-C3 is part of line d3. Line d3 is a line that indicates a mass ratio where the concentration (mass%) of _CF3I is 1 mass%. In the region on the _CF3I apex side of the triangular composition diagram from line d3, the concentration of _CF3I in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 3, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1234yf = y, and the mass percentage of _CF3I = z, the line showing the mass ratio where the concentration of _CF3I is 1 mass% is approximated to the line represented by the following formula.

A line showing the mass ratio where CF ₃ I is 1% by mass:
A part of the line d3 connecting points A3 and C3 (line A3-C3 in Figure 3)
y=1.0
z=100-xy
26≦x≦60

(2-4) HFO-1132(E) / HFO-1243zf / HFO-1234ze(E) (Fig. 4)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1132(E) as the ethylenic fluorinated hydrocarbon having the first double bond, and contains HFO-1234ze(E) as the third component,
When the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234ze(E) based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A4 (60, 39, 1),
Point B4 (55, 1, 44),
Point C4 (26, 73, 1) and Point D4 (28, 1, 71)
The point is located within the area of the figure enclosed by lines A4-B4, B4-D4, D4-C4, and C4-A4, which respectively connect the four points, or on the lines A4-B4 and D4-C4,
The line segment D4-C4 is
It is expressed by coordinates (x, 17x ^{^2} - 954x + 13385, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), relative to the entire refrigerant, is preferably 99.5 mass% or more.

Both points A4 and B4, which are lines connecting points A4 and B4, are on line a4. In other words, line A4-B4 is a part of line a4. Line a4 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1132(E) of the triangular composition diagram than line a4, the disproportionation reaction can occur.

In Figure 4, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFO-1234ze(E) = z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a4 connecting points A4 and B4 (line A4-B4 in Figure 4)
y=8x-440
z=100-xy
55≦x≦60

Both points B4 and D4, which are lines connecting points B4 and D4, are on line b4. In other words, line B4-D4 is part of line b4. Line b4 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b4 in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 4, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of HFO-1234ze(E) = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
A part of the line b4 connecting points B4 and D4 (line B4-D4 in Figure 4)
y=1
z=100-xy
28≦x≦55

Both points C4 and D4 on the line connecting points C4 and D4 are on curve c4. Curve c4 is a curve showing the mass ratio where the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side of the triangular composition diagram from curve c4, the refrigeration capacity of the ternary refrigerant mixture exceeds 90% of that of propane.

Curve c4 can be found as follows:

Table 4 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) is 26, 27, or 28 mass%. Curve c4 is shown as a line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of HFO-1234ze(E) = z, curve c4 is approximated by the formula in Table 4 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf, and HFO-1234ze(E) as the basis, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1234ze(E) is z, the line segment D4-C4 (curve c4) is the locus of coordinates (x, ^17x² - 954x + 13385, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 26 mass% or more and 28 mass% or less, i.e., 26≦x≦28.

Both points A4 and C4, which are lines connecting points A4 and C4, are on line d4. In other words, line A4-C4 is part of line d4. Line d4 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1234ze(E) is 1 mass%. In the region on the apex HFO-1234ze(E) side of the triangular composition diagram from line d4, the concentration of HFO-1234ze(E) in the ternary refrigerant mixture exceeds 1 mass%.

In Figure 4, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1234yf = y, and the mass percentage of HFO-1234ze(E) = z, the line segment showing the mass ratio where the concentration of HFO-1234ze(E) is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1234ze(E) is 1% by mass :
A part of the line d4 connecting points A4 and C4 (line A4-C4 in Figure 4)
y=1.0
z=100-xy
26≦x≦60

(2-5) HFO-1132(E) / HFO-1243zf / FO-1216 (Fig. 5)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1132(E) as the ethylenic fluorinated hydrocarbon having the first double bond, and contains HFO-1216 as the third component,
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1216, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1216,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A5 (60, 39, 1),
Point B5 (55, 1, 44),
Point C5 (26, 73, 1) and Point D5 (13, 1, 86)
The point is located within the area of the figure enclosed by the lines A5-B5, B5-D5, D5-C5, and C5-A5, which respectively connect the above four points, or on the lines A5-B5 and D5-C5,
The line segment D5-C5 is
It is expressed as coordinates (x, ^-0.0531x² + 7.6099x - 88.952, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1216, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A5 and B5, which are lines connecting points A5 and B5, are on the line a5. In other words, the line A5-B5 is a part of the line a5. The line a5 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1132(E) side of the triangular composition diagram than the line a5, the disproportionation reaction can occur.

In Figure 5, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1243zf = y, and the mass percentage of FO-1216 = z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a5 connecting points A5 and B5 (line A5-B5 in Figure 5)
y=8x-440
z=100-xy
55≦x≦60

Both points B5 and D5, which are lines connecting points B5 and D5, are on line b5. In other words, line B5-D5 is part of line b5. Line b5 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b5 in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 5, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of FO-1216 = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
Part of the line b5 connecting points B5 and D5 (line B5-D5 in Figure 5)
y=1
z=100-xy
13≦x≦55

Both points C5 and D5 on the line connecting points C5 and D5 are on curve c5. Curve c5 is a curve showing the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side of the triangular composition diagram from curve c5, the refrigeration capacity of the three-component mixed refrigerant exceeds 90% of that of propane.

Curve c5 can be found as follows:

Table 5 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) is 13, 20, or 26 mass%. Curve c5 is shown as a line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of FO-1216 = z, curve c5 is approximated by the formula in Table 5 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf, and HFO-1216 as the base, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1216 is z, the line segment D5-C5 (curve c5) is the locus of coordinates (x, ^-0.0531x2 + 7.6099x - 88.952, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 13 mass% or more and 26 mass% or less, i.e., 13≦x≦26.

Both points A5 and C5 on the line connecting points A5 and C5 are on the line d5. In other words, the line A5-C5 is a part of the line d5. The line d5 is a line showing the mass ratio where the concentration (mass%) of FO-1216 is 1 mass%. In the region on the FO-1216 side of the triangular composition diagram from the line d5, the concentration of FO-1216 in the three-component mixed refrigerant exceeds 1 mass%.

In Figure 5, when the mass % of HFO-1132(E) = x, the mass % of HFO-1234yf = y, and the mass % of FO-1216 = z, the line segment showing the mass ratio where the concentration of FO-1216 is 1 mass % is approximated by the line segment expressed by the following formula.

A line showing the mass ratio where FO-1216 is 1% by mass :
A part of the line d5 connecting points A5 and C5 (line A5-C5 in Figure 5)
y=1.0
z=100-xy
26≦x≦60

(2-6) HFO-1132(E) / HFO-1243zf /HFO-1123 (Figure 6)
In one embodiment, the composition containing the refrigerant of the present disclosure comprises HFO-1243zf, and preferably, the ethylenic fluorinated hydrocarbon having a first double bond comprises HFO-1132(E), and the ethylenic fluorinated hydrocarbon having a second double bond of the third component comprises HFO-1123,
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1123, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1123, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A6 (59, 40, 1),
Point B6 (1, 40, 59),
Point C6 (25, 74, 1) and Point D6 (1, 75, 24)
The point is located within the area of the figure enclosed by the lines A6-B6, B6-D6, D6-C6, and C6-A6, which respectively connect the four points, or on the lines A6-B6 and D6-C6,
The line segment D6-C6 is
It is expressed as coordinates (x, ^-0.0032x² + 0.0417x + 74.962, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1123, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A6 and B6, which are lines connecting points A6 and B6, are on line a6. In other words, line A6-B6 is a part of line a6. Line a6 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. Disproportionation reaction can occur in the region on the apex HFO-1132(E) side and the HFO-1123 side of the triangular composition diagram from line a6.

In Figure 6, when the mass percentage of HFO-1132(E) = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFO-1123 = z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a6 connecting points A6 and B6 (line A6-B6 in Figure 6)
y=40
z=100-xy
1≦x≦25

Both points B6 and D6, which are lines connecting points B6 and D6, lie on line b6. In other words, line segment B6-D6 is part of line b6. Line b6 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1132(E) is 1 mass%. In the region on the apex HFO-1132(E) side of the triangular composition diagram from line b6, the concentration of HFO-1132(E) in the ternary refrigerant mixture exceeds 1 mass%.

In Figure 6, when the mass % of HFO-1132(E) = x, the mass % of HFO-1243zf = y, and the mass % of HFO-1123 = z, the line segment showing the mass ratio where the concentration of HFO-1132(E) is 1 mass% is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1132(E) is 1% by mass :
A part of the line b6 connecting points B6 and D6 (line B6-D6 in Figure 6)
x=1
z=100-xy
40≦y≦75

Both points C6 and D6, which are lines connecting points C6 and D6, are on curve c6. Curve c6 is a curve showing the mass ratio where the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1132(E) side of the triangular composition diagram from curve c6, the refrigeration capacity of the ternary refrigerant mixture exceeds 90% of that of propane.

Curve c6 can be found as follows:

Table 6 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1132(E) = 1, 12, or 25 mass%. Curve c6 is shown as a line connecting these three points, and when the mass% of HFO-1132(E) = x, the mass% of HFO-1243zf = y, and the mass% of HFO-1123 = z, curve c6 is approximated by the formula in Table 6 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1132(E), HFO-1243zf, and HFO-1123 as the basis, when the mass percentage of HFO-1132(E) is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1123 is z, line segment D6-C6 (curve c6) is the locus of coordinates (x, ^-0.0032x2 + 0.0417x + 74.962, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 1 mass% or more and 25 mass% or less, i.e., 1≦x≦25.

