RU2791930C2 - Composition containing refrigerant and method for cooling, using specified composition, method for operation of refrigeration unit, and refrigeration unit - Google Patents

Abstract

FIELD: refrigeration equipment.

SUBSTANCE: invention relates to a cooling method including operation of a refrigeration cycle, in which an evaporation temperature is from -75 to -5°C, using a refrigerant composition containing a refrigerant. In this case, the refrigerant contains trans-1,2-difluorethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluorpropene (HFO-1234yf), where HFO-1132 (E) is present in amount from 35.0 to 65.0% by wt., and HFO-1234yf is present in amount from 65.0 to 35.0% by wt. per the total weight of HFO-1132 (E) and HFO-1234yf. The invention also relates to options of a refrigerant composition, a cooling method, a method for operation of a refrigeration unit, a refrigeration unit.

EFFECT: composition has a coefficient of performance (COP) and cooling capacity equivalent or higher than a coefficient of performance and cooling capacity of R404A and R134a, and it has sufficiently low GWP.

32 cl, 1 dwg, 13 tbl

Description

Technical field

[0001]

The present invention relates to a refrigerant-containing composition and a refrigeration method, a refrigeration apparatus operation method, and a refrigeration apparatus, all of which use the composition.

State of the art

[0002]

In the context of the worldwide discussion about global warming as a very serious problem, the development of environmentally friendly air conditioners, refrigeration equipment, etc. is gaining more and more importance.

[0003]

Various blended refrigerants have now been proposed that have a low global warming potential (GWP) and can replace R404A used as a refrigerant for air conditioners such as home air conditioners. For example, Patent Document (PTL) 1 and TD 2 disclose as an alternative refrigerant for R404A a refrigerant composition containing difluoromethane (R32), pentafluoroethane (R125), 2,3,3,3-tetrafluoropropane (R1234yf) and 1, 1,1,2-tetrafluoroethane (R134a).

[0004]

In addition, various blended refrigerants have been proposed which have a low GWP and which can replace 1,1,1,2-tetrafluoroethane (HFC-134a or R134a) used as a refrigerant for air conditioners such as domestic air conditioners (e.g. PD 3).

Citation list

patent document

[0005]

PD 1: WO 2010/059677

PD 2: WO 2011/163117

PD 3: WO 2005/105947

The essence of the invention

Technical task

[0006]

The purpose of the present invention is to provide a composition containing a refrigerant having a coefficient of performance (COP) and a cooling capacity (which may be expressed as "cooling capacity" or "capacity") equivalent to or higher than the CC and cooling capacity of R404A, and having relatively low GWP. Another object of the present invention is to provide a composition containing a refrigerant having a coefficient of performance (COP) and a cooling capacity (which may be expressed as "cooling capacity" or "capacity") equivalent to or higher than R404A's CC and cooling capacity, and having a sufficiently low GWP. . Yet another object of the present invention is to provide a refrigeration method, a refrigeration apparatus operation method, and a refrigeration apparatus all of which use the above composition.

The solution of the problem

[0007]

The present description proposes the invention in accordance with the following embodiments.

Paragraph 1.

A composition containing a refrigerant

moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 35.0 to 65.0% wt., and HFO-1234yf is present in an amount of from 65.0 to 35.0% of the mass. based on the combined weight of HFO-1132(E) and HFO-1234yf, and

where the refrigerant is intended for use in the operation of the refrigeration cycle, in which the evaporation temperature is from -75 to -5°C.

Point 2.

The composition in accordance with paragraph 1, where HFO-1132 (E) is present in an amount of from 41.3 to 53.5% wt., and HFO-1234yf is present in an amount of from 58.7 to 46.5% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Point 3.

Composition according to point 1 or 2, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 4.

A composition containing a refrigerant

moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 40.5 to 49.2% wt., and HFO-1234yf is present in an amount of from 59.5 to 50.8% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 5.

Composition in accordance with paragraph 4, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 6.

Composition according to point 4 or 5, where the refrigerant is intended for use in the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 15°C.

Item 7.

Composition according to any one of paragraphs 1-6 which is intended to be used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R51A or R51A.

Item 8.

A composition containing a refrigerant

moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 31.1 to 39.8% wt., and HFO-1234yf is present in an amount of from 68.9 to 60.2% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 9.

The composition in accordance with paragraph 8, where HFO-1132 (E) is present in an amount of from 31.1 to 37.9% wt., and HFO-1234yf is present in an amount of from 68.9 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 10.

Composition according to item 8 or 9, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 11.

A composition according to any one of paragraphs 8-10, wherein the refrigerant is for use in a refrigeration cycle operating in which the evaporation temperature is -75 to 15°C.

Item 12.

A composition according to any of paragraphs 8-11 which is intended to be used as an alternative refrigerant for R134a, R1234yf or CO ₂ (R744).

Item 13.

A composition containing a refrigerant

moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 21.0 to 28.4% wt., and HFO-1234yf is present in an amount of from 79.0 to 71.6% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 14.

Composition in accordance with paragraph 13, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 15.

Composition according to point 13 or 14 which is intended to be used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R547, R514yf.ze or R12

Item 16.

A composition containing a refrigerant

moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 12.1 to 72.0% wt., and HFO-1234yf is present in an amount of from 87.9 to 28.0% of the mass. based on the combined weight of HFO-1132(E) and HFO-1234yf, and

where the refrigerant is intended for use in an air conditioning system for vehicles.

Item 17.

A composition according to claim 16 wherein the air conditioning system is for gasoline vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles.

Item 18.

Composition according to item 16 or 17, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 19.

A composition according to any one of paragraphs 16-18 which is intended to be used as an alternative refrigerant for R12, R134a or R1234yf.

Item 20.

A composition according to any one of paragraphs 1-19, containing at least one substance selected from the group consisting of water, tracers, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors.

Item 21.

A composition according to any one of paragraphs 1-20, wherein the composition further comprises a refrigeration oil and is intended for use as a working fluid in a refrigeration apparatus.

Item 22.

The composition in accordance with paragraph 21, where the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG (PAG)), complex polyol ether (POE (POE)) and simple polyvinyl ether (PVE (PVE) ).

Item 23.

A refrigeration method comprising operating a refrigeration cycle using a composition according to any one of paragraphs 1-22.

Item 24.

A refrigeration method comprising operating a refrigeration cycle in which the evaporation temperature is -75 to -5°C, using a composition containing a refrigerant, the refrigerant containing trans-1,2-difluoroethylene (HFO-1132 (E)) and 2, 3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 35.0 to 65.0% wt., and HFO-1234yf is present in an amount of from 65.0 to 35.0% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 25.

The cooling method according to item 24, wherein HFO-1132 (E) is present in an amount of 41.3 to 53.5 wt%, and HFO-1234yf is present in an amount of 58.7 to 46.5 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 26.

The refrigeration method according to items 24 or 25, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 27.

A refrigeration method comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 40.5 to 49.2% wt., and HFO-1234yf is present in an amount of from 59.5 to 50.8% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 28.

The refrigeration method according to item 27, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 29.

The refrigeration method according to item 27 or 28, wherein the refrigerant has an evaporating temperature of -75 to 15°C in the refrigeration cycle.

Item 30.

A refrigeration method comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 31.1 to 39.8% wt., and HFO-1234yf is present in an amount of from 68.9 to 60.2% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 31.

The cooling method according to item 30, wherein HFO-1132 (E) is present in an amount of 31.1 to 37.9% by mass, and HFO-1234yf is present in an amount of 68.9 to 62.1% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 32.

The refrigeration method according to item 30 or 31, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 33.

The refrigeration method according to any one of items 30-32, wherein the refrigerant has an evaporation temperature of -75 to 15°C in the refrigeration cycle.

Item 34.

A refrigeration method comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 21.0 to 28.4% wt., and HFO-1234yf is present in an amount of from 79.0 to 71.6% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

Item 35.

The refrigeration method according to item 34, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 36.

A refrigeration method comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

where HFO-1132 (E) is present in an amount of from 12.1 to 72.0% wt., and HFO-1234yf is present in an amount of from 87.9 to 28.0% of the mass. based on the combined weight of HFO-1132(E) and HFO-1234yf, and where the refrigerant is intended for use in a vehicle air conditioning system.

Item 37.

The cooling method according to item 36, wherein the air conditioning system is for gasoline vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles.

Item 38.

The refrigeration method according to item 36 or 37, where the refrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 39.

A method of operating a refrigeration apparatus configured to operate a refrigeration cycle using a composition according to any one of paragraphs 1-22.

Item 40.

A refrigeration apparatus containing a composition according to any one of paragraphs 1-22 as a working fluid.

Item 41.

Refrigeration unit according to item 40, which is an air-conditioning system, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated display case, a freezer display case, a freezer and refrigeration unit, a refrigeration machine for freezer and cold stores, an air conditioning system for vehicles , turbo chiller or screw chiller.

Item 42.

A composition according to any one of paragraphs 1-22 which is intended to be used as a refrigerant.

Item 43.

The composition according to paragraph 42, which is intended for use as a refrigerant in a refrigeration apparatus.

Item 44.

The composition according to paragraph 43, where the refrigeration unit is an air conditioning system, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated display case, a freezer display case, a freezer and refrigeration unit, a refrigeration machine for freezer and cold stores, an air conditioning system for transport means, a turbo-refrigeration unit or a screw chiller.

Item 45.

The use of a composition according to any one of paragraphs 1-22 as a refrigerant.

Item 46.

Application in accordance with point 45 in a refrigeration apparatus.

Item 47.

Application according to item 46, where the refrigeration unit is an air conditioning system, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated display case, a freezer display case, a freezer and refrigeration unit, a refrigeration machine for freezer and cold stores, an air conditioning system for transport means, a turbo-refrigeration unit or a screw chiller.

Positive effects of the invention

[0008]

The composition containing the refrigerant according to the present invention is characterized by having a coefficient of performance (COP) and a cooling capacity equivalent to or higher than that of R404A and having a sufficiently low GWP. In addition, the refrigerant-containing composition according to the present invention is characterized by having a COP and a cooling capacity equivalent to or higher than that of R134a and having a sufficiently low GWP.

Brief description of the drawings

[0009]

FIG. 1 is a diagram illustrating an experimental setup for assessing flammability (flammable or non-flammable).

Description of Embodiments

[0010]

In order to solve the above problem, intensive studies have been carried out and it has been found that a composition containing a mixed refrigerant containing trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), has the characteristics described above.

[0011]

The present invention has been made as a result of further studies based on the above findings. The present invention covers the following embodiments.