Both points A6 and C6, which are lines connecting points A6 and C6, are on line d6. In other words, line A6-C6 is part of line d6. Line d6 is a line that indicates a mass ratio where the concentration (mass%) of FO-1216 is 1 mass%. In the region on the apex HFO-1123 side of the triangular composition diagram from line d6, the concentration of HFO-1123 in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 6, when the mass % of HFO-1132(E) = x, the mass % of HFO-1234yf = y, and the mass % of HFO-1123 = z, the line segment showing the mass ratio where the concentration of HFO-1123 is 1 mass% is approximated by the line segment expressed by the following formula.

A line showing the mass ratio where HFO-1123 is 1% by mass :
A part of the line d6 connecting points A6 and C6 (line A6-C6 in Figure 6)
y=1.0
z=100-xy
25≦x≦59

(2-7) HFO-1123 / HFO-1243zf / HFO-1234yf (Figure 7)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1123 as the ethylenic fluorinated hydrocarbon having the first double bond and HFO-1234yf as the third component.
When the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1123, HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A7 (60, 39, 1),
Point B7 (55, 1, 44),
Point C7 (24, 75, 1) and Point D7 (17, 1, 82)
The point is located within the area of the figure bounded by the lines A7-B7, B7-D7, D7-C7, and C7-A7, which respectively connect the four points above, or on the lines A7-B7 and D7-C7,
The line segment D7-C7 is
It is expressed by coordinates (x, ^-0.7738x² + 42.298x - 494.43, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1123, HFO-1243zf, and HFO-1234yf, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A7 and B7, which are lines connecting points A7 and B7, are on the line a7. In other words, the line A7-B7 is a part of the line a7. The line a7 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region on the apex HFO-1123 side of the triangular composition diagram from the line a7, the disproportionation reaction can occur.

In Figure 7, when the mass percentage of HFO-1123 = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFO-1234yf = z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a7 connecting points A7 and B7 (line A7-B7 in Figure 7)
y=8x-440
z=100-xy
55≦x≦60

Both points B7 and D7, which are lines connecting points B7 and D7, are on line b7. In other words, line B7-D7 is part of line b7. Line b7 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of the triangular composition diagram from line b7, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 7, when the mass % of HFO-1123 = x, the mass % of HFO-1243zf = y, and the mass % of HFO-1234yf = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
Part of the line b7 connecting points B7 and D7 (line B7-D7 in Figure 7)
y=1
z=100-xy
17≦x≦55

Both points C7 and D7 on the line connecting points C7 and D7 are on curve c7. Curve c7 is a curve showing the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1123 side of the triangular composition diagram from curve c7, the refrigeration capacity of the three-component mixed refrigerant exceeds 90% of that of propane.

Curve c7 can be found as follows:

Table 7 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1123 is 17, 20, or 24 mass%. Curve c7 is shown as a line connecting these three points, and when the mass% of HFO-1123 = x, the mass% of HFO-1243zf = y, and the mass% of HFO-1234yf = z, curve c7 is approximated by the formula in Table 7 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

When the sum of HFO-1123, HFO-1243zf, and HFO-1234yf is used as the basis, and the mass percentage of HFO-1123 is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFO-1234yf is z, the line segment D7-C7 (curve c7) is the locus of coordinates (x, ^-0.7738x2 + 42.298x - 494.43, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 17 mass% or more and 24 mass% or less, i.e., 17≦x≦24.

Both points A7 and C7, which are lines connecting points A7 and C7, are on line d7. In other words, line A7-C7 is part of line d7. Line d7 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1234yf is 1 mass%. In the region on the apex HFO-1234yf side of line d7 in the triangular composition diagram, the concentration of HFO-1234yf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 7, when the mass % of HFO-1123 = x, the mass % of HFO-1234yf = y, and the mass % of HFO-1234yf = z, the line segment showing the mass ratio where the concentration of HFO-1234yf is 1 mass% is approximated by the line segment expressed by the following formula.

A line segment showing the mass ratio where HFO-1234yf is 1% by mass :
A part of the line d7 connecting points A7 and C7 (line A7-C7 in Figure 7)
y=1.0
z=100-xy
24≦x≦60

(2-8) HFO-1123 / HFO-1243zf / HFC-32 (Fig. 8)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1123 as the ethylenic fluorinated hydrocarbon having the first double bond, and contains HFC-32 as the third component;
Based on the total amount of HFO-1123, HFO-1243zf and HFC-32, the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A8 (60, 39, 1),
Point B8 (65, 1, 34),
Point C8 (23, 76, 1),
Point D8 (1, 86, 13),
Point E8 (1, 25, 74) and Point F8 (25, 1, 74)
The point lies within the area of the figure bounded by the lines A8-B8, B8-F8, F8-E8, E8-D8, D8-C8, and C8-A8, which respectively connect the above six points, or on the lines A8-B8, F8-E8, and D8-C8,
The line segment D8-C8 is,
It is expressed as coordinates (x, ^-0.0034x² - 0.3909x + 86.794, 100-xy).

In a composition containing the refrigerant of the present disclosure, the total concentration of the three components, HFO-1123, HFO-1243zf, and HFC-32, relative to the entire refrigerant is preferably 99.5 mass% or more.

Both points A8 and B8, which are lines connecting points A8 and B8, are on the line a8. In other words, the line A8-B8 is a part of the line a8. The line a8 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region closer to the apex HFO-1123 side of the triangular composition diagram than the line a8, the disproportionation reaction can occur.

In Figure 8, when the mass percentage of HFO-1123 = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFC-32 = z, the line indicating that the disproportionation reaction is suppressed at 3 MPa is approximated by the line expressed by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a8 connecting points A8 and B8 (line A8-B8 in Figure 8)
y=-8x-520
z=100-xy
60≦x≦65

Both points B8 and F8, which are lines connecting points B8 and F8, are on line b8. In other words, line B8-F8 is part of line b8. Line b8 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b8 in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 8, when the mass % of HFO-1123 = x, the mass % of HFO-1243zf = y, and the mass % of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
Part of the line b8 connecting points B8 and F8 (line B8-D8 in Figure 8)
y=1
z=100-xy
25≦x≦65

Both points E8 and F8, which are lines connecting points E8 and F8, are on line c8. That is, line E8-F8 is a part of line c8. Line c8 is a line indicating GWP=500. In the region on the apex HFO-1123 side and the apex HFO-1243zf side of the triangular composition diagram from line c8, the GWP is smaller than 500.

In Figure 8, when the mass percentage of HFO-1123 = x, the mass percentage of HFO-1243zf = y, and the mass percentage of HFC-32 = z, the line segment showing GWP = 500 is approximated by the line segment expressed by the following formula.

Line showing GWP=500 :
Part of the line c8 connecting points E8 and F8 (line E8-F8 in Figure 8)
y=-x+26
z=100-xy
1≦x≦25

Both points D8 and E8, which are lines connecting points D8 and E8, are on line d8. In other words, line D8-E8 is part of line d8. Line d8 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1123 is 1 mass%. In the region on the apex HFO-1123 side of the triangular composition diagram from line d8, the concentration of HFO-1123 in the ternary refrigerant mixture exceeds 1 mass%.

In Figure 8, when the mass % of HFO-1123 = x, the mass % of HFO-1243zf = y, and the mass % of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFO-1123 is 1 mass % is approximated by the line segment expressed by the following formula.

A line showing the mass ratio where HFO-1123 is 1% by mass :
A part of the line d8 connecting points D8 and E8 (line D8-E8 in Figure 8)
x=1
z=100-xy
25≦y≦86

Both points C8 and D8 on the lines connecting points C8 and D8 are on curve c8. Curve c8 is a curve showing the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1123 side and the apex HFC-32 side of the triangular composition diagram from curve c8, the refrigeration capacity of the ternary refrigerant mixture exceeds 90% of that of propane.

Curve c8 can be found as follows:

Table 8 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1123 is 1, 9, or 23 mass%. Curve c8 is shown as a line connecting these three points, and when the mass% of HFO-1123 = x, the mass% of HFO-1243zf = y, and the mass% of HFC-32 = z, curve c8 is approximated by the formula in Table 8 using the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1123, HFO-1243zf, and HFC-32 as the base, when the mass percentage of HFO-1123 is x, the mass percentage of HFO-1243zf is y, and the mass percentage of HFC-32 is z, the line segment D8-C8 (curve c8) is the locus of coordinates (x, ^-0.0034x2 - 0.3909x + 86.794, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 1 mass% or more and 23 mass% or less, i.e., 1≦x≦23.

Both points A8 and C8 on the lines connecting points A8 and C8 are on line f8. In other words, line A8-C8 is part of line f8. Line f8 is a line that indicates a mass ratio where the concentration (mass%) of HFC-32 is 1 mass%. In the region on the HFC-32 apex side of the triangular composition diagram from line f8, the concentration of HFC-32 in the ternary refrigerant mixture exceeds 1 mass%.

In Figure 8, when the mass % of HFO-1123 = x, the mass % of HFO-1234yf = y, and the mass % of HFC-32 = z, the line segment showing the mass ratio where the concentration of HFC-32 is 1 mass % is approximated by the line segment expressed by the following formula.

Line segment showing mass ratio where HFC-32 is 1% by mass :
A part of the line f8 connecting points A8 and C8 (line A8-C8 in Figure 8)
y=100-xz
z=1
23≦x≦60

(2-9) HFO-1123 / HFO-1243zf / CF3I ₍ Figure 9)
In one embodiment, the composition containing the refrigerant of the present disclosure contains HFO-1243zf, and preferably contains HFO-1123 as the ethylenic fluorinated hydrocarbon having the first double bond, and contains CF ₃ I as the third component,
Based on the total of HFO-1123, HFO-1243zf and CF ₃ I, the mass percentages of each component are x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for CF ₃ I, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A9 (60, 39, 1),
Point B9 (50, 1, 49),
Point C9 (24, 75, 1) and Point D9 (10, 1, 89)
The point is located within the area of the figure bounded by the lines A9-B9, B9-D9, D9-C9, and C9-A9, which respectively connect the above four points, or on the lines A9-B9 and D9-C9,
The line segment D9-C9 is
It is expressed by coordinates (x, ^-0.254x² + 13.921x - 112.81, 100-xy).

In a composition containing a refrigerant according to the present disclosure, the total concentration of the three components, HFO-1123, HFO-1243zf, and CF ₃ I, relative to the entire refrigerant is preferably 99.5 mass % or more.

Both points A9 and B9, which are lines connecting points A9 and B9, are on the line a9. In other words, the line A9-B9 is a part of the line a9. The line a9 is a line indicating that the disproportionation reaction is suppressed at 3 MPa. In the region on the apex HFO-1123 side of the triangular composition diagram from the line a9, the disproportionation reaction can occur.

In FIG. 9, when the mass % of HFO-1123 = x, the mass % of HFO-1243zf = y, and the mass % of _CF3I = z, the line showing that the disproportionation reaction is suppressed at 3 MPa is approximated to the line represented by the following formula.

Line indicating that the disproportionation reaction is inhibited at 3 MPa :
A part of the line a9 connecting points A9 and B9 (line A9-B9 in Figure 9)
y=4x-200
z=100-xy
50≦x≦60

Both points B9 and D9, which are lines connecting points B9 and D9, are on line b9. In other words, line BD is part of line b9. Line b9 is a line that indicates a mass ratio where the concentration (mass%) of HFO-1243zf is 1 mass%. In the region on the apex HFO-1243zf side of line b in the triangular composition diagram, the concentration of HFO-1243zf in the ternary mixed refrigerant exceeds 1 mass%.

In FIG. 9, when the mass % of HFO-1123 = x, the mass % of HFO-1243zf = y, and the mass % of _CF3I = z, the line segment showing the mass ratio where the concentration of HFO-1243zf is 1 mass % is approximated to a line segment represented by the following formula.

Line segment showing mass ratio where HFO-1243zf is 1% by mass :
A part of the line b9 connecting points B9 and D9 (line B9-D9 in Figure 9)
y=1
z=100-xy
10≦x≦50

Both points C9 and D9 on the line connecting points C9 and D9 are on curve c9. Curve c9 is a curve showing the mass ratio at which the refrigeration capacity is 90% of that of propane. In the region on the apex HFO-1123 side of the triangular composition diagram from curve c9, the refrigeration capacity of the three-component mixed refrigerant exceeds 90% of that of propane.

Curve c9 can be found as follows:

Table 9 shows three points where the refrigeration capacity ratio to propane is 90% when HFO-1123 is 10, 19, or 24 mass%. Curve c9 is shown as a line connecting these three points, and when the mass% of HFO-1123 = x, the mass% of HFO-1243zf = y, and the mass% of _CF3I = z, curve c is approximated by the formula in Table 9 by the least squares method.

Curve showing mass ratio at which the refrigeration capacity is 90% compared to propane :

Taking the sum of HFO-1123, HFO-1243zf and CF ₃ I as the basis, when the mass percentage of HFO-1123 is x, the mass percentage of HFO-1243zf is y, and the mass percentage of CF ₃ I is z, the line segment D9-C9 (curve c9) is the locus of coordinates (x, -0.254x ² + 13.921x - 112.81, 100-xy).

The mass percent (x) of HFO-1132(E) is preferably 10 mass% or more and 24 mass% or less, i.e., 18≦x≦26.

Both points A9 and C9, which are lines connecting points A9 and C9, are on line d9. In other words, line A9-C9 is part of line d9. Line d9 is a line that indicates a mass ratio where the concentration (mass%) of CF ₃ I is 1 mass%. In the region on the CF ₃ I apex side of the triangular composition diagram from line d9, the concentration of CF ₃ I in the ternary mixed refrigerant exceeds 1 mass%.

In Figure 9, when the mass % of HFO-1123 = x, the mass % of HFO-1234yf = y, and the mass % of _CF3I = z, the line showing the mass ratio where the _CF3I concentration is 1 mass % is approximated to a line represented by the following formula.

A line showing the mass ratio where CF ₃ I is 1% by mass:
A part of the line d9 connecting points A9 and C9 (line A9-C9 in Figure 9)
y=1.0
z=100-xy
24≦x≦60

The composition containing the refrigerant disclosed herein has the above-mentioned configuration, and as a result, has the following characteristics: low GWP, excellent COP and refrigeration capacity, and suppression of disproportionation reactions.

The composition containing the refrigerant of the present disclosure has a low GWP and excellent COP and refrigeration capacity, particularly due to the inclusion of an ethylene-based fluorinated hydrocarbon having a double bond, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, etc., and can achieve a refrigeration capacity of 90% or more compared to that of propane. The composition containing the refrigerant of the present disclosure has excellent energy consumption efficiency, since the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle for propane (coefficient of performance (COP)) is preferably 90% or more. The composition containing the refrigerant of the present disclosure has a GWP of 500 or less, and therefore can significantly reduce the environmental load from the perspective of global warming compared to other general-purpose refrigerants.

The composition containing the refrigerant of the present disclosure contains HFO-1243zf, which suppresses the disproportionation reaction of ethylenic fluorinated hydrocarbons having double bonds, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, and FO-1114. The composition containing the refrigerant of the present disclosure suppresses the disproportionation reaction, for example, at a saturation temperature of 150°C and a saturation pressure of 1 MPa to 7 MPa (for example, 3 MPa).

Disproportionation is a chemical reaction in which two or more of the same chemical species (each component of an ethylenic fluorinated hydrocarbon with a double bond) react with each other to give two or more different products.

In this disclosure, the pressure conditions that suppress the disproportionation reaction refer to absolute pressure.

In the present disclosure, the composition containing the refrigerant is used to operate a refrigeration cycle with an evaporation temperature of -75 to -5°C. The composition containing the refrigerant of the present disclosure exhibits excellent refrigeration capacity when used to operate a refrigeration cycle with an evaporation temperature of -75 to -5°C.

(3) Alternative Refrigerants The compositions containing the refrigerants disclosed herein are preferably used as alternative refrigerants to 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.

2. Other Components The composition containing the refrigerant of the present disclosure (refrigerant composition) preferably further contains at least one other component in addition to the refrigerant of the present disclosure. The refrigerant composition of the present disclosure may contain at least one of the following other components as necessary.

The composition containing the refrigerant of the present disclosure contains at least the refrigerant of the present disclosure, and further contains at least one substance selected from the group consisting of water, a tracer, an ultraviolet fluorescent dye, a stabilizer, and a polymerization inhibitor, and can be used for the same purposes as the composition containing the refrigerant of the present disclosure.

The refrigerant composition of the present disclosure can also be used to obtain a working fluid for a refrigeration system by mixing it with at least a refrigeration oil.

When the refrigerant composition of the present disclosure is used as a working fluid in a refrigeration device, it is usually mixed with at least a refrigeration oil.

Here, the refrigerant composition of the present disclosure preferably does not substantially contain refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure preferably has a refrigerating machine oil content of 0% by mass to 1% by mass, more preferably 0% by mass to 0.5% by mass, even more preferably 0% by mass to 0.25% by mass, and particularly preferably 0% by mass to 0.1% by mass relative to the entire refrigerant composition.

(1) Water The refrigerant-containing composition of the present disclosure may further contain at least one substance selected from the group consisting of water, a tracer, an ultraviolet fluorescent dye, a stabilizer, and a polymerization inhibitor.

Compositions containing the refrigerant disclosed herein may contain trace amounts of water.

The water content in the composition containing the refrigerant of the present disclosure is preferably 0% to 0.1% by mass, more preferably 0% to 0.075% by mass, even more preferably 0% to 0.05% by mass, and particularly preferably 0% to 0.025% by mass, based on the total amount of the refrigerant.

When the composition containing the refrigerant of the present disclosure contains a small amount of water, the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant are stabilized, and the oxidation of the unsaturated fluorocarbon compound is also less likely to occur, improving the stability of the refrigerant composition. From the viewpoint of obtaining the above-mentioned effects of containing water, the lower limit of the water content is about 0.001% by mass. For example, the water content can be adjusted within the range of 0.001% by mass to 0.1% by mass, 0.001% by mass to 0.075% by mass, 0.001% by mass to 0.05% by mass, or 0.001% by mass to 0.025% by mass.

(2) Tracer . A tracer is added to the refrigerant compositions of the present disclosure in a detectable concentration to enable tracing of any changes to the refrigerant compositions of the present disclosure if they are diluted, contaminated, or otherwise altered.

The refrigerant composition of the present disclosure may contain one type of the above tracer alone or two or more types.

The above tracer is not particularly limited and can be appropriately selected from among commonly used tracers. Preferably, a compound that cannot be an impurity that is inevitably mixed into the refrigerant of the present disclosure is selected as the tracer.

Examples of the tracer include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, nitrous oxide (N ₂ O), etc. Among these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are preferred.