[0012]

Definition of terms

The numerical interval expressed with "before" in the present description indicates a range that includes the numerical values before and after "before" given as the minimum and maximum values, respectively.

[0013]

In the present description, the terms "comprises" and "includes" encompass the concepts "consisting essentially of" and "consisting of".

[0014]

In the present description, the term “refrigerant” includes at least compounds that are defined in ISO817 (International Organization for Standardization) and assigned a refrigerant number (ASHRAE number). air conditioning unit) showing the type of refrigerant with an "R" at the beginning; and also includes refrigerants that have characteristics equivalent to those of such refrigerants, even if a refrigerant number has not yet been assigned.

[0015]

Refrigerants, in terms of compound structure, are broadly divided into fluorocarbon-based compounds and non-fluorocarbon compounds. Fluorocarbon compounds include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717) and the like.

[0016]

The term "composition containing a refrigerant", as used in the present description, at least includes:

(1) the refrigerant itself (including a mixture of refrigerants, that is, a mixed refrigerant);

(2) a composition that can be used to make a refrigeration fluid by further including one or more other components and mixing with at least a refrigeration oil;

(3) a refrigeration fluid containing refrigerant oil.

[0017]

Of these three forms, composition (2) is referred to herein as "refrigerant composition" to distinguish from the refrigerant itself (including mixed refrigerant). In addition, the working fluid for the refrigeration apparatus (3) is referred to as "refrigeration oil-containing working fluid" to distinguish from "refrigerant composition".

[0018]

In this specification, when using the term "alternative" in the context in which the first refrigerant is replaced with a second refrigerant, the first type of alternative means that equipment designed to operate using the first refrigerant can operate using the second refrigerant under optimal conditions, optionally with replacement only a small number of items (at least one of the following: refrigerant oil, gasket, packing, expansion valve, dryer, other parts) and equipment adjustment. In other words, this type of alternative means that the same equipment works with an alternative refrigerant. Embodiments of this type of alternative include a plug-in alternative, a nearly plug-in alternative, and partial modifications, in an order in which the degree of change and adjustment required to replace the first refrigerant with the second refrigerant is small.

[0019]

The term "alternative" also includes a second type of alternative, which means that equipment designed to use the second refrigerant operates in the same application as the existing use of the first refrigerant using the second refrigerant. This type of alternative means that the same application is achieved with an alternative refrigerant.

[0020]

In the present description, the term "refrigerator" in a broad sense refers to devices in general, which remove heat from an object or space, making it cooler than the temperature of the surrounding air, and maintaining a low temperature. In other words, refrigeration devices broadly refer to converting devices that receive energy from outside to do work and that convert energy to transfer heat from a place where the temperature is lower to a place where the temperature is higher. In the present description, "refrigerator" is broadly synonymous with "heat pump".

[0021]

In the present invention, the term "refrigerator" is distinguished from the term "heat pump" in a narrow sense, depending on the difference between the applied temperature range and the operating temperature. In this case, an apparatus whose low-temperature heat source is in a temperature range lower than the air temperature can be called a "refrigeration apparatus", while an apparatus whose low-temperature heat source is close to the air temperature, in order to use the heat generation caused by starting the refrigeration cycle, may be called a "heat pump". In addition, there are such apparatuses that have both the function of refrigeration devices in the narrow sense and the function of heat pumps in the narrow sense, although they are one machine, such as air conditioners, which provide both a cooling mode and a heating mode. In the present description, unless otherwise indicated, the terms "refrigerator" and "heat pump" are used in a broad sense throughout the description.

[0022]

In the present description, the term "temperature hysteresis" can be rephrased as the absolute value of the difference between the start temperature and the end temperature of the phase change process of the composition containing the refrigerant in accordance with the present invention, in the constituent elements of the thermal cycle system.

[0023]

In the present description, the term "vehicle air conditioning system" is a type of refrigeration device for use in vehicles such as gasoline vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles. A vehicle air conditioning system refers to a refrigeration device that has a refrigeration cycle in which heat exchange is carried out by an evaporator using a liquid refrigerant, the vaporized refrigerant gas is absorbed by a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied by a condenser, the liquefied refrigerant is adiabatically expanded by passing it through the expansion valve, and then the refrigerant is again supplied as a liquid to the evaporator.

[0024]

In the present description, the term "turbo-chiller" means a type of large chiller refrigeration unit and refers to a refrigeration plant that has a refrigeration cycle in which heat exchange is carried out by an evaporator using a liquid refrigerant, the vaporized refrigerant gas is absorbed by a centrifugal compressor, the adiabatically compressed refrigerant gas is cooled and liquefied by means of a condenser, the liquefied refrigerant is adiabatically expanded by passing it through an expansion valve, and then the refrigerant is again fed as a liquid to the evaporator. The term "large chiller" is a type of chiller and refers to a large air conditioner that is designed to air-condition a separate section of a building.

[0025]

In the present description, the term "saturated pressure" refers to the pressure of saturated vapor. In the present description, the term "saturated temperature" refers to the temperature of saturated steam.

[0026]

In the present description, the expression "evaporation temperature in the refrigeration cycle" refers to the temperature at which the refrigerant liquid absorbs heat and turns into vapor in the evaporation stage of the refrigeration cycle. The evaporation temperature in the refrigeration cycle can be determined by measuring the evaporator inlet and/or evaporator outlet temperature. The evaporation temperature of a simple refrigerant or an azeotropic refrigerant is constant. However, the evaporation temperature of a non-azeatropic refrigerant is the average of the evaporator inlet temperature and the dew point temperature. More specifically, the evaporation temperature of a non-azeatropic refrigerant can be calculated using the following equation:

Evaporating temperature = (evaporator inlet temperature + dew point temperature)/2.

[0027]

In the present description, the term "discharge temperature" refers to the temperature of the mixed refrigerant at the outlet of the compressor.

[0028]

In the present description, the term "evaporation pressure" refers to the saturation pressure at the evaporation temperature. In the present description, the term "condensing pressure" refers to the saturation pressure at the condensation temperature.

[0029]

In the present description, the term "critical temperature" refers to the temperature at the critical point and temperature boundary; that is, as long as the temperature is not equal to or lower than the critical temperature, the gas will not be converted to liquid by compressing the gas.

[0030]

As used herein, the term “non-flammable” refrigerants refers to refrigerants whose worst case flammability composition (WCF), which is the most flammable point in the allowable refrigerant concentration range according to US ANSI/ASHRAE Standard 34-2013, is classified as Class 1.

[0031]

As used herein, the term "flammable refrigerants" refers to refrigerants whose WCF composition is classified as class 2L according to ANSI/ASHRAE Standard 34-2013.

[0032]

As used herein, the term “low flammability refrigerants” refers to refrigerants whose WCF composition is classified as Class 2 according to ANSI/ASHRAE Standard 34-2013.

[0033]

In the present description, the GWP (GWP) (AR4) is estimated based on the values presented in the fourth report of the Intergovernmental Panel on Climate Change (IPCC)).

[0034]

1. Composition

The composition in accordance with the present invention contains a refrigerant. Examples of the refrigerant include Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, and Refrigerant 5. Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, and Refrigerant 5 are described below. In the present description, "refrigerant according to the present invention" refers to Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, or Refrigerant 5.

[0035]

1.1 Refrigerant 1

In an embodiment of the invention, the refrigerant in the composition in accordance with the present invention contains HFO-1132 (E) and HFO-1234yf, where HFO-1132 (E) is present in an amount of from 35.0 to 65.0% wt., and HFO-1234yf is present in an amount of 65.0 to 35.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 1".

[0036]

In the present invention, Refrigerant 1 is intended for use in the operation of a refrigeration cycle in which the evaporation temperature is -75 to -5°C.

[0037]

Refrigerant 1 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC equal to or higher than the IC of R404A; and (3) it has a cooling capacity equal to or greater than that of R404A.

[0038]

Since Refrigerant 1 contains HFO-1132 (E) in the amount of 35.0% of the mass. or more based on the combined weight of HFO-1132(E) and HFO-1234yf, Refrigerant 1 has a cooling capacity equivalent to or greater than that of R404A. Moreover, since Refrigerant 1 contains HFO-1132 (E) in the amount of 65.0% of the mass. or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of Refrigerant 1 at a saturation temperature of 40°C in the refrigeration cycle can be maintained within an acceptable range (in particular, 2.10 MPa or less).

[0039]

The refrigerant 1 may have a cooling capacity of 95% or more, preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more, compared to R404A.

[0040]

Since the GWP is 100 or less, Refrigerant 1 can significantly reduce the burden on the environment from a global warming perspective compared to other general purpose refrigerants.

[0041]

In Refrigerant 1, the ratio of the cooling capacity to the power consumed in the refrigeration cycle (COP (COP)), with respect to the COP of R404A, is preferably high in terms of energy efficiency. More specifically, the IC compared to the IC of R404A is preferably 98% or more, more preferably 100% or more, and particularly preferably 102% or more.

[0042]

In Refrigerant 1, it is preferable that HFO-1132 (E) is present in an amount of 40.5 to 59.0% by mass, and HFO-1234yf is present in an amount of 59.5 to 41.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99% or more of that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0043]

In Refrigerant 1, it is more preferred that HFO-1132 (E) is present in an amount of 41.3 to 59.0% by mass, and HFO-1234yf is present in an amount of 58.7 to 41.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99.5% or more of that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0044]

In Refrigerant 1, it is also preferred that HFO-1132 (E) is present in an amount of 41.3 to 55.0% by mass, and HFO-1234yf is present in an amount of 58.7 to 45.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99.5% or more of that of R404A. In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0045]

In Refrigerant 1, it is particularly preferred that HFO-1132 (E) is present in an amount of 41.3 to 53.5% by mass and HFO-1234yf is present in an amount of 58.7 to 46.5% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0046]

In Refrigerant 1, it is particularly preferred that HFO-1132 (E) is present in an amount of 41.3 to 51.0% by mass, and HFO-1234yf is present in an amount of 58.7 to 49.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99% or more of that of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0047]

In Refrigerant 1, it is most preferred that HFO-1132 (E) is present in an amount of 41.3 to 49.2 wt % and HFO-1234yf is present in an amount of 58.7 to 50.8 wt %. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0048]

In Refrigerant 1, the saturation pressure at a saturation temperature of 40°C is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1 .88 MPa or less. If the saturation pressure at saturation temperature of 40°C is within the above range, Refrigerant 1 is applicable to commercially available refrigeration units for R404A without major design changes.

[0049]

In Refrigerant 1, the saturation pressure at a saturation temperature of 40°C is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1 .76 MPa or more. If the saturation pressure at saturation temperature of 40°C is within the above range, Refrigerant 1 is applicable to commercially available refrigeration units for R404A without major design changes.

[0050]

In the present invention, when Refrigerant 1 is used to operate the refrigeration cycle, the discharge temperature is preferably 150°C or less, more preferably 140°C or less, even more preferably 130°C or less, and particularly preferably 120°C or less in terms of extending the life of commercially available refrigeration components for R404A.

[0051]

The use of refrigerant 1 for operating a refrigeration cycle in which the evaporating temperature is -75 to -5°C is advantageous in terms of providing a cooling capacity equivalent to or higher than that of R404A.

[0052]

In the refrigeration cycle using the Refrigerant 1 according to the present invention, when the evaporating temperature exceeds -5°C, the compression ratio becomes less than 2.5, which reduces the efficiency of the refrigeration cycle. In the refrigeration cycle using the Refrigerant 1 according to the present invention, when the evaporating temperature is less than -75°C, the evaporating pressure becomes less than 0.02 MPa, which makes it difficult to suck the refrigerant into the compressor. The compression ratio is calculated using the following equation:

Compression ratio=condensing pressure (MPa)/evaporating pressure (MPa) .

[0053]

In the refrigeration cycle using the Refrigerant 1 of the present invention, the evaporating temperature is preferably -7.5°C or less, more preferably -10°C or less, and even more preferably -35°C or less.

[0054]

In the refrigeration cycle using the Refrigerant 1 of the present invention, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0055]

In the refrigeration cycle using the Refrigerant 1 according to the present invention, the evaporating temperature is preferably -65°C or more and -5°C or less, more preferably -60°C or more and -5°C or less, even more preferably -55°C or more and -7.5°C or less, and particularly preferably -50°C or more and -10°C or less.

[0056]

In the refrigeration cycle using the Refrigerant 1 according to the present invention, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more in terms of improving the suction of the refrigerant into the compressor.

[0057]

In the refrigeration cycle using the Refrigerant 1 according to the present invention, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more. in terms of improving the efficiency of the refrigeration cycle. In the refrigeration cycle using the Refrigerant 1 according to the present invention, 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.

[0058]

Refrigerant 1 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% of the mass. or more. In the present invention, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7% of the mass. or more, more preferably 99.8% of the mass. or more and even more preferably 99.9% of the mass. or more from total Refrigerant 1.

[0059]

Refrigerant 1 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above performance does not deteriorate. In this case, the content of additional refrigerant is preferably 0.5 wt%. or less, more preferably 0.3% of the mass. or less, even more preferably 0.2% of the mass. or less and particularly preferably 0.1% of the mass. or less of the total Refrigerant 1. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants commonly used in the art. Refrigerant 1 may contain one additional refrigerant or two or more additional refrigerants.

[0060]

It is particularly preferred that Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 1 is particularly preferably equal to 100 wt%. from total Refrigerant 1.

[0061]

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 35.0 to 65.0 wt%, and HFO-1234yf is usually present in an amount of 65.0 up to 35.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. Refrigerant 1 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC equal to or higher than the IC of R404A; and (3) it has a cooling capacity equal to or greater than that of R404A.

[0062]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 40.5 to 59.0 mass%, and HFO-1234yf is present in an amount of 59, 5 to 41.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99% or more of that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0063]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 41.3 to 59.0% by mass, and HFO-1234yf is present in an amount of 58, 7 to 41.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99.5% or more of that of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0064]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is also preferred that HFO-1132 (E) is present in an amount of 41.3 to 55.0% by mass, and HFO-1234yf is present in an amount of 58, 7 to 45.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 101% or more relative to the IC of R404A, and a cooling capacity of 99.5% or more of that of R404A. In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0065]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 41.3 to 53.5% by weight, and HFO-1234yf is present in an amount of 58, 7 to 46.5% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0066]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 41.3 to 51.0% by mass, and HFO-1234yf is present in an amount of 58, 7 to 49.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99% or more of that of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0067]

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) is present in an amount of from 41.3 to 49.2 wt%, and HFO-1234yf is present in an amount of from 58, 7 to 50.8% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0068]

1.2 Refrigerant 2

In an embodiment of the invention, the refrigerant in the composition in accordance with the present invention contains HFO-1132 (E) and HFO-1234yf, where HFO-1132 (E) is present in an amount of from 40.5 to 49.2 wt%, and HFO-1234yf is present in an amount of 59.5 to 50.8 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 2".

[0069]

Refrigerant 2 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC equal to or higher than the IC of R404A; (3) it has a cooling capacity equivalent to or greater than that of R404A; and (4) it is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0070]

Since Refrigerant 2 contains HFO-1132 (E) in the amount of 40.5% of the mass. or more based on the combined weight of HFO-1132(E) and HFO-1234yf, Refrigerant 2 has a cooling capacity equivalent to or greater than that of R404A. Moreover, since Refrigerant 2 contains HFO-1132 (E) in the amount of 49.2% of the mass. or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of refrigerant 2 at a saturation temperature of 40°C in the refrigeration cycle can be maintained within an acceptable range (in particular, 2.10 MPa or less).

[0071]

The refrigerant 2 may have a cooling capacity of 99% or more, preferably 100% or more, more preferably 101% or more, even more preferably 102% or more, and particularly preferably 103% or more, relative to the cooling capacity of R404A.

[0072]

Since the GWP is 100 or less, Refrigerant 2 can significantly reduce the burden on the environment from a global warming perspective compared to other general purpose refrigerants.

[0073]

In the Refrigerant, the ratio of cooling capacity to the power consumed in the refrigeration cycle (COP) in comparison with R404A CC is preferably high in terms of energy efficiency. More specifically, the IC relative to the IC of R404A is preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more.

[0074]

In Refrigerant 2, it is preferred that HFO-1132 (E) is present in an amount of 41.3 to 49.2 wt% and HFO-1234yf is present in an amount of 58.7 to 50.8 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0075]

In the Refrigerant, it is preferable that HFO-1132 (E) is present in an amount of from 43.0 to 49.2 wt%, and HFO-1234yf is present in an amount of from 57.0 to 50.8 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 101% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigerants without significant design changes.

[0076]

In Refrigerant 2, it is also preferred that HFO-1132 (E) is present in an amount of 44.0 to 49.2 wt % and HFO-1234yf is present in an amount of 56.0 to 50.8 wt %. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 101% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0077]

In Refrigerant 2, it is particularly preferred that HFO-1132 (E) is present in an amount of 45.0 to 49.2 wt% and HFO-1234yf is present in an amount of 55.0 to 50.8 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 102% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0078]

In Refrigerant 2, it is particularly preferred that HFO-1132 (E) is present in an amount of 45.0 to 48.0% by mass and HFO-1234yf is present in an amount of 55.0 to 52.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102.5% or more of the IC of R404A, and a cooling capacity of 102.5% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L) . Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0079]

In Refrigerant 2, it is most preferred that HFO-1132 (E) is present in an amount of 45.0 to 47.0 wt % and HFO-1234yf is present in an amount of 55.0 to 53.0 wt %. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102.5% or more of the IC of R404A, and a cooling capacity of 102.5% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L) . Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.85 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0080]

In Refrigerant 2, the saturation pressure at a saturation temperature of 40°C is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1 .88 MPa or less. If the saturation pressure at saturation temperature of 40°C is within the above range, Refrigerant 2 is applicable to commercially available refrigeration units for R404A without major design changes.

[0081]

In Refrigerant 2, the saturation pressure at a saturation temperature of 40°C is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1 .76 MPa or more. If the saturation pressure at saturation temperature of 40°C is within the above range, Refrigerant 2 is applicable to commercially available refrigeration units for R404A without major design changes.

[0082]

In the present invention, when Refrigerant 2 is used to operate the refrigeration cycle, the discharge temperature is preferably 150°C or less, more preferably 140°C or less, even more preferably 130°C or less, and particularly preferably 120°C or less from the point of view of extending the life of commercially available refrigeration components for R404A.

[0083]

In the present invention, Refrigerant 2 is preferably used to operate a refrigeration cycle in which the evaporating temperature is -75 to 15°C in terms of obtaining a cooling capacity equivalent to or higher than that of R404A.

[0084]

In the refrigeration cycle using the Refrigerant 2 according to the present invention, the evaporating temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less. .

[0085]

In the refrigeration cycle using the Refrigerant 2 of the present invention, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0086]

In the refrigeration cycle using the Refrigerant 2 according to the present invention, the evaporating temperature is preferably -65°C or more and 10°C or less, more preferably -60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and especially preferably -50°C or more and -5°C or less.

[0087]

In the refrigeration cycle using the Refrigerant 2 according to the present invention, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more in terms of improving the suction of the refrigerant into the compressor.

[0088]

In the refrigeration cycle using Refrigerant 2 according to the present invention, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more. in terms of improving the efficiency of the refrigeration cycle.

[0089]

Refrigerant 2 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% of the mass. or more. In the present invention, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7% of the mass. or more, more preferably 99.8% of the mass. or more and even more preferably 99.9% of the mass. or more from total Refrigerant 2.

[0090]

Refrigerant 2 may also contain an additional refrigerant besides HFO-1132(E) and HFO-1234yf as long as the above performance is not degraded. In this case, the content of additional refrigerant is preferably 0.5 wt%. or less, more preferably 0.3% of the mass. or less, even more preferably 0.2% of the mass. or less and particularly preferably 0.1% of the mass. or less of all Refrigerant 2. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants commonly used in the art. Refrigerant 2 may contain one additional refrigerant or two or more additional refrigerants.

[0091]

It is especially preferred that Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the Refrigerant is particularly preferably equal to 100 wt%. from all Refrigerant 2.

[0092]

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is usually present in an amount of 40.5 to 49.2 wt%, and HFO-1234yf is usually present in an amount of 59.5 up to 50.8% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. Refrigerant 2 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC equal to or higher than the IC of R404A; (3) it has a cooling capacity equivalent to or greater than that of R404A; and (4) it is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0093]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 41.3 to 49.2 wt%, and HFO-1234yf is present in an amount of 58, 7 to 50.8% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a refrigeration capacity of 99.5% or more of that of R404A, and is flame-retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0094]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 43.0 to 49.2 wt%, and HFO-1234yf is present in an amount of 57, 0 to 50.8% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 101% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0095]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is also preferred that HFO-1132 (E) is present in an amount of 44.0 to 49.2 wt%, and HFO-1234yf is present in an amount of 56 0 to 50.8% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 101% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0096]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 45.0 to 49.2 wt% and HFO-1234yf is present in an amount of 55 0 to 50.8% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102% or more of the IC of R404A, and a cooling capacity of 102% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0097]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 45.0 to 48.0 wt% and HFO-1234yf is present in an amount of 55 .0 to 52.0 wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has a GWP of 100 or less, an IC of 102.5% or more of the IC of R404A, and a cooling capacity of 102.5% or more of that of R404A, and is flame retardant according to ASHRAE Standards (Class 2L) . Further, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40°C, and is therefore applicable to commercially available R404A refrigeration apparatuses without significant design changes.