Specifically, the following compounds (hereinafter also referred to as tracer compounds) are more preferable as the tracer.
FC-14 (Tetrafluoromethane, _CF4 )
HCC-40 (chloromethane, _CH3Cl )
HFC-23 (Trifluoromethane, _CHF3 )
HFC-41 (fluoromethane, _CH3F )
HFC-125 (Pentafluoroethane _{, CF3CHF2} )
HFC-134a (1,1,1,2 _{-tetrafluoroethane, CF3CH2F )}
HFC-134 (1,1,2,2-tetrafluoroethane _{, CHF2CHF2} )
HFC-143a (1,1,1-trifluoroethane _{, CF3CH3} )
HFC-143 (1,1,2-trifluoroethane _{, CHF2CH2F} )
HFC-152a (1,1- _{difluoroethane} , _CHF2CH3 )
HFC-152 (1,2-Difluoroethane _{, CH2FCH2F} )
HFC-161 (Fluoroethane _{, CH3CH2F} )
HFC-245fa (1,1,1,3,3- _{Pentafluoropropane} , _{CF3CH2CHF2 )}
HFC-236fa (1,1,1,3,3,3 _- hexafluoropropane, _{CF3CH2CF3 )}
HFC-236ea (1,1,1,2,3,3 _- Hexafluoropropane, _CF3CHFCHF2 )
HFC-227ea (1,1,1,2,3,3,3 _- heptafluoropropane, _CF3CHFCF3 )
HCFC-22 (Chlorodifluoromethane, _CHClF2 )
HCFC-31 (Chlorofluoromethane, _CH2ClF )
CFC-1113 (Chlorotrifluoroethylene, _CF2 =CClF)
HFE-125 (trifluoromethyl-difluoromethyl ether _{, CF3OCHF2} )
HFE-134a (trifluoromethyl-fluoromethyl ether _{, CF3OCH2F} )
HFE-143a (trifluoromethyl ether _{, CF3OCH3} )
HFE-227ea (trifluoromethyl-tetrafluoroethyl ether _{, CF3OCHFCF3} )
HFE-236fa (trifluoromethyl- _{trifluoroethyl} ether _{, CF3OCH2CF3} )

The tracer compound may be present in the refrigerant composition at a total concentration of 10 parts per million (ppm) to 1000 ppm. Preferably, the tracer compound is present in the refrigerant composition at a total concentration of 30 ppm to 500 ppm, more preferably at a total concentration of 50 ppm to 300 ppm, even more preferably at a total concentration of 75 ppm to 250 ppm, and especially preferably at a total concentration of 100 ppm to 200 ppm.

(3) UV-Fluorescent Dye The refrigerant composition of the present disclosure may contain one type of UV-fluorescent dye alone, or may contain two or more types.

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

Examples of the ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as derivatives thereof. Among these, naphthalimide and coumarin are preferred.

The content of the ultraviolet fluorescent dye is not particularly limited, and is usually 0.01% to 5% by mass, preferably 0.05% to 3% by mass, more preferably 0.1% to 2% by mass, even more preferably 0.25% to 1.5% by mass, and particularly preferably 0.5% to 1% by mass, based on the total amount of the refrigerant.

(4) Stabilizer The refrigerant composition of the present disclosure may contain one type of stabilizer alone, or may contain two or more types of stabilizers.

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

Examples of the stabilizers include nitro compounds, ethers, amines, etc.

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

Examples of ethers include 1,4-dioxane.

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

In addition to the above nitro compounds, ethers, and amines, other examples of the stabilizers include butylhydroxyxylene, benzotriazole, etc.

The content of the stabilizer is not particularly limited, and is usually 0.01% to 5% by mass, preferably 0.05% to 3% by mass, more preferably 0.1% to 2% by mass, even more preferably 0.25% to 1.5% by mass, and particularly preferably 0.5% to 1% by mass, based on the total refrigerant.

The method for evaluating the stability of the refrigerant composition of the present disclosure is not particularly limited, and can be evaluated by a commonly used method. One example of such a method is a method in which the amount of free fluorine ions is used as an indicator according to ASHRAE Standard 97-2007. Another example is a method in which the total acid number is used as an indicator. This method can be performed, for example, according to ASTM D 974-06.

(5) Polymerization Inhibitor The refrigerant composition of the present disclosure may contain one type of polymerization inhibitor alone, or may contain two or more types of polymerization inhibitors.

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

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

The content of the polymerization inhibitor is not particularly limited, and is usually 0.01% to 5% by mass, preferably 0.05% to 3% by mass, more preferably 0.1% to 2% by mass, even more preferably 0.25% to 1.5% by mass, and particularly preferably 0.5% to 1% by mass, based on the total amount of the refrigerant.

(6) Other Components That May Be Included in the Refrigerant Composition The refrigerant composition of the present disclosure may also include the following components.

For example, it may contain a fluorinated hydrocarbon other than the above-mentioned refrigerant. The fluorinated hydrocarbon as the other component is not particularly limited, and may be at least one fluorinated hydrocarbon selected from the group consisting of HCFC-1122, HCFC-124, and CFC-1113.

As other components, for example, at least _{one halogenated organic compound represented by the formula (A): CmHnXp [} wherein X each independently represents a fluorine atom, a chlorine atom, or a bromine atom, m is 1 or 2, 2m+2≧n+p, and p≧1.] may be contained. The halogenated organic compound is not particularly limited, and for example, difluorochloromethane, chloromethane, 2-chloro-1,1,1,2,2-pentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene, trifluoroethylene, and the like are preferred.

As other components, for example, at _least one organic compound represented by the formula (B): _CmHnXp [wherein X each independently represents an atom other than a halogen atom, m is 1 or 2, 2m+2≧n ₊ p, and p≧1] may be contained. The organic compound is not particularly limited, and for example, propane, isobutane, etc. are preferred.

The contents of these fluorinated hydrocarbons, the halogenated organic compound represented by formula (A), and the organic compound represented by formula (B) are not limited, but the total amount of these is preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and particularly preferably 0.1 mass% or less, based on the total amount of the refrigerant composition.

3. Refrigerant Oil-Containing Working Fluid The refrigerant-containing composition of the present disclosure further contains a refrigerant oil and is used as a working fluid for a refrigeration device. The refrigerant oil preferably contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

The refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and a refrigerating machine oil, and is used as a working fluid in a refrigeration device. Specifically, the refrigerating machine oil-containing working fluid of the present disclosure is obtained by mixing the refrigerating machine oil used in the compressor of the refrigeration device with the refrigerant or refrigerant composition.

The content of the refrigeration oil is not particularly limited, and is usually 10% to 50% by mass, preferably 12.5% to 45% by mass, more preferably 15% to 40% by mass, even more preferably 17.5% to 35% by mass, and particularly preferably 20% to 30% by mass, based on the total refrigeration oil-containing working fluid.

(1) Refrigerating Machine Oil The composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oil.

The refrigeration oil is not particularly limited and may be appropriately selected from among commonly used refrigeration oils. In this case, as necessary, a refrigeration oil that is superior in terms of miscibility with the mixture of refrigerants disclosed herein (mixed refrigerant disclosed herein) and in terms of improving the stability of the mixed refrigerant disclosed herein may be appropriately selected.

The base oil for the refrigeration oil is preferably at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE).

The refrigeration oil may further contain additives in addition to the base oil.

The additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and antifoaming agents.

From the viewpoint of lubrication, it is preferable that the refrigeration oil has a kinematic viscosity of 5 cSt to 400 cSt at 40°C.

The refrigerant oil-containing working fluid of the present disclosure may further contain at least one additive, if necessary. Examples of additives include the following compatibilizers.

(2) Compatibilizer The refrigerating machine oil-containing working fluid of the present disclosure may contain one type of compatibilizer alone or two or more types.

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

Examples of the compatibilizer include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, 1,1,1-trifluoroalkanes, etc. Among these, polyoxyalkylene glycol ethers are preferred.

(3) Refrigeration Device The refrigeration device of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and a refrigerating machine oil as a working fluid (refrigerating machine oil-containing working fluid).

The refrigeration device is preferably an air conditioner, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerated showcase, a freezer showcase, a freezer/refrigerator unit, a freezer for a freezer/refrigerator warehouse, an in-vehicle air conditioner, a turbo freezer, or a screw freezer.

4. Method for Operating a Refrigerator The method for operating a refrigerator of the present disclosure is a method for operating a refrigerator using a composition containing the refrigerant of the present disclosure. The method for operating a refrigerator of the present disclosure is a refrigeration method including a step of operating a refrigeration cycle using a composition containing the refrigerant of the present disclosure.

Specifically, the method of operating a refrigerator disclosed herein includes a step of circulating the refrigerant disclosed herein in the refrigerator. The method of operating a refrigerator disclosed herein is a method of operating a refrigeration device in which the refrigerant disclosed herein operates a refrigeration cycle in the refrigerator.

5. Method for Inhibiting a Disproportionation Reaction The method for inhibiting a disproportionation reaction disclosed herein is a method for inhibiting a disproportionation reaction of an ethylenic fluorinated hydrocarbon having a double bond using a disproportionation inhibitor, and the disproportionation inhibitor includes 3,3,3-trifluoropropene (HFO-1243zf).

The method of suppressing the disproportionation reaction disclosed herein is preferably applied to a composition containing a refrigerant that includes an ethylenically fluorinated hydrocarbon having a double bond, which is used in a refrigeration cycle.

The ethylenic fluorinated hydrocarbon having a double bond is preferably at least one component selected from the group consisting of trifluoroethylene (HFO-1123), trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), and tetrafluoroethylene (FO-1114), and more preferably at least one component selected from the group consisting of HFO-1123 and HFO-1132(E).