[0098]

1.3 Refrigerant 3

In an embodiment of the invention, the refrigerant in the composition in accordance with the present invention contains HFO-1132 (E) and HFO-1234yf, where HFO-1132 (E) is present in an amount of from 31.1 to 39.8% wt., and HFO -1234yf is present in an amount of 68.9 to 60.2% by weight, based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 3".

[0099]

The refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an HC nearly equivalent to R134a's HC; (3) it has a cooling capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90°C or less.

[0100]

Since Refrigerant 3 contains HFO-1132 (E) in the amount of 31.1% of the mass. or more based on the combined weight of HFO-1132 (E) and HFO-1234yf, Refrigerant 3 has a cooling capacity of 150% or more of that of R134a. Moreover, since Refrigerant 3 contains HFO-1132 (E) in the amount of 39.8% of the mass. or less based on the total weight of HFO-1132 (E) and HFO-1234yf, the discharge temperature of the refrigerant 3 in the refrigeration cycle can be maintained at 90°C or less, and a long service life of the refrigeration system components for R134a can be ensured.

[0101]

The refrigerant 3 may have a cooling capacity of 150% or more, preferably 151% or more, more preferably 152% or more, even more preferably 153% or more, and particularly preferably 154% or more, relative to the cooling capacity of R134a.

[0102]

The refrigerant 3 has a discharge temperature of preferably 90.0°C or less, more preferably 89.7°C or less, even more preferably 89.4°C or less, and particularly preferably 89.0°C or less in the refrigeration cycle.

[0103]

Since the GWP is 100 or less, Refrigerant 3 can significantly reduce the burden on the environment from a global warming perspective compared to other general purpose refrigerants.

[0104]

In Refrigerant 3, the ratio of refrigeration capacity to power consumed in the refrigeration cycle (Coefficient of Performance (COP)), relative to CC R134a, is preferably high in terms of energy efficiency. More specifically, the IC in comparison with the IC of R134a is preferably 90% or more, more preferably 91% or more, even more preferably 91.5% or more, and particularly preferably 92% or more.

[0105]

In Refrigerant 3, HFO-1132 (E) is typically present in an amount of 31.1 to 39.8 wt%, and HFO-1234yf is typically present in an amount of 68.9 to 60.2 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. The refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an HC nearly equivalent to R134a's HC; (3) it has a cooling capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90.0°C or less.

[0106]

In Refrigerant 3, it is preferred that HFO-1132 (E) is present in an amount of 31.1 to 37.9 wt% and HFO-1234yf is present in an amount of 68.9 to 62.1 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 150% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0107]

In Refrigerant 3, it is more preferred that HFO-1132 (E) is present in an amount of 32.0 to 37.9 wt% and HFO-1234yf is present in an amount of 68.0 to 62.1 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 151% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less, and (5) the critical temperature is 81°C or more.

[0108]

In Refrigerant 3, it is also preferred that HFO-1132 (E) is present in an amount of 33.0 to 37.9% by mass, and HFO-1234yf is present in an amount of 67.0 to 62.1% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 152% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0109]

In Refrigerant 3, it is even more preferred that HFO-1132 (E) is present in an amount of 34.0 to 37.9 wt% and HFO-1234yf is present in an amount of 66.0 to 62.1 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 153% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0110]

In Refrigerant 3, it is particularly preferred that HFO-1132 (E) is present in an amount of 35.0 to 37.9% by mass and HFO-1234yf is present in an amount of 65.0 to 62.1% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 155% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0111]

In the present invention, when Refrigerant 3 is used to operate the refrigeration cycle, the discharge temperature is preferably 90.0°C or less, more preferably 89.7°C or less, even more preferably 89.4°C or less, and particularly preferably 89. 0°C or less in terms of extending the life of commercially available refrigeration apparatus components for R134a.

[0112]

In the present invention, when Refrigerant 3 is used to operate the refrigeration cycle, the refrigeration cycle requires a refrigerant liquefaction (condensation) process; that is, the critical temperature must be markedly higher than the temperature of the cooling water or cooling air to liquefy the refrigerant. From this point of view, in the refrigeration cycle in which the Refrigerant 3 of the present invention is used, the critical temperature is preferably 80°C or more, more preferably 81°C or more, even more preferably 81.5°C or more, and particularly preferably 82°C. C or more.

[0113]

In the present invention, Refrigerant 3 is generally used to operate a refrigeration cycle in which the evaporating temperature is -75 to 15°C, in terms of obtaining a cooling capacity of 150% or more relative to that of R134a.

[0114]

In the refrigeration cycle using the Refrigerant 3 according to the present invention, the evaporating temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less. .

[0115]

In the refrigeration cycle using the Refrigerant 3 of the present invention, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0116]

In the refrigeration cycle using the Refrigerant 3 according to the present invention, the evaporating temperature is preferably -65°C or more and 15°C or less, more preferably -60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and especially preferably -50°C or more and -5°C or less.

[0117]

In the refrigeration cycle using the Refrigerant 3 according to the present invention, the critical temperature of the refrigerant is preferably 80°C or more, more preferably 81°C or more, even more preferably 81.5°C or more, and particularly preferably 82°C. or more in terms of performance improvement.

[0118]

Refrigerant 3 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% of the mass. or more. In the present invention, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7% of the mass. or more, more preferably 99.8% of the mass. or more and even more preferably 99.9% of the mass. or more from total Refrigerant 3.

[0119]

Refrigerant 3 may also contain an additional refrigerant besides HFO-1132(E) and HFO-1234yf as long as the above performance is not degraded. In this case, the content of additional refrigerant is preferably 0.5 wt%. or less, more preferably 0.3% of the mass. or less, even more preferably 0.2% of the mass. or less, and especially preferably 0.1% of the mass. or less of the total Refrigerant 3. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants commonly used in the art. Refrigerant 3 may contain one additional refrigerant or two or more additional refrigerants.

[0120]

It is particularly preferred that Coolant 3 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 3 is particularly preferably equal to 100 wt%. from all Refrigerant 3.

[0121]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is typically present in an amount of 31.1 to 39.8 wt%, and HFO-1234yf is typically present in an amount of 68.9 to 60.2% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. The refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an HC nearly equivalent to R134a's HC; (3) it has a cooling capacity of 150% or more relative to that of R134a; and (4) the discharge temperature is 90°C or less.

[0122]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 31.1 to 37.9% by mass, and HFO-1234yf is present in an amount of 68, 9 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 150% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0123]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, it is more preferable that HFO-1132 (E) is present in an amount of 32.0 to 37.9% by mass, and HFO-1234yf is present in an amount of 68 .0 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 151% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0124]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) is present in an amount of 33.0 to 37.9 wt. %, and HFO-1234yf is present in an amount of from 67.0 to 62.1% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 152% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0125]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, it is also preferred that HFO-1132 (E) is present in an amount of 34.0 to 37.9% by mass, and HFO-1234yf is present in an amount of 66 .0 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 153% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0126]

When Refrigerant 3 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132(E) is present in an amount of 35.0 to 37.9 wt% and HFO-1234yf is present in an amount of 65 .0 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an IC of 92% or more relative to the IC of R134a; (3) it has a cooling capacity of 155% or more relative to that of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0127]

1.4 Refrigerant 4

In an embodiment of the invention, the refrigerant in the composition in accordance with the present invention contains HFO-1132 (E) and HFO-1234yf, where HFO-1132 (E) is present in an amount of from 21.0 to 28.4% wt., and HFO-1234yf is present in an amount of 79.0 to 71.6 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 4."

[0128]

The refrigerant 4 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an HC almost equivalent to that of R1234yf; (3) it has a cooling capacity of 140% or more relative to that of R1234yf; and (4) it is flame retardant according to ASHRAE standards (Class 2L). In addition, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0129]

Since Refrigerant 4 contains HFO-1132 (E) in the amount of 21.0% of the mass. or more based on the combined weight of HFO-1132 (E) and HFO-1234yf, Refrigerant 4 has a cooling capacity of 140% or more of that of R1234yf. Moreover, Refrigerant 4 contains HFO-1132 (E) in the amount of 28.4 wt%. or less based on the combined weight of HFO-1132(E) and HFO-1234yf. This makes it easy to achieve a critical temperature of 83.5°C or more.

[0130]

The refrigerant 4 may have a cooling capacity of 140% or more, preferably 142% or more, more preferably 143% or more, even more preferably 145% or more, and particularly preferably 146% or more, relative to the cooling capacity of R1234yf.

[0131]

Since the GWP is 100 or less, Refrigerant 4 can significantly reduce the burden on the environment from a global warming perspective compared to other general purpose refrigerants.

[0132]

In Refrigerant 4, the ratio of cooling capacity to power consumed in the refrigeration cycle (COP) relative to R1234yf CC is preferably high from the point of view of energy efficiency. More specifically, the IC relative to the IC of R1234yf is preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, and particularly preferably 98% or more.

[0133]

In Refrigerant 4, it is preferred that HFO-1132 (E) is present in an amount of 21.5 to 28.0 wt% and HFO-1234yf is present in an amount of 78.5 to 72.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available refrigeration apparatuses for R1234yf without major changes in design.

[0134]

In Refrigerant 4, it is more preferred that HFO-1132 (E) is present in an amount of 22.0 to 27.7% by mass, and HFO-1234yf is present in an amount of 78.0 to 72.3% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0135]

In Refrigerant 4, it is even more preferred that HFO-1132 (E) is present in an amount of 22.5 to 27.5 wt% and HFO-1234yf is present in an amount of 77.5 to 72.5 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0136]

In Refrigerant 4, it is particularly preferred that HFO-1132 (E) is present in an amount of 23.0 to 27.2% by mass, and HFO-1234yf is present in an amount of 77.0 to 72.8% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 141% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0137]

In Refrigerant 4, it is also particularly preferred that HFO-1132 (E) is present in an amount of 23.5 to 27.0% by mass, and HFO-1234yf is present in an amount of 76.5 to 73.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 142% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available refrigeration apparatuses for R1234yf without significant design changes.

[0138]

In Refrigerant 4, it is most preferred that HFO-1132 (E) is present in an amount of 24.0 to 26.7 wt% and HFO-1234yf is present in an amount of 76.0 to 73.3 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 144% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.6°C or less; and the critical temperature is 84.0° C. or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0139]

In Refrigerant 4, the saturation pressure at a saturation temperature of -10° C. is usually 0.420 MPa or less, preferably 0.418 MPa or less, more preferably 0.417 MPa or less, even more preferably 0.415 MPa or less, and particularly preferably 0.413 MPa or less. When the saturation pressure is within this range, Refrigerant 4 is applicable to commercially available R1234yf refrigeration units without major design changes.

[0140]

In Refrigerant 4, the saturation pressure at a saturation temperature of -10°C is usually 0.380 MPa or more, preferably 0.385 MPa or more, more preferably 0.390 MPa or more, even more preferably 0.400 MPa or more, and particularly preferably 0.410 MPa or more. In these cases, Refrigerant 4 is applicable to commercially available R1234yf chillers without major design changes.

[0141]

In the present invention, when Refrigerant 4 is used to operate the refrigeration cycle, the discharge temperature is preferably 65°C or less, more preferably 64.8°C or less, even more preferably 64.7°C or less, and particularly preferably 64.5°C. C or less in terms of extending the life of commercially available refrigeration apparatus components for R1234yf.

[0142]

In the present invention, Refrigerant 4 is preferably used to operate a refrigeration cycle in which the evaporating temperature is -75 to 20°C from the viewpoint of obtaining a cooling capacity of 140% or more relative to that of R1234yf.

[0143]

In the refrigeration cycle using the Refrigerant 4 of the present invention, the evaporating temperature is preferably 20°C or less, more preferably 15°C or less, even more preferably 10°C or less, and particularly preferably 5°C or less in terms of obtaining a cooling capacity of 140% or more relative to the cooling capacity of R1234yf.

[0144]

In the refrigeration cycle using the Refrigerant 4 of the present invention, the evaporating temperature is preferably -75 to 20°C, more preferably -65 to 15°C, even more preferably -60 to 10°C, also preferably - 55 to 7.5°C, and particularly preferably -50 to 5°C, in terms of obtaining a cooling capacity of 140% or more relative to the cooling capacity of R1234yf.

[0145]

In the refrigeration cycle using the Refrigerant 4 according to the present invention, the evaporating temperature is preferably -75°C or more and 20°C or less, more preferably -65°C or more and 10°C or less, also preferably - 60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and particularly preferably -50°C or more and -5°C or less, from the viewpoint of obtaining a cooling capacity of 140 % or more relative to the cooling capacity of R1234yf.

[0146]

In the refrigeration cycle using the Refrigerant 4 according to the present invention, the discharge temperature is preferably 65.0°C or less, more preferably 64.9°C or less, even more preferably 64.8°C or less, and particularly preferably 64.7°C or less, in terms of extending the life of commercially available refrigeration apparatus components for R1234yf.

[0147]

In the present invention, when Refrigerant 4 is used to operate the refrigeration cycle, the refrigeration cycle requires a refrigerant liquefaction (condensation) process; that is, the critical temperature must be markedly higher than the temperature of the cooling water or cooling air to liquefy the refrigerant. From this point of view, in the refrigeration cycle using the Refrigerant 4 of the present invention, the critical temperature is preferably 83.5°C or more, more preferably 83.8°C or more, even more preferably 84.0°C or more, and particularly preferably 84.5° C. or more.

[0148]

The refrigerant 4 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above performance does not deteriorate. In this case, the content of additional refrigerant is preferably 0.5 wt%. or less, more preferably 0.3% of the mass. or less, even more preferably 0.2% of the mass. or less and particularly preferably 0.1% of the mass. or less of the total Refrigerant 4. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants commonly used in the art. Refrigerant 4 may contain one additional refrigerant or two or more additional refrigerants.

[0149]

It is particularly preferred that Coolant 4 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 4 is particularly preferably 100% by weight. from all Refrigerant 4.

[0150]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is typically present in an amount of 21.0 to 28.4% by weight, and HFO-1234yf is typically present in an amount of 79.0 up to 71.6% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. The refrigerant 4 has the features described above and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has an HC almost equivalent to that of R1234yf; (3) it has a cooling capacity of 140% or more relative to that of R1234yf; and (4) it is flame retardant according to ASHRAE standards (Class 2L). In addition, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0151]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 21.5 to 28.0% by mass, and HFO-1234yf is present in an amount of 78, 5 to 72.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available refrigeration apparatuses for R1234yf without major changes in design.

[0152]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is more preferable that HFO-1132 (E) is present in an amount of 22.0 to 27.7% by mass, and HFO-1234yf is present in an amount of 78 .0 to 72.3% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0153]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) is present in an amount of from 22.5 to 27.5% by weight, and HFO-1234yf is present in an amount of from 77.5 to 72.5% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 140% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0154]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 23.0 to 27.2% by weight and HFO-1234yf is present in an amount of 77 .0 to 72.8 wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 141% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available refrigeration apparatuses for R1234yf without significant design changes.

[0155]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is also particularly preferred that HFO-1132 (E) is present in an amount of from 23.5 to 27.0 wt%, and HFO-1234yf is present in an amount of from 76.5 to 73.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 142% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available refrigeration apparatuses for R1234yf without significant design changes.

[0156]

When Refrigerant 4 is composed of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) is present in an amount of 24.0 to 26.7% by weight and HFO-1234yf is present in an amount of 76 0 to 73.3% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: GWP is 100 or less; it has an IC of 98% or more relative to the IC of R1234yf; it has a cooling capacity of 144% or more relative to that of R1234yf; it is flame retardant according to ASHRAE standards (Class 2L); the discharge temperature is 64.6°C or less; and the critical temperature is 84.0° C. or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10°C, and is therefore applicable to commercially available R1234yf refrigeration apparatuses without significant design changes.

[0157]

The refrigerant 5 according to the present invention is described below.

[0158]

Technical description

Before describing Refrigerant 5, the difference between gasoline-powered vehicles and electric-powered vehicles and the benefits of heat pumps are discussed.

[0159]

The difference between gasoline powered vehicles and electric powered vehicles

Gasoline-powered vehicles recycle engine exhaust gases to provide warm air for the heating function, while electric-powered vehicles do not have a heat source to recycle and therefore use electricity for heating. In conventional electrically heated air conditioners, the use of the heater directly results in energy consumption, which greatly reduces the actual driving distance. Heat pumps that heat the interior using the temperature difference between the refrigerant and the outside air provide a heating effect that is higher than the power input, making it possible to heat the vehicle interior with less power than before.

[0160]

Advantages of heat pumps

When heated, the following steps take place: (a) the step of compressing the refrigerant gas, which is evaporated by absorbing heat from the outside air in the heat exchanger, in the compressor to form high temperature high pressure gas, and (b) converting the cold air inside the vehicle into warm air by heat exchange and blowing warm air into the vehicle from the vents of the air conditioner. This corresponds to the reverse cycle of the cycle in which the heat absorbed from the interior of the vehicle is released from the outdoor heat exchanger to provide a cooling and heating function in summer. Heat pumps, which can be used for both cooling and heating with a single refrigerant circulation system, have a higher coefficient of performance (COP) than the COP of heating with conventional electric heaters.

[0161]

1.5 Refrigerant 5

In an embodiment of the invention, the refrigerant in the composition in accordance with the present invention contains HFO-1132 (E) and HFO-1234yf, where HFO-1132 (E) is present in an amount of from 12.1 to 72.0% wt., and HFO-1234yf is present in an amount of 87.9 to 28.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 5".

[0162]

In the present invention, Refrigerant 5 is used for the air conditioning system of vehicles.

[0163]

The refrigerant 5 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has an HC almost equivalent to that of R1234yf; (3) it has a cooling capacity of 128% or more relative to that of R1234yf; and (4) the burning speed is less than 10.0 cm/sec.

[0164]

Refrigerant 5 contains HFO-1132 (E) in the amount of 12.1% of the mass. or more based on the combined weight of HFO-1132(E) and HFO-1234yf. This makes it possible to achieve a boiling point of -40° C. or less, which is useful when an electric motor vehicle is heated using a heat pump. Boiling point -40°C or less means that the saturation pressure is equal to or higher than atmospheric pressure at -40°C. For the above application, a lower boiling point, which is not higher than -40°C, is preferred.

[0165]

Since the boiling point of HFO-1234yf is -29°C, the saturation pressure at an evaporation temperature of -30°C or less is equal to or less than atmospheric pressure. Thus, there is a problem that the heating operation cannot be carried out using a heat pump in an electric vehicle. Even if the heating operation can be carried out, there is a problem that the suction pressure of the compressor is very low, resulting in insufficient performance, resulting in a long period of time for heating. In this case, since a heat pump highly efficient in heating cannot be used in vehicles with an electric motor, there is a problem that heating must be performed using an inefficient electric heater. On the contrary, with a refrigerant having a boiling point of -40°C or less, the heating operation can be performed with a heat pump in vehicles with an electric motor at an evaporating temperature of up to -40°C. Therefore, heat pump heating can be possible in vehicles with an electric motor in almost all regions of the world.

[0166]

Refrigerant 5 contains HFO-1132 (E) in the amount of 72.0% of the mass. or less based on the combined weight of HFO-1132(E) and HFO-1234yf. This allows for a burning rate of less than 10.0 cm/sec, which contributes to safety when used in a vehicle air conditioning system.

[0167]

The refrigerant 5 may have a cooling capacity of 128% or more, preferably 130% or more, more preferably 140% or more, even more preferably 150% or more, and particularly preferably 160% or more, relative to the cooling capacity of R1234yf.

[0168]

Since the GWP is 5 or more and 100 or less, Refrigerant 5 can significantly reduce the burden on the environment from a global warming perspective compared to other general purpose refrigerants.

[0169]

In Refrigerant 5, the ratio of cooling capacity to power consumed in the refrigeration cycle (COP) relative to R1234yf CC can be 100% or more in terms of energy efficiency.

[0170]

The use of refrigerant 5 for the air conditioning system of vehicles provides heating with a heat pump, which consumes less energy than electric heaters.

[0171]

The air conditioning system for which Refrigerant 5 is used is preferably for gasoline vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles. From the viewpoint of improving the driving distance of a vehicle when the interior of a vehicle is heated by a heat pump, an air conditioning system for which Refrigerant 5 is used, among others, is especially preferable for vehicles with an electric motor. More specifically, in the present invention, the Coolant 5 is particularly preferably used in the case of vehicles with an electric motor.

[0172]

In the present invention, Refrigerant 5 is used for vehicle air conditioning systems. In the present invention, Refrigerant 5 is preferably used for air conditioning systems for gasoline vehicles, air conditioning systems for hybrid vehicles, air conditioning systems for electric vehicles, or air conditioning systems for hydrogen vehicles. In the present invention, Refrigerant 5 is particularly preferred in air conditioning systems for electric vehicles.