In the method of inhibiting a disproportionation reaction disclosed herein, in addition to the disproportionation inhibitor (including HFO-1243zf) and the ethylenic fluorinated hydrocarbon having a double bond, trifluoroiodomethane (CF3I), difluoromethane (HFC- ₃₂ ), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), hexafluoropropene (FO-1216), perfluoromethane (PFC-14), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-135), 1,1,1,2-tetrafluoroethane (HFC-136), 1,1,1,2-tetrafluoroethane (HFC-137), 1,1,1,2-tetrafluoroethane (HFC-138), 1,1,1,2-tetrafluoroethane (HFC-139), 1,1,1,2-tetrafluoroethane (HFC-140), 1,1,1,2-tetrafluoroethane (HFC-139 ... The fuel may contain at least one component selected from the group consisting of HFC-134a, 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), _CF3SCF3 , _propane , cyclopropane, propylene, isobutene, and isobutane.

The method for suppressing disproportionation reactions disclosed herein has the above-mentioned configuration, and thus has the characteristic of suppressing the disproportionation reactions of ethylenic fluorinated hydrocarbons having double bonds, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, and other ethylenic fluorinated hydrocarbons having double bonds (or refrigerant compositions containing the same).

The method for suppressing disproportionation reactions disclosed herein is particularly capable of suppressing the disproportionation reaction of ethylenic fluorinated hydrocarbons having double bonds, for example, HFO-1243zf is added as a disproportionation inhibitor to a composition containing a refrigerant such as an ethylenic fluorinated hydrocarbon having a double bond, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, or FO-1114.

The method for suppressing the disproportionation reaction disclosed herein can provide a composition containing a refrigerant in which the disproportionation reaction is suppressed, for example, at a saturation temperature of 150°C and a saturation pressure of 1 MPa to 7 MPa (e.g., 3 MPa) (absolute pressure).

Disproportionation is a chemical reaction in which two or more of the same chemical species (individual components of ethylenic fluorinated hydrocarbons with double bonds, such as HFO-1132(E)) react with each other to give two or more different products.

6. Storage Method The storage method of the present disclosure is a method for storing an ethylenic fluorinated hydrocarbon having a double bond, and is a method for storing the same in the presence of 3,3,3-trifluoropropene (HFO-1243zf).

The method of preserving (keeping in its original state) the ethylenic fluorinated hydrocarbon having a double bond of the present disclosure includes a method of storing (saving, storing, etc.) the ethylenic fluorinated hydrocarbon having a double bond.

In the preservation method of the present disclosure, the amount of HFO-1243zf may be an amount sufficient to inhibit disproportionation of ethylenic fluorinated hydrocarbons having double bonds.

The preservation method of the present disclosure is preferably applied to a composition containing a refrigerant containing an ethylenic fluorinated hydrocarbon having a double bond, which is used in a refrigeration cycle.

As in the method for suppressing the disproportionation reaction, the ethylenic fluorinated hydrocarbon having a double bond is preferably at least one component selected from the group consisting of HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, and FO-1114, and more preferably at least one component selected from the group consisting of HFO-1123 and HFO-1132(E).

In the storage method of the present disclosure, in addition to the disproportionation inhibitor (including HFO-1243zf) and the ethylenic fluorinated hydrocarbon having a double bond, like the method for inhibiting the disproportionation reaction, the mixture may contain at least one component selected from the group consisting of _CF3I , HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye(Z), HFO-1225ye(E), _CF3SCF3 , _propane , cyclopropane, propylene, isobutene, and isobutane.

The storage method of the present disclosure has the above-mentioned configuration, and thus has the characteristic of suppressing the disproportionation reaction of ethylenic fluorinated hydrocarbons having double bonds (or refrigerant compositions containing the same) when storing ethylenic fluorinated hydrocarbons having double bonds, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, etc. (or refrigerant compositions containing the same).

The storage method of the present disclosure is particularly useful when storing a composition containing a refrigerant such as an ethylenic fluorinated hydrocarbon having a double bond, for example, HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, etc., by adding and allowing a sufficient amount of HFO-1243zf to be present, it becomes possible to suppress the disproportionation reaction of the ethylenic fluorinated hydrocarbon having a double bond.

The storage (including preservation) container used is preferably a container capable of preserving or storing a composition containing the refrigerant, and is not particularly limited as long as it is sealed.

The storage container may be a container used for transport, such as a land transport container or a marine transport container. The storage container is, for example, preferably a sealed container such as a service can, a 5 L to 1,000 L cylinder, an ISO container, a lorry tank, or a stationary storage tank. In addition, when the refrigerant composition is already stored, the storage container may be, preferably, a sealed container such as a stationary storage tank, or equipment such as a cooling/heating device, a freezer, a refrigerator, or a hot water supply device.

The storage container to be used should preferably be a small airtight container, such as a service can, NRC container (non-refillable container), or rotating container (5L to 1,000L).

The storage container to be used should preferably be a large airtight container, such as an ISO container or storage tank.

The storage method disclosed herein can provide a composition containing a refrigerant in which the disproportionation reaction is suppressed, for example, at a saturation temperature of 150°C and a saturation pressure of 1 MPa to 7 MPa (for example, 3 MPa) (absolute pressure), after the composition containing the refrigerant is stored.

7. Method for Transporting The method for transporting disclosed herein is a method for transporting an ethylenic fluorinated hydrocarbon having a double bond, and is a method for transporting the same in the presence of 3,3,3-trifluoropropene (HFO-1243zf).

The transportation method disclosed herein is a method for transporting ethylenic fluorinated hydrocarbons having double bonds in the presence of HFO-1243zf in a transport vessel such as a land transport vessel or a marine transport container.

In the transportation method disclosed herein, the amount of HFO-1243zf may be sufficient to suppress disproportionation of ethylenic fluorinated hydrocarbons having double bonds during transportation.

The transport method of the present disclosure is preferably applied to a composition containing a refrigerant including an ethylenically fluorinated hydrocarbon having a double bond, for use in a refrigeration cycle.

As in the method for suppressing the disproportionation reaction, the ethylenic fluorinated hydrocarbon having a double bond is preferably at least one component selected from the group consisting of HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, and FO-1114, and more preferably at least one component selected from the group consisting of HFO-1123 and HFO-1132(E).

In the transportation method of the present disclosure, in addition to the disproportionation inhibitor (including HFO-1243zf) and the ethylenic fluorinated hydrocarbon having a double bond, the transport mixture may contain at least one component selected from the group consisting of _CF3I , HFC-32, HFO-1234yf, HFO-1234ze(E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye(Z), HFO-1225ye(E), _CF3SCF3 , _propane , cyclopropane, propylene, isobutene, and isobutane, as in the method of inhibiting the disproportionation reaction.

The transportation method of the present disclosure has the above-mentioned configuration, and thus has the characteristic of suppressing the disproportionation reaction of ethylenic fluorinated hydrocarbons having double bonds (or refrigerant compositions containing the same) when transporting ethylenic fluorinated hydrocarbons having double bonds, such as HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, etc.

The transportation method of the present disclosure is particularly useful when transporting a composition containing a refrigerant such as an ethylenic fluorinated hydrocarbon having a double bond, for example, HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, FO-1114, etc., by adding and allowing a sufficient amount of HFO-1243zf to be present, and thereby suppressing the disproportionation reaction of the ethylenic fluorinated hydrocarbon having a double bond.

The transport container to be used is preferably a land transport container, a sea transport container, or the like, capable of storing and transporting the composition containing the refrigerant, and is not particularly limited as long as it is sealed. The transport container is, for example, preferably a service can, a 5 L to 1,000 L cylinder, an ISO container, a lorry tank, a sealed container such as a stationary storage tank, or the like. In addition, when the refrigerant composition is already stored, it may further preferably be a sealed container such as a stationary storage tank, or equipment such as a cooling/heating appliance, a freezer, a refrigerator, or a hot water supply appliance.

The transport container to be used should preferably be a small sealed container, such as a service can, NRC container (non-refillable container), or rotating container (5L to 1,000L).

The transport container to be used should preferably be a large sealed container, such as an ISO container or storage tank.

The transportation method disclosed herein can provide a composition containing a refrigerant in which the disproportionation reaction is suppressed, for example, at a saturation temperature of 150°C and a saturation pressure of 1 MPa to 7 MPa (for example, 3 MPa) (absolute pressure), after the composition containing the refrigerant is transported.

8. Compositions used in the method for inhibiting a disproportionation reaction, the method for storing, and the method for transporting The compositions used in 5. The method for inhibiting a disproportionation reaction , 6. The method for storing , and 7. The method for transporting of the present disclosure may use the compositions described in the sections for each of the above methods, as well as the compositions described in the sections for 1. Compositions ((1) binary composition, (2) ternary composition, etc.) , 2. Other components , and 3. Refrigerating machine oil-containing working fluid .

Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

The following provides a more detailed explanation using examples. However, the present disclosure is not limited to these examples.

(1) Test procedure A mixed refrigerant was prepared by mixing each component (refrigerant) contained in the composition containing the refrigerant in the mass % shown in each table, based on the total sum of the components.

The GWP of compositions containing each refrigerant in the table was evaluated based on the values in the Fourth Assessment Report (AR4) of the Intergovernmental Panel on Climate Change (IPCC). The GWP of HFO-1132(E) was assumed to be 1, the GWP of HFO-1132a was assumed to be 1 or less, and the GWP of HFO-1123 was assumed to be 0.3.

For the compositions (mixed refrigerants) containing each refrigerant in each table, the Coefficient of Performance (COP) ratio and refrigeration capacity ratio were calculated, with propane as the standard (100%). In other words, the "COP ratio" and "refrigeration capacity ratio" indicate the percentage relative to propane.

The COP, refrigeration capacity, and compression efficiency (condensation pressure/evaporation pressure) of the mixed refrigerant were determined by performing theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions using Refprop 10.0 (manufactured by the National Institute of Science and Technology (NIST)).