[0173]

In the present invention, Refrigerant 5 is preferably used for a refrigeration apparatus for vehicles such as gasoline vehicles, hybrid vehicles, plug-in hybrid vehicles, electric vehicles, hydrogen vehicles, and fuel cell vehicles. Of these, Refrigerant 5 is particularly preferably used for a refrigeration apparatus for electric motor vehicles in which engine exhaust heat cannot be used.

[0174]

In addition, in a situation in which engine exhaust heat cannot be used, such as because of a thermostat failure when starting the engine, the use of heat pump heating with Refrigerant 5 can immediately heat the interior of vehicles even when the vehicles are gasoline powered vehicles, hybrid vehicles, plug-in hybrid vehicles, hydrogen vehicles and fuel cell vehicles.

[0175]

In the present invention, Refrigerant 5 has a boiling point of preferably -51.2 to -40.0°C, more preferably -50.0 to -42.0°C, and even more preferably -48.0 to -44.0 °C, since at -40°C a pressure equal to or higher than atmospheric pressure is required when heating the interior of a vehicle using a heat pump.

[0176]

In Refrigerant 5, it is preferred that HFO-1132 (E) is present in an amount of 15.0 to 65.0% by mass, and HFO-1234yf is present in an amount of 85.0 to 35.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0177]

In Refrigerant 5, it is more preferred that HFO-1132 (E) is present in an amount of 20.0 to 55.0% by mass, and HFO-1234yf is present in an amount of 80.0 to 45.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0178]

In Refrigerant 5, it is even more preferred that HFO-1132 (E) is present in an amount of 25.0 to 50.0 wt% and HFO-1234yf is present in an amount of 75.0 to 50.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0179]

In Refrigerant 5, it is particularly preferred that HFO-1132 (E) is present in an amount of 30.0 to 45.0% by mass, and HFO-1234yf is present in an amount of 70.0 to 55.0% by mass. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0180]

In Refrigerant 5, it is most preferred that HFO-1132 (E) is present in an amount of 35.0 to 40.0 wt% and HFO-1234yf is present in an amount of 65.0 to 60.0 wt%. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0181]

In the present invention, the combustion speed of the refrigerant 5 is preferably less than 10.0 cm/sec, more preferably less than 5.0 cm/sec, even more preferably less than 3.0 cm/sec, and particularly preferably less than 2.0 cm/sec.

[0182]

In the present invention, Refrigerant 5 is preferably used to operate a refrigeration cycle in which the evaporating temperature is -40 to 10°C from the viewpoint of obtaining a cooling capacity equivalent to or higher than that of R1234yf.

[0183]

In the present invention, when Refrigerant 5 is used to operate the refrigeration cycle, the discharge temperature is preferably 79°C or less, more preferably 75°C or less, even more preferably 70°C or less, and particularly preferably 67°C or less.

[0184]

The refrigerant 5 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% of the mass. or more. In the present invention, the total amount of HFO-1132 (E) and HFO-1234yf is preferably 99.7% of the mass. or more, more preferably 99.8% of the mass. or more and even more preferably 99.9% of the mass. or more from total Refrigerant 5.

[0185]

The refrigerant 5 may also contain an additional refrigerant in addition to HFO-1132(E) and HFO-1234yf, as long as the above performance does not deteriorate. In this case, the content of additional refrigerant is preferably 0.5 wt%. or less, more preferably 0.3% of the mass. or less, even more preferably 0.2% of the mass. or less and particularly preferably 0.1% of the mass. or less of the total Refrigerant 5. The additional refrigerant is not limited and may be selected from a wide range of known refrigerants commonly used in the art. Refrigerant 5 may contain one additional refrigerant or two or more additional refrigerants.

[0186]

It is particularly preferred that Coolant 5 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in Refrigerant 5 is particularly preferably 100% by weight. from all Refrigerant 5.

[0187]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E) is typically present in an amount of 12.1 to 72.0 wt%, and HFO-1234yf is typically present in an amount of 87.9 up to 28.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0188]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 15.0 to 65.0 wt%, and HFO-1234yf is present in an amount of 85, 0 to 35.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0189]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is more preferable that HFO-1132 (E) is present in an amount of 20.0 to 55.0 wt%, and HFO-1234yf is present in an amount of 80 .0 to 45.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0190]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is even more preferred that HFO-1132 (E) is present in an amount of 25.0 to 50.0 wt%, and HFO-1234yf is present in an amount of from 75.0 to 50.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0191]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferred that HFO-1132 (E) is present in an amount of 30.0 to 45.0 wt%, and HFO-1234yf is present in an amount of 70, 0 to 55.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0192]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is most preferred that HFO-1132 (E) is present in an amount of 35.0 to 40.0 wt%, and HFO-1234yf is present in an amount of 65, 0 to 60.0% wt. based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0193]

1.6 Application

The refrigerant-containing composition according to the present invention can be widely used as a working fluid for known refrigerant applications in 1) a refrigeration method involving refrigeration cycle operation, and 2) a refrigeration apparatus operation method that controls a refrigeration cycle.

[0194]

The refrigeration cycle in this case means carrying out energy conversion by circulating a refrigerant (Refrigerant 1, 2, 3, 4 or 5 in accordance with the present invention) in the refrigeration apparatus in the state of a simple refrigerant or in the state of a refrigerant composition or working fluid containing refrigerant oil, discussed down through the compressor.

[0195]

The composition containing the refrigerant in accordance with the present invention is not limited; however, it is suitable for use in a vapor-compression refrigeration cycle. The vapor-compression refrigeration cycle consists of a series of cycles of (1) compressing the refrigerant in the gaseous state in the compressor, (2) cooling the refrigerant to liquid state at high pressure in the condenser, (3) reducing the pressure using an expansion valve, and (4) evaporating the liquid refrigerant at low temperature in the evaporator and heat removal due to the heat of evaporation. Depending on the refrigerant gas compression system, vapor compression refrigeration cycles can be classified into turbo cycle (centrifugal), reciprocating cycle, twin screw cycle, single screw cycle, scroll compressor cycle, etc., and can be selected according to the heat capacity, compression ratio and size.

[0196]

The composition containing the refrigerant in accordance with the present invention is not limited and is suitable as a refrigerant used for large chillers, and especially turbochargers (centrifugal).

[0197]

The present invention includes the use of the refrigerant (or refrigerant-containing composition) according to the present invention in a refrigeration method, the use of the refrigerant (or refrigerant-containing composition) according to the present invention in the operation method of a refrigeration apparatus, etc., and a refrigeration apparatus or the like containing refrigerant (or refrigerant-containing composition) in accordance with the present invention.

[0198]

The composition containing the Refrigerant 1 in accordance with the present invention is used to operate a refrigeration cycle in which the evaporation temperature is from -75 to -5°C.

[0199]

By using the composition containing the Refrigerant 1 of the present invention to operate a refrigeration cycle in which the evaporating temperature is -75 to -5°C, there is an advantage that a cooling capacity that is equivalent to or higher than that of R404A can be obtained. In the refrigeration cycle using the composition containing the Refrigerant 1 of the present invention, the evaporating temperature is preferably -65 to -5°C, more preferably -60 to -7.5°C, even more preferably -55 to - 10°C and particularly preferably from -50 to -35°C.

[0200]

In the refrigeration cycle using the composition containing the Refrigerant 1 according to the present invention, the evaporating temperature is preferably -7.5°C or less, more preferably -10°C or less, even more preferably -35°C or less.

[0201]

In the refrigeration cycle using the composition containing the Refrigerant 1 according to the present invention, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0202]

From the point of view of obtaining a cooling capacity that is equivalent to or higher than that of R404A, the composition containing the Refrigerant 2 of the present invention is preferably used to operate a refrigeration cycle in which the evaporating temperature is -75 to 15°C. In the refrigeration cycle using the composition containing Refrigerant 2 according to the present invention, the evaporating temperature is preferably -65 to 10°C, more preferably -60 to 5°C, even more preferably -55 to 0°C. and particularly preferably -50 to -5°C.

[0203]

In the refrigeration cycle using the composition containing the Refrigerant 2 according to the present invention, the evaporating temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5° C or less.

[0204]

In the refrigeration cycle in which the composition containing the Refrigerant 2 according to the present invention is used, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0205]

From the point of view of obtaining a cooling capacity that is equivalent to or higher than that of R134a, the composition containing the Refrigerant 3 of the present invention is preferably used to operate a refrigeration cycle in which the evaporation temperature is -75 to 15°C. In the refrigeration cycle using the composition containing the Refrigerant 3 according to the present invention, the evaporating temperature is preferably -65 to 15°C, more preferably -60 to 5°C, even more preferably -55 to 0°C. and particularly preferably -50 to -5°C.

[0206]

In the refrigeration cycle using the composition containing the Refrigerant 3 according to the present invention, the evaporating temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C. C or less.

[0207]

In the refrigeration cycle using the composition containing the Refrigerant 3 of the present invention, the evaporating temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50 °C or more.

[0208]

In the refrigeration cycle using the composition containing the Refrigerant 3 of the present invention, the evaporating temperature is preferably -65°C or more to 15°C or less, more preferably -60°C or more to 5°C or less, even more preferably -55°C or more to 0°C or less, and particularly preferably -50°C or more to -5°C or less.

[0209]

From the viewpoint of obtaining a cooling capacity of 140% or more compared to that of R1234yf, the composition containing the Refrigerant 4 of the present invention is preferably used to operate a refrigeration cycle in which the evaporating temperature is -75 to 20°C. In the refrigeration cycle using the composition containing the Refrigerant 4 of the present invention, the evaporating temperature is preferably -65 to 15°C, more preferably -60 to 10°C, even more preferably -55 to 7.5°C. and particularly preferably -50 to 5°C.

[0210]

From the point of view of obtaining a cooling capacity of 140% or more compared to that of R1234yf in the refrigeration cycle using the composition containing the Refrigerant 4 of the present invention, the evaporating temperature is preferably 20°C or less, more preferably 15°C or less, even more preferably 10°C or less, and particularly preferably 5°C or less.

[0211]

From the point of view of obtaining a cooling capacity of 140% or more compared to that of R1234yf in the refrigeration cycle using the composition containing the Refrigerant 4 of the present invention, the evaporating temperature is preferably -75°C or more, more preferably -60°C or more, even more preferable

-55°C or more, and especially preferably -50°C or more.

[0212]

Preferred examples of refrigeration units to which the Refrigerant 1, 2, 3 or 4 (or refrigerant-containing composition) of the present invention can be used include air conditioning systems, refrigerators, freezers, water coolers, ice makers, refrigerated display cases, freezer display cases, freezer and refrigeration units, freezer and cold store chillers, vehicle air conditioning systems, turbo chillers or screw chillers. Of these, air conditioning systems for vehicles are preferred. Of the air conditioning systems for vehicles, air conditioning systems for gas-powered vehicles, air conditioning systems for hybrid vehicles, air conditioning systems for electric vehicles, and air conditioning systems for hydrogen vehicles are more preferable. Of the air conditioning systems for vehicles, an air conditioning system for vehicles with an electric motor is particularly preferred.

[0213]

The composition containing Refrigerant 1 or 2 of the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A . The composition containing Refrigerant 1 or 2 of the present invention is suitably used as an alternative refrigerant for R22, R404A, R407F, R407H, R448A, R449A, R454C, R455A or R465A. In addition, since the composition containing the Refrigerant 1 or 2 of the present invention has a cooling capacity equivalent to R404A, which has found wide application, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R404A.

[0214]

The composition containing the Refrigerant 3 of the present invention is suitably used as an alternative refrigerant for R134a, R1234yf or CO ₂ . The composition containing the Refrigerant 3 of the present invention is suitably used as an alternative refrigerant for R134a. In addition, since the composition containing the Refrigerant 3 of the present invention has a cooling capacity of 150% or more relative to that of R134a, which is widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R134a.

[0215]

The composition containing the Refrigerant 4 of the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A , R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or. The composition containing the Refrigerant 4 of the present invention is suitably used as an alternative refrigerant for R12, R134a, R404A, R407C, R449C, R454C, R1234yf or R1234ze. In addition, since the composition containing the Refrigerant 4 of the present invention has a cooling capacity of 140% or more relative to that of R1234yf, which is widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.

[0216]

The composition containing Refrigerant 5 of the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A , R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or. The composition containing the Refrigerant 5 of the present invention is suitably used as an alternative refrigerant for R12, R134a or R1234yf. In addition, since the composition containing the Refrigerant 5 of the present invention has a cooling capacity of 140% or more relative to that of R1234yf, which is widely used, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.

[0217]

The composition containing the Refrigerant 5 according to the present invention is preferably used in an air conditioning system for vehicles. Air conditioning systems for vehicles are preferably air conditioning systems for gas-powered vehicles, air conditioning systems for hybrid vehicles, air conditioning systems for electric vehicles, or air conditioning systems for hydrogen vehicles. Of the vehicle air conditioning systems, electric vehicle air conditioning systems are particularly preferred. That is, in the present invention, the composition containing the Refrigerant 5 is particularly preferably used for vehicles with an electric motor.

[0218]

2. Refrigerant composition

The refrigerant composition of the present invention includes at least the refrigerant of the present invention and can be used for the same applications as the refrigerant of the present invention.

[0219]

In addition, the refrigerant composition according to the present invention is mixed with at least refrigerant oil. Therefore, the refrigerant composition can be used to provide a working fluid for a refrigeration unit.

[0220

The composition of the refrigerant in accordance with the present invention further contains at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may optionally contain at least one of the other components described below.

[0221]

As described above, when the refrigerant composition according to the present invention is used as a working fluid for a refrigeration apparatus, it is usually mixed with at least a refrigeration oil for use.

[0222]

Preferably, the refrigerant composition according to the present invention is substantially free of refrigerant oil. More specifically, in the refrigerant composition of the present invention, the amount of refrigerant oil relative to the total refrigerant composition is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, even more preferably 0 to 0.25% by mass. and especially preferably from 0 to 0.1% of the mass.

[0223]

2.1 Water

The refrigerant composition according to the present invention may contain a small amount of water.

[0224]

The water content of the refrigerant composition 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 especially preferably from 0 to 0.025% of the mass. for the total refrigerant.

[0225]

The small amount of water present in the refrigerant composition stabilizes the double bonds in the unsaturated fluorocarbon molecules that may be present in the refrigerant and makes the unsaturated fluorocarbon compounds less likely to oxidize, thereby improving the stability of the refrigerant composition. To achieve the effects described above, obtained due to the presence of water, the lower limit of the water content is approximately 0.001% of the mass. For example, the water content may be adjusted in the range of 0.001 to 0.1% by mass, 0.001 to 0.075% by mass, 0001 to 0.05% by mass. and from 0.001 to 0.025% of the mass.

[0226]

2.2 Tracer

The tracer is added to the refrigerant composition in accordance with the present invention at a detectable concentration so that when diluted, contaminated, or some other change in the composition, the tracer can track these changes.

[0227]

The refrigerant composition according to the present invention may contain a single tracer or two or more tracers.

[0228]

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

[0229]

Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrogen oxides (N ₂ O). Of these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are preferred.

[0230]

More specifically, the following compounds (sometimes referred to below as "tracer compounds") are more preferred as tracers:

HCC-40 (chloromethane, CH ₃ Cl), HFC-41 (fluoromethane, CH ₃ F), HFC-161 (fluoroethane, CH ₃ CH ₂ F), HFC-245fa (1,1,1,3,3-pentafluoropropane , CF ₃ CH ₂ CHF ₂ ), HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF ₃ CH ₂ CF ₃ ), HFC-236ea (1,1,1,2,3,3 -hexafluoropropane, CF ₃ CHFCHF ₂ ), HCFC-22 (chlorodifluoromethane, CHClF ₂ ), HCFC-31 (chlorofluoromethane, CH ₂ ClF), CFC-1113 (chlorotrifluoroethylene, CF ₂ =CClF), HFE-125 (trifluoromethyl-difluoro- methyl ether, CF ₃ OCHF ₂ ), HFE-134a (trifluoromethyl fluoromethyl ether, CF ₃ OCH ₂ F), HFE-143a (trifluoromethyl methyl ethyl ether, CF ₃ OCH ₃ ), HFE-227ea (trifluoromethyl tetrafluoroethyl ether, CF ₃ OCHFCF ₃ ) and HFE-236fa (trifluoromethyl trifluoroethyl ether, CF ₃ OCH ₂ CF ₃ ).

[0231]

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

[0232]

2.3 UV fluorescent dye

The refrigerant composition of the present invention may contain one ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.

[0233]

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

[0234]

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

[0235]

The amount of ultraviolet fluorescent dye is not 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% wt. and especially preferably from 0.5 to 1% of the mass. for the total refrigerant.

[0236]

2.4 Stabilizer

The refrigerant composition of the present invention may contain one stabilizer, or two or more stabilizers.

[0237]

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

[0238]

Examples of stabilizers include nitro compounds, ethers and amines.

[0239]

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

[0240]

Examples of ethers include 1,4-dioxane.

[0241]

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

[0242]

Examples of stabilizers, in addition to nitro compounds, ethers and amines, also include butylhydroxyxylene and benzotriazole.

[0243]

The amount of stabilizer is not limited. Usually the amount of stabilizer is from 0.01 to 5 wt%, preferably from 0.05 to 3 wt%, more preferably from 0.1 to 2 wt%, even more preferably from 0.25 to 1.5 wt%. . and especially preferably from 0.5 to 1% of the mass. for the total refrigerant.

[0244]

The stability of the refrigerant composition of the present invention can be evaluated by well-known methods without limitation. Examples of such methods include the estimation method using free fluorine ions as an indicator according to ASHRAE Standard 97-2007 and others. There is, for example, another estimation method using total acid number as an indicator. This method can be performed, for example, according to ASTM D 974-06.

[0245]

2.5 Polymerization inhibitor

The refrigerant composition of the present invention may contain one polymerization inhibitor, or two or more polymerization inhibitors.

[0246]

The polymerization inhibitor is not limited, and may be appropriately selected from commonly used polymerization inhibitors.

[0247]

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

[0248]

The amount of the polymerization inhibitor is not limited. Typically, the amount of polymerization inhibitor is 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% wt. and especially preferably from 0.5 to 1% of the mass. for the total refrigerant.

[0249]

2.6 Other components that may be present in the refrigerant composition

The refrigerant composition of the present invention may also contain the following components.

[0250]

For example, fluorinated hydrocarbons may be present, which are different from the refrigerants mentioned above. Examples of fluorinated hydrocarbons used as other components are not limited. At least one fluorinated hydrocarbon selected from the group consisting of HCFC-1122, HCFC-124 and CFC-1113 can be used.

[0251]

As another component, at least one halogenated organic compound represented by formula (A) may be present: C _m H _n X _p , where each X is independently fluorine, chlorine or bromine; m is 1 or 2; 2m+2 is greater than or equal to n+p; and p is greater than or equal to 1. The halogenated organic compound is not limited, and preferred examples include difluorochloromethane, chloromethane, 2-chloro-1,1,1,2,2-pentafluoroethane, 2-chloro-1,1,1, 2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene and trifluoroethylene.

[0252]

As another component, at least one organic compound represented by formula (B) may be present: C _m H _n X _p , where each X is independently an atom other than a halogen atom; m is 1 or 2; 2m+2 is greater than or equal to n+p; and p is greater than or equal to 1. The organic compound is not limited, and preferred examples include propane and isobutane.

[0253]

The amount of the fluorinated hydrocarbon, the halogenated organic compound represented by formula (A), and the organic compound represented by formula (B) is not limited. Their total amount is preferably 0.5% of the mass. or less, more preferably 0.3% of the mass. or less and particularly preferably 0.1% of the mass. or less relative to the total amount of the refrigerant composition.

[0254]

3. Refrigeration oil-containing working fluid

The refrigerant oil-containing working fluid according to the present invention includes at least a refrigerant or refrigerant composition according to the present invention and a refrigerant oil, and is used as a working fluid in a refrigeration apparatus. More specifically, the refrigerant oil-containing working fluid according to the present invention can be obtained by mixing together a refrigerant or refrigerant composition with a refrigerant oil used in a refrigeration compressor.

[0255]

The amount of refrigerant oil is not 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 especially preferably from 20 to 30% of the mass. relative to the entire working fluid containing refrigerant oil.

[0256]

3.1 Refrigeration oil

The composition of the present invention may contain one refrigeration oil, or two or more refrigeration oils.

[0257]

The refrigeration oil is not limited and may be appropriately selected from commonly used refrigeration oils. In this case, for example, refrigerant oils which are excellent in terms of improving miscibility with the refrigerant blend of the present invention (mixed refrigerant of the present invention) and stability of the blended refrigerant are suitably selected as needed.

[0258]

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

[0259]

The refrigeration oil may also contain an additive in addition to the base oil.

[0260]

The additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, anti-corrosion agents, lubricating agents, and anti-foaming agents.

[0261]

Refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40°C is preferred from a lubrication point of view.