"Evaporation temperature" is the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration device.

"Condensation temperature" is the condensation temperature of the mixed refrigerant in the condenser of the refrigeration device.

Compression efficiency (compression ratio) = condensation pressure (Mpa) / evaporation pressure (Mpa)
Coefficient of performance (COP) = (refrigeration capacity or heating capacity) / power consumption

<Test to check for the presence or absence of disproportionation reaction>
The presence or absence of disproportionation reaction was examined using the following test method and conditions.

Test method: The refrigerant composition to be tested was transferred and filled into a test container and heated to 150°C. A voltage was then applied to the Pt wire in the container to melt it, giving the refrigerant composition 30 J of energy. The presence or absence of a disproportionation reaction was determined by a sudden increase in pressure and temperature inside the device.

Test conditions Test container: 38cc SUS container Test temperature: 150℃
Pressure: 1 MPa to 7 MPa
Voltage: 30 V
Current: 40A
Pt wire diameter: 0.3 mm
Pt wire length: 50 mm

Criterion for "non-explosive": The temperature or pressure after Pt filament melting is less than twice as high as that before, and no sudden disproportionation reaction occurs.
"Explosion": The temperature or pressure after Pt wire melting reached more than double the normal level, causing a sudden disproportionation reaction.

(2) Binary composition: HFO-1132(E) / HFO-1243zf
Mixed refrigerants were prepared by mixing HFO-1132(E) and HFO-1243zf at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Theoretical calculation conditions for refrigeration cycle>
Evaporation temperature: 5°C (Table 10), -5°C (Table 11), -50°C (Table 12) and -60°C (Table 13)
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results of Table 11 (evaporation temperature -5°C) and Table 12 (evaporation temperature -50°C), it can be seen that in a composition containing a refrigerant, when the refrigerant contains HFO-1132(E) and HFO-1243zf, and the content of HFO-1132(E) is 24% to 60% by mass and the content of HFO-1243zf is 76% to 40% by mass relative to the total mass of HFO-1132(E) and HFO-1243zf, the GWP is low, the COP and refrigeration capacity are excellent, and disproportionation reactions are suppressed. It can be seen that a composition containing this refrigerant is useful as a refrigerant used to operate a refrigeration cycle with an evaporation temperature of -50°C to -5°C.

In a composition containing this refrigerant, it is found that by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, this HFO-1243zf acts as a disproportionation inhibitor that suppresses the disproportionation reaction of HFO-1132(E). It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

When HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, the HFO-1243zf inhibits the disproportionation reaction of HFO-1132(E), making this composition useful as a method for storing or transporting a composition containing a refrigerant.

When a composition containing this refrigerant is used in a refrigeration cycle with an evaporation temperature of -5°C or lower, the compression ratio is 4 or higher, and it is found that the efficiency of the refrigeration cycle is improved.When a composition containing this refrigerant is used in a refrigeration cycle with an evaporation temperature of -50°C or higher, the evaporation pressure is 0.04MPa or higher, and it is found that the load on the compressor related to the intake of the refrigerant is reduced.

It is understood that a composition containing this refrigerant, in particular, with a content of HFO-1132(E) of 24 mass% or more and a content of HFO-1243zf of 76 mass% or less relative to the total mass of HFO-1132(E) and HFO-1243zf, can achieve a refrigeration capacity of 70% or more of that of propane.

It is understood that the disproportionation reaction is suppressed at a saturation pressure of 3 MPa (absolute pressure) in a composition containing this refrigerant, in particular because the content of HFO-1132(E) is 60 mass% or less and the content of HFO-1243zf is 40 mass% or more relative to the total mass of HFO-1132(E) and HFO-1243zf.

From the results of the comparative example in Table 10 (evaporation temperature 5°C), it can be seen that when the evaporation temperature is 5°C, the compression ratio is less than 4.

From the results of the comparative example in Table 13 (evaporation temperature -60°C), it can be seen that when the evaporation temperature is -60°C, the evaporation pressure is less than 0.04 MPa.

(3) Ternary composition: HFO-1132(E) / HFO-1243zf / HFO-1234yf
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and HFO-1234yf at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Theoretical calculation conditions for refrigeration cycle>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 14 and FIG. 1, when a composition containing a refrigerant contains HFO-1243zf, HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and HFO-1234yf as a third component, the mass% of each component is defined as x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234yf, based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234yf,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A1 (60, 39, 1),
Point B1 (55, 1, 44),
Point C1 (26, 73, 1) and Point D1 (18, 1, 81)
When the above four points are within the range of a figure surrounded by straight lines A1-B1, B1-D1, line segment D1-C1, and line segment C1-A1 respectively connecting these four points, or on said straight lines A1-B1 and line segment D1-C1, and said line segment D1-C1 is expressed as (x, ^-1.75x2 + 86x - 980, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234yf, in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant, in particular, suppress disproportionation reactions, achieve a refrigeration capacity of 90% or more of that of propane, and have a high evaporation pressure.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is understood that this HFO-1243zf acts as a disproportionation inhibitor that suppresses the disproportionation reaction of HFO-1132(E), even when HFO-1234yf (third component) is included. It is understood that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if HFO-1234yf (third component) is also contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1132(E), and therefore this is found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1132(E), HFO-1243zf, and HFO-1234yf is not within the range of the area enclosed by the figure passing through the four points (A1, B1, C1, and D1), it is clear that disproportionation reactions will occur, the refrigeration capacity will not reach 90% or more of the refrigeration capacity of propane, and the evaporation pressure will be low.

(4) Ternary composition: HFO-1132(E) / HFO-1243zf / HFC-32
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and HFC-32 at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 15 and FIG. 2, when a composition containing a refrigerant contains HFO-1243zf, HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and HFC-32 as a third component, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFC-32 based on the sum of HFO-1132(E), HFO-1243zf, and HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A2 (60, 39, 1),
Point B2 (65, 1, 34),
Point C2 (24, 75, 1),
Point D2 (1, 77, 22),
Point E2 (1, 25, 74) and Point F2 (25, 1, 74)
When the above six points are within the range of a figure surrounded by lines A2-B2, B2-F2, F2-E2, E2-D2, line segment D2-C2, and line segment C2-A2 respectively connecting these six points, or on the lines A2-B2, F2-E2, and D2-C2, and the line segment D2-C2 is represented by the coordinates (x, ^-0.0079x2 + 0.1107x + 76.897, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFC-32, in the entire refrigerant is 99.5% by mass or more.

In particular, compositions containing this refrigerant suppress disproportionation reactions, achieve a refrigeration capacity of 90% or more of that of propane, and have a GWP (global warming potential) of less than 500.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is understood that this HFO-1243zf acts as a disproportionation inhibitor, suppressing the disproportionation reaction of HFO-1132(E), even when HFC-32 (third component) is included. It is understood that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

When HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if HFC-32 (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1132(E), and this composition is found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1132(E), HFO-1243zf, and HFC-32 is not within the area enclosed by the figure passing through the six points (A2, B2, C2, D2, E2, and F2), it is clear that disproportionation reactions will occur, the refrigeration capacity will not reach 90% or more of the refrigeration capacity of propane, and the GWP (global warming potential) will exceed 500.

(5) Ternary composition: HFO-1132(E) / HFO-1243zf / _CF3I
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and _CF3I at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio relative to propane (100%), and refrigeration capacity ratio are shown.

<Theoretical calculation conditions for refrigeration cycle>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 16 and FIG. 3, when a composition containing a refrigerant contains HFO-1243zf, HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and CF ₃ I as a third component, the mass percentages of each component based on the total of HFO-1132(E), HFO-1243zf, and CF ₃ I are x mass % for HFO-1132(E), y mass % for HFO-1243zf, and z mass % for CF ₃ I,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A3 (60, 39, 1),
Point B3 (50, 1, 49),
Point C3 (26, 73, 1), and Point D3 (20, 1, 79)
When the above four points are within the range of a figure surrounded by lines A3-B3, B3-D3, D3-C3, and C3-A3, which respectively connect the above four points, or on the lines A3-B3 and D3-C3, and the line segment D3-C3 is expressed by the coordinates (x, ^5.1429x2 - 224.57x + 2435.3, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and CF ₃ I, relative to the entire refrigerant is 99.5 mass % or more.

It has been found that compositions containing this refrigerant in particular suppress disproportionation reactions and achieve a refrigeration capacity of 90% or more of that of propane.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is found that this HFO-1243zf acts as a disproportionation inhibitor that suppresses the disproportionation reaction of HFO-1132(E) even when CF ₃ I (third component) is contained. It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In a composition containing this refrigerant, when HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if _CF3I (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1132(E), and it is therefore found to be useful as a method for storing or transporting a composition containing a refrigerant.

It is clear that if the mass ratio of the three components, HFO-1132(E), HFO-1243zf, and _CF3I , is not within the area enclosed by the figure passing through the four points (A3, B3, C3, and D3), disproportionation reactions will occur or the refrigeration capacity will not achieve 90% or more of the refrigeration capacity of propane.

(6) Ternary composition: HFO-1132(E) / HFO-1243zf / HFO-1234ze(E)
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and HFO-1234ze(E) at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 17 and FIG. 4 , when a composition containing a refrigerant contains HFO-1243zf, HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and HFO-1234ze(E) as a third component, the mass% of each component is defined as x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234ze(E) based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234ze(E),
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A4 (60, 39, 1),
Point B4 (55, 1, 44),
Point C4 (26, 73, 1) and Point D4 (28, 1, 71)
When the above four points are within the range of a figure surrounded by lines A4-B4, B4-D4, D4-C4, and C4-A4 respectively connecting the above four points, or on the line A4-B4 and D4-C4, and the line D4-C4 is represented by the coordinates (x, ^17x2 - 954x + 13385, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant in particular suppress disproportionation reactions and achieve a refrigeration capacity of 90% or more of that of propane.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is found that this HFO-1243zf acts as a disproportionation inhibitor, suppressing the disproportionation reaction of HFO-1132(E), even when HFO-1234ze(E) (third component) is included. It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if HFO-1234ze(E) (third component) is also contained, the HFO-1243zf inhibits the disproportionation reaction of HFO-1132(E), and this proves to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1132(E), HFO-1243zf, and HFO-1234ze(E) is not within the range of the area enclosed by the figure passing through the four points (A4, B4, C4, and D4), it is clear that disproportionation reactions will occur and the refrigeration capacity will not be 90% or more of the refrigeration capacity of propane.

(7) Ternary composition: HFO-1132(E) / HFO-1243zf / FO-1216
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and FO-1216 at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 18 and FIG. 5, when a composition containing a refrigerant contains HFO-1243zf, HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and HFO-1216 as a third component, the mass% of each component is defined as x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1216 based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1216,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A5 (60, 39, 1),
Point B5 (55, 1, 44),
Point C5 (26, 73, 1) and Point D5 (13, 1, 86)
When the above four points are within the range of a figure surrounded by lines A5-B5, B5-D5, D5-C5, and C5-A5 respectively connecting these four points, or on the line A5-B5 and D5-C5, and the line D5-C5 is expressed by the coordinates (x, ^-0.0531x2 + 7.6099x - 88.952, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and FO-1216, in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant in particular suppress disproportionation reactions and achieve a refrigeration capacity of 90% or more of that of propane.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is understood that this HFO-1243zf acts as a disproportionation inhibitor, suppressing the disproportionation reaction of HFO-1132(E), even when FO-1216 (third component) is included. It is understood that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if FO-1216 (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1132(E), and it is therefore found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1132(E), HFO-1243zf, and FO-1216 is not within the range of the area enclosed by the figure passing through the four points (A5, B5, C5, and D5), it is clear that disproportionation reactions will occur and the refrigeration capacity will not be 90% or more of the refrigeration capacity of propane.

(8) Ternary composition: HFO-1132(E) / HFO-1243zf / HFO-1123
Mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1243zf, and HFO-1123 at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 19 and FIG. 6 above, when a composition containing a refrigerant contains HFO-1243zf, contains HFO-1132(E) as an ethylenic fluorinated hydrocarbon having a first double bond, and contains HFO-1123 as the ethylenic fluorinated hydrocarbon having a second double bond as a third component, the mass% of each component is defined as x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1123 based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1123,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A6 (59, 40, 1),
Point B6 (1, 40, 59),
Point C6 (25, 74, 1) and Point D6 (1, 75, 24)
When the above four points are within the range of a figure surrounded by lines A6-B6, B6-D6, D6-C6, and C6-A6 respectively connecting these four points, or on the line A6-B6 and the line segment D6-C6, and the line segment D6-C6 is expressed by the coordinates (x, ^-0.0032x2 + 0.0417x + 74.962, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1123, in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant, in particular, suppress the disproportionation reaction, achieve a refrigeration capacity of 90% or more of that of propane, have a high compression ratio, and have a high evaporation pressure.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1132(E) as a refrigerant, it is found that this HFO-1243zf acts as a disproportionation inhibitor, suppressing the disproportionation reaction of HFO-1132(E), even when HFO-1123 (third component) is included. It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1132(E) as a refrigerant, even if HFO-1123 (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1132(E), and it is therefore found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1132(E), HFO-1243zf, and HFO-1123 is not within the area enclosed by the figure passing through the four points (A6, B6, C6, and D6), it is clear that disproportionation reactions will occur, the refrigeration capacity will not reach 90% or more of the refrigeration capacity of propane, the compression ratio will be low, or the evaporation pressure will be low.

(9) Ternary composition: HFO-1123/HFO-1243zf/HFO-1234yf
Mixed refrigerants were prepared by mixing HFO-1123, HFO-1243zf, and HFO-1234yf at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 20 and FIG. 7, when a composition containing a refrigerant contains HFO-1243zf, contains HFO-1123 as an ethylenic fluorinated hydrocarbon having a first double bond, and contains HFO-1234yf as the third component, the mass% of each component is, based on the sum of HFO-1123, HFO-1243zf, and HFO-1234yf, respectively, x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for HFO-1234yf,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A7 (60, 39, 1),
Point B7 (55, 1, 44),
Point C7 (24, 75, 1) and Point D7 (17, 1, 82)
When the above four points are within the range of the figure surrounded by lines A7-B7, B7-D7, D7-C7, and C7-A7 respectively connecting these four points, or on the line A7-B7 and D7-C7, and the line D7-C7 is expressed by the coordinates (x, ^-0.7738x2 + 42.298x-494.43, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1123, HFO-1243zf, and HFO-1234yf, in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant in particular suppress disproportionation reactions and achieve a refrigeration capacity of 90% or more of that of propane.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1123 as a refrigerant, it is found that this HFO-1243zf acts as a disproportionation inhibitor that suppresses the disproportionation reaction of HFO-1123, even when HFO-1234yf (third component) is included. It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1123 as a refrigerant, even if HFO-1234yf (third component) is also contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1123, and it is therefore found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1123, HFO-1243zf, and HFO-1234yf is not within the range of the area enclosed by the figure passing through the four points (A7, B7, C7, and D7), it is clear that disproportionation reactions will occur and the refrigeration capacity will not be 90% or more of the refrigeration capacity of propane.

(10) Ternary composition: HFO-1123/HFO-1243zf/HFC-32
Mixed refrigerants were prepared by mixing HFO-1123, HFO-1243zf, and HFC-32 at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 21 and FIG. 8, when a composition containing a refrigerant contains HFO-1243zf, HFO-1123 as an ethylenic fluorinated hydrocarbon having a first double bond, and HFC-32 as a third component, the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for HFC-32 based on the sum of HFO-1123, HFO-1243zf, and HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A8 (60, 39, 1),
Point B8 (65, 1, 34),
Point C8 (23, 76, 1),
Point D8 (1, 86, 13),
Point E8 (1, 25, 74) and Point F8 (25, 1, 74)
When the above six points are within the range of a figure enclosed by straight lines A8-B8, B8-F8, F8-E8, E8-D8, line segment D8-C8, and line segment C8-A8 respectively connecting these six points, or on the straight lines A8-B8, F8-E8, and D8-C8, and the line segment D8-C8 is represented by the coordinates (x, ^-0.0034x2 - 0.3909x + 86.794, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1123, HFO-1243zf, and HFC-32, in the entire refrigerant is 99.5% by mass or more.

It has been found that compositions containing this refrigerant, in particular, suppress disproportionation reactions and have a GWP (global warming potential) of not more than 500.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1123 as a refrigerant, it is found that this HFO-1243zf acts as a disproportionation inhibitor, suppressing the disproportionation reaction of HFO-1123, even when HFC-32 (third component) is included. It is found that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In this refrigerant-containing composition, when HFO-1243zf is added to a composition containing HFO-1123 as a refrigerant, even if HFC-32 (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1123, and it is therefore found to be useful as a method for storing or transporting a composition containing a refrigerant.

If the mass ratio of the three components HFO-1123, HFO-1243zf, and HFC-32 is not within the area enclosed by the figure passing through the six points (A8, B8, C8, D8, E8, and F8), it is clear that disproportionation reactions will occur and the GWP (global warming potential) will exceed 500.

(11) Ternary composition: HFO-1123/HFO-1243zf / _CF3I
Mixed refrigerants were prepared by mixing HFO-1123, HFO-1243zf, and _CF3I at the indicated mass%, with the sum of these being taken as the standard (100 mass%). For each mixed refrigerant, the GWP, coefficient of performance (COP) ratio with propane as the standard (100%), and refrigeration capacity ratio are shown.

<Refrigeration cycle theoretical calculation conditions>
Evaporation temperature: 5℃
Condensation temperature 45℃
Overheat temperature 5K
Supercooling temperature: 5K
Compression efficiency 0.7 (70%)

From the results in Table 22 and FIG. 9, when a composition containing a refrigerant contains HFO-1243zf, HFO-1123 as an ethylenic fluorinated hydrocarbon having a first double bond, and CF ₃ I as a third component, the mass percentages of each component are x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for CF ₃ I, based on the total of HFO-1123, HFO-1243zf, and CF ₃ I,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A9 (60, 39, 1),
Point B9 (50, 1, 49),
Point C9 (24, 75, 1) and Point D9 (10, 1, 89)
When the above four points are within the range of a figure surrounded by lines A9-B9, B9-D9, D9-C9, and C9-A9 respectively connecting these four points, or on the lines A9-B9 and D9-C9, and the line segment D9-C9 is expressed by the coordinates (x, ^-0.254x2 + 13.921x - 112.81, 100-xy), it can be seen that the GWP is low, the COP and refrigeration capacity are excellent, and the disproportionation reaction is suppressed.

The total concentration of the three components, HFO-1123, HFO-1243zf, and CF ₃ I, relative to the entire refrigerant is 99.5 mass % or more.

It has been found that compositions containing this refrigerant in particular suppress disproportionation reactions and achieve a refrigeration capacity of 90% or more of that of propane.

In a composition containing this refrigerant, by adding HFO-1243zf to a composition containing HFO-1123 as a refrigerant, it is understood that this HFO-1243zf acts as a disproportionation inhibitor that suppresses the disproportionation reaction of HFO-1123, even when CF ₃ I (third component) is contained. It is understood that a composition containing this refrigerant is useful as a method for suppressing the disproportionation reaction of a refrigerant.

In a composition containing this refrigerant, when HFO-1243zf is added to a composition containing HFO-1123 as a refrigerant, even if _CF3I (third component) is contained, the HFO-1243zf suppresses the disproportionation reaction of HFO-1123, and therefore it is found to be useful as a method for storing or transporting a composition containing a refrigerant.

It is clear that if the mass ratio of the three components, HFO-1123, HFO-1243zf, and _CF3I , is not within the area enclosed by the figure passing through the four points (A9, B9, C9, and D9), disproportionation reactions will occur or the refrigeration capacity will not be able to achieve 90% or more of the refrigeration capacity of propane.

Claims (18)

A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
3,3,3-trifluoropropene (HFO-1243zf); and
2,3,3,3-tetrafluoropropene (HFO-1234yf);
When the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A1 (60, 39, 1),
Point B1 (55, 1, 44),
Point C1 (26, 73, 1) and Point D1 (18, 1, 81)
The point is located within a range of a figure enclosed by lines A1-B1, B1-D1, D1-C1, and C1-A1, which respectively connect the above four points, or on said lines A1-B1 and D1-C1,
The line segment D1-C1 is
It is expressed as (x, ^-1.75x² + 86x - 980, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234yf, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
3,3,3-trifluoropropene (HFO-1243zf); and difluoromethane (HFC-32);
Based on the total amount of HFO-1132(E), HFO-1243zf and HFC-32, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A2 (60, 39, 1),
Point B2 (65, 1, 34),
Point C2 (24, 75, 1),
Point D2 (1, 77, 22),
Point E2 (1, 25, 74) and Point F2 (25, 1, 74)
The point is located within a range of a figure enclosed by lines A2-B2, B2-F2, F2-E2, E2-D2, D2-C2, and C2-A2, which respectively connect the above six points, or on said lines A2-B2, F2-E2, and D2-C2,
The line segment D2-C2 is
It is expressed by the coordinates (x, ^-0.0079x² + 0.1107x + 76.897, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFC-32, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
3,3,3-trifluoropropene (HFO-1243zf); and trifluoroiodomethane ( _CF3I );
With the sum of HFO-1132(E), HFO-1243zf and CF ₃ I as the basis, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for CF ₃ I, respectively. In a triangular composition diagram with these three components as the vertices, the coordinates (x, y, z) are
Point A3 (60, 39, 1),
Point B3 (50, 1, 49),
Point C3 (26, 73, 1), and Point D3 (20, 1, 79)
The point is located within the area of the figure enclosed by the lines A3-B3, B3-D3, D3-C3, and C3-A3, which respectively connect the above four points, or on the lines A3-B3 and D3-C3,
The line segment D3-C3 is
It is expressed by the coordinates (x, 5.1429x ² - 224.57x + 2435.3, 100-xy) ,
A composition , wherein the total concentration of the three components, HFO-1132(E), HFO-1243zf, and CF ₃ I, is 99.5 mass % or more relative to the entire refrigerant. A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
Contains 3,3,3-trifluoropropene (HFO-1243zf); and trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)); and when the mass percentages of each component are based on the sum of HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), respectively, HFO-1132(E) is x mass%, HFO-1243zf is y mass%, and HFO-1234ze(E) is z mass%,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A4 (60, 39, 1),
Point B4 (55, 1, 44),
Point C4 (26, 73, 1) and Point D4 (28, 1, 71)
The point is located within the area of the figure enclosed by lines A4-B4, B4-D4, D4-C4, and C4-A4, which respectively connect the four points, or on the lines A4-B4 and D4-C4,
The line segment D4-C4 is
It is expressed by the coordinates (x, 17x ² - 954x + 13385, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1234ze(E), relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
3,3,3-trifluoropropene (HFO-1243zf); and hexafluoropropene (HFO-1216);
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1216, the mass% of each component is x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1216,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A5 (60, 39, 1),
Point B5 (55, 1, 44),
Point C5 (26, 73, 1) and Point D5 (13, 1, 86)
The point is located within the area of the figure enclosed by the lines A5-B5, B5-D5, D5-C5, and C5-A5, which respectively connect the above four points, or on the lines A5-B5 and D5-C5,
The line segment D5-C5 is
It is expressed by the coordinates (x, ^-0.0531x2 + 7.6099x - 88.952, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1216, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
trans-1,2-difluoroethylene (HFO-1132(E));
3,3,3-trifluoropropene (HFO-1243zf); and trifluoroethylene (HFO-1123);
Based on the total of HFO-1132(E), HFO-1243zf and HFO-1123, the mass percentages of each component are x mass% for HFO-1132(E), y mass% for HFO-1243zf and z mass% for HFO-1123, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A6 (59, 40, 1),
Point B6 (1, 40, 59),
Point C6 (25, 74, 1) and Point D6 (1, 75, 24)
The point is located within the area of the figure enclosed by the lines A6-B6, B6-D6, D6-C6, and C6-A6, which respectively connect the four points, or on the lines A6-B6 and D6-C6,
The line segment D6-C6 is
It is expressed by the coordinates (x, ^-0.0032x2 + 0.0417x + 74.962, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1132(E), HFO-1243zf, and HFO-1123, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
Trifluoroethylene (HFO-1123);
3,3,3-trifluoropropene (HFO-1243zf); and
2,3,3,3-tetrafluoropropene (HFO-1234yf);
When the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf, and z mass% for HFO-1234yf based on the sum of HFO-1123, HFO-1243zf, and HFO-1234yf, respectively,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A7 (60, 39, 1),
Point B7 (55, 1, 44),
Point C7 (24, 75, 1) and Point D7 (17, 1, 82)
The point is located within the area of the figure bounded by the lines A7-B7, B7-D7, D7-C7, and C7-A7, which respectively connect the four points above, or on the lines A7-B7 and D7-C7,
The line segment D7-C7 is
It is expressed by the coordinates (x, -0.7738x ² + 42.298x - 494.43, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1123, HFO-1243zf, and HFO-1234yf, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
Trifluoroethylene (HFO-1123);
3,3,3-trifluoropropene (HFO-1243zf); and difluoromethane (HFC-32);
Based on the total amount of HFO-1123, HFO-1243zf and HFC-32, the mass% of each component is x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for HFC-32,
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A8 (60, 39, 1),
Point B8 (65, 1, 34),
Point C8 (23, 76, 1),
Point D8 (1, 86, 13),
Point E8 (1, 25, 74) and Point F8 (25, 1, 74)
The point lies within the area of the figure bounded by the lines A8-B8, B8-F8, F8-E8, E8-D8, D8-C8, and C8-A8, which respectively connect the above six points, or on the lines A8-B8, F8-E8, and D8-C8,
The line segment D8-C8 is
It is expressed by the coordinates (x, -0.0034x ² - 0.3909x + 86.794, 100-xy) ,
A composition , wherein a total concentration of the three components, HFO-1123, HFO-1243zf, and HFC-32, relative to the entire refrigerant is 99.5 mass% or more . A composition containing a refrigerant,
The refrigerant is
Trifluoroethylene (HFO-1123);
3,3,3-trifluoropropene (HFO-1243zf); and trifluoroiodomethane ( _CF3I );
Based on the total of HFO-1123, HFO-1243zf and CF ₃ I, the mass percentages of each component are x mass% for HFO-1123, y mass% for HFO-1243zf and z mass% for CF ₃ I, respectively.
In a triangular composition diagram with the three components as vertices, the coordinates (x, y, z) are:
Point A9 (60, 39, 1),
Point B9 (50, 1, 49),
Point C9 (24, 75, 1) and Point D9 (10, 1, 89)
The point is located within the area of the figure enclosed by the lines A9-B9, B9-D9, D9-C9, and C9-A9, which respectively connect the above four points, or on the lines A9-B9 and D9-C9,
The line segment D9-C9 is
It is expressed by the coordinates (x, -0.254x ² + 13.921x - 112.81, 100-xy) ,
A composition , wherein the total concentration of the three components, HFO-1123, HFO-1243zf, and CF ₃ I, is 99.5 mass % or more relative to the entire refrigerant. The composition according to any one of claims 1 to 9, containing at least one substance selected from the group consisting of water, a tracer, an ultraviolet fluorescent dye, a stabilizer, and a polymerization inhibitor. The composition according to any one of claims 1 to 10, further comprising a refrigeration oil and used as a working fluid for a refrigeration device. The composition according to claim 11, wherein the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE). A refrigeration method comprising a step of operating a refrigeration cycle using the composition according to any one of claims 1 to 12. A method for operating a refrigeration system that uses a composition according to any one of claims 1 to 12 to operate a refrigeration cycle. A refrigeration device comprising the composition according to any one of claims 1 to 12 as a working fluid. The refrigeration device according to claim 15, which is an air conditioner, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a freezer showcase, a freezer/refrigerator unit, a freezer for a freezer/refrigerator warehouse, an in-vehicle air conditioner, a turbo freezer, or a screw freezer. A method for suppressing a disproportionation reaction of an ethylenically fluorinated hydrocarbon having a double bond by using a disproportionation inhibitor, comprising the steps of:
The method wherein the disproportionation inhibitor comprises 3,3,3-trifluoropropene (HFO-1243zf). The method according to claim 17, wherein the ethylenic fluorinated hydrocarbon having a double bond is at least one component selected from the group consisting of trifluoroethylene (HFO-1123), trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 1,1-difluoroethylene (HFO-1132a), and tetrafluoroethylene (FO-1114).

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