[0262]

The refrigeration oil-containing working fluid of the present invention may optionally further contain at least one additive. Examples of additives include the compatibilizers described below.

[0263]

3.2 Compatibility-improving agents

The refrigeration oil-containing working fluid according to the present invention may contain one compatibilizer or two or more compatibilizers.

[0264]

The compatibilizer is not limited, and may be appropriately selected from commonly used compatibilizers.

[0265]

Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkane. Of these, polyoxyalkylene glycol ether is preferred.

Examples

[0266]

Below is a more detailed explanation with reference to examples. However, the present invention is not limited to the following examples.

[0267]

Test Example 1-1

The GWP of each blended refrigerant shown in Examples 1-1 to 1-13, Comparative Examples 1-1 and 1-2, and Reference Example 1-1 (R404A) is estimated based on the values of the fourth IPCC report.

[0268]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (National Institute of Science and Technology). Science and Technology (NIST)) and a database of thermodynamic and transport properties of reference liquids (Refprop 10.0) under the conditions below.

Evaporation temperature: -50°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0269]

"Evaporation temperature -50°C" means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration unit is -50°C. In addition, "condensing temperature 40°C" means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration unit is 40°C.

[0270]

Table 1 shows the results of Test Example 1-1. Table 1 shows examples and comparative examples for the refrigerant 1 of the present invention. In Table 1, "HC ratio" and "cooling capacity ratio" mean the ratio (%) when compared with R404A. In Table 1, "saturated pressure (40°C)" refers to the saturation pressure at a saturation temperature of 40°C. In Table 1, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical refrigeration cycle calculations for the mixed refrigerant.

[0271]

The coefficient of performance (CC) is calculated according to the following equation:

XK \u003d (cooling capacity or heat capacity) / amount of electricity consumed.

[0272]

The compression ratio is calculated using the following equation:

Compression ratio=condensing pressure (MPa)/evaporating pressure (MPa)

[0273]

The flammability of the mixed refrigerant is determined by setting the fractionation of the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate of 0 to 10 cm/s is classified as Class 2L (flammable), a refrigerant with a burning rate of more than 10 cm/s is classified as Class 2 (low flammability), and a refrigerant with no flame spread is classified as Class 1 (non-flammable). In Table 1, the ASHRAE Flammability Classification shows results based on these criteria.

[0274]

Burn rate tests are carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is subjected to deaeration by repeating the cycle of freezing, pumping and thawing until no traces of air are noted on the vacuum gauge. The burning rate is measured by a closed method. The starting temperature is the ambient temperature. Ignition is carried out by creating an electrical spark between the electrodes in the center of the sample cell. The duration of the discharge is from 1.0 to 9.9 ms and the ignition energy is typically about 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light was used as the sample cell, and a xenon lamp was used as the light source. The schlieren image of the flame was recorded using a high speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0275]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0276]

More specifically, a 12 L spherical glass flask is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is built up in the glass bulb during combustion, the gas is allowed to leave the bulb through the top cap. Ignition is carried out using an electric discharge from electrodes placed one third of the distance from the bottom.

[0277]

Test conditions

Test vessel: diameter 280 mm, spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio refrigerant composition/air: 1% vol. in steps of ±0.2% vol.

Refrigerant composition blend: ±0.1% wt.

Ignition method: AC discharge, voltage 15KV, electric current 30mA, neon transducer

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Criteria for evaluation

When the flame propagates at an angle greater than 90° from the ignition point, it is judged that flame propagation is present (flammable).

When the flame spreads at an angle of 90° or less from the ignition point, it is judged that there is no flame propagation (non-flammable).

[0278]

Table 1

[0279]

Test Example 1-2

The GWP of each blended refrigerant shown in Examples 1-14 to 1-26, Comparative Examples 1-3 and 1-4, and Reference Example 1-2 (R404A) is estimated based on the values of the fourth IPCC report.

[0280]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at saturated temperature of 40°C, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0 under the following conditions .

Evaporation temperature: -35°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0281]

The definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0282]

Table 2 shows the results of Test Example 1-2. Table 2 shows examples and comparative examples regarding Refrigerant 1 of the present invention. In Table 2, the definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0283]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0284]

The flammability of the mixed refrigerant was evaluated as in Test Example 1-1. Burn rate tests are carried out as in Test Example 1-1.

[0285]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0286]

table 2

[0287]

Test Example 1-3

The GWP of each blended refrigerant shown in Examples 1-27 to 1-39, Comparative Examples 1-5 and 1-6, and Reference Example 1-3 (R404A) is estimated based on the values of the fourth IPCC report.

[0288]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at saturated temperature of 40°C, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0 under the following conditions .

Evaporation temperature: -10°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0289]

The definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0290]

Table 3 shows the results of Test Example 1-3. Table 3 shows examples and comparative examples regarding Refrigerant 1 of the present invention. In Table 3, the definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0291]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0292]

The flammability of the mixed refrigerant was evaluated as in Test Example 1-1. Burn rate tests are carried out as in Test Example 1-1.

[0293]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0294]

Table 3

[0295]

Test Example 1-4

The GWP of each blended refrigerant shown in Comparative Examples 1-7 to 1-21 and Reference Example 1-4 (R404A) is estimated based on the values of the fourth IPCC report.

[0296]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0, with the following conditions.

Evaporation temperature: -80°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0297]

The definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0298]

Table 4 shows the results of Test Example 1-4. Table 4 shows comparative examples regarding Refrigerant 1 of the present invention. In Table 4, the definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0299]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0300]

The flammability of the mixed refrigerant was evaluated as in Test Example 1-1. Burn rate tests are carried out as in Test Example 1-1.

[0301]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0302]

Table 4

[0303]

Test Example 1-5

The GWP of each blended refrigerant shown in Comparative Examples 1-22 to 1-36 and Reference Example 1-5 (R404A) is estimated based on the values of the fourth IPCC report.

[0304]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop, 10.0, at following conditions.

Evaporation temperature: 10°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0305]

The definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0306]

Table 5 shows the results of Test Example 1-5. Table 5 shows comparative examples regarding Refrigerant 1 of the present invention. In Table 5, the definitions of the terms are the same as the definitions of the terms in Test Example 1-1.

[0307]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0308]

The flammability of the mixed refrigerant was evaluated as in Test Example 1-1. Burn rate tests are carried out as in Test Example 1-1.

[0309]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0310]

Table 5

[0311]

Test Example 2-1

The GWP of each blended refrigerant shown in Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-9, and Reference Example 2-1 (R404A) is estimated based on the values of the fourth IPCC report.

[0312]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and database of thermodynamic and transport properties of reference liquids (Refprop 10.0) under the following conditions.

Evaporation temperature: -50°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0313]

"Evaporation temperature -50°C" means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration unit is -50°C. In addition, "condensing temperature 40°C" means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration unit is 40°C.

[0314]

Table 6 shows the results of Test Example 2-1. Table 6 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 6, "HC ratio" and "cooling capacity ratio" mean the ratio (%) compared to R404A. In Table 6, "saturated pressure (40°C)" refers to the saturation pressure at a saturation temperature of 40°C. In Table 6, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0315]

The coefficient of performance (CC) is calculated according to the following equation:

XK \u003d (cooling capacity or heat capacity) / amount of electricity consumed.

[0316]

The compression ratio is calculated using the following equation:

Compression ratio=condensing pressure (MPa)/evaporating pressure (MPa).

[0317]

The flammability of the mixed refrigerant is determined by setting the fractionation of the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate between 0 cm/s and 10 cm/s is classified as Class 2L (flammable), a refrigerant with a burning rate greater than 10 cm/s is classified as Class 2 (low flammability), and a refrigerant with no flame spread is classified as Class 1 ( nonflammable). In Table 6, the ASHRAE flammability classification shows results based on these criteria.

[0318]

Burn rate tests are carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is subjected to deaeration by repeating the cycle of freezing, pumping and thawing until no traces of air are noted on the vacuum gauge. The burning rate is measured by a closed method. The starting temperature is the ambient temperature. Ignition is carried out by creating an electrical spark between the electrodes in the center of the sample cell. The duration of the discharge is from 1.0 to 9.9 ms and the ignition energy is typically about 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light was used as the sample cell, and a xenon lamp was used as the light source. The schlieren image of the flame was recorded using a high speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0319]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0320]

More specifically, a 12 L spherical glass flask is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is built up in the glass bulb during combustion, the gas is allowed to leave the bulb through the top cap. Ignition is carried out using an electric discharge from electrodes placed one third of the distance from the bottom.

[0321]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio refrigerant composition/air: 1% vol. in steps of ±0.2% vol.

Refrigerant composition blend: ±0.1% wt.

Ignition method: AC discharge, voltage 15KV, electric current 30mA, neon transducer

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Criteria for evaluation

When the flame propagates at an angle greater than 90° from the ignition point, it is judged that flame propagation is present (flammable).

When the flame spreads at an angle of 90° or less from the ignition point, it is judged that there is no flame propagation (non-flammable).

[0322]

Table 6

[0323]

Test Example 2-2

The GWP of each blended refrigerant shown in Examples 2-7 to 2-12, Comparative Examples 2-10 to 1-18, and Reference Example 2-2 (R404A) is estimated based on the values of the fourth IPCC report.

[0324]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0, with the following conditions.

Evaporation temperature: -35°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0325]

The definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0326]

Table 7 shows the results of Test Example 2-2. Table 7 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 7, the definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0327]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0328]

The flammability of the mixed refrigerant was evaluated as in Test Example 2-1. Burn rate tests are carried out as in Test Example 2-1.

[0329]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0330]

Table 7

[0331]

Test Example 2-3

The GWP of each blended refrigerant shown in Examples 2-13 to 2-18, Comparative Examples 2-19 to 2-27, and Reference Example 2-3 (R404A) is estimated based on the values of the fourth IPCC report.

[0332]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0, with the following conditions.

Evaporation temperature: -10°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0333]

The definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0334]

Table 8 shows the results of Test Example 2-3. Table 8 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 8, the definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0335]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0336]

The flammability of the mixed refrigerant was evaluated as in Test Example 2-1. Burn rate tests are carried out as in Test Example 2-1.

[0337]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0338]

Table 8

[0339]

Test Example 2-4

The GWP of each blended refrigerant shown in Examples 2-19 to 2-24, Comparative Examples 2-28 to 2-36, and Reference Example 2-4 (R404A) is estimated based on the values of the fourth IPCC report.

[0340]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0, with the following conditions.

Evaporation temperature: -80°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0341]

The definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0342]

Table 9 shows the results of Test Example 2-4. Table 9 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 9, the definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0343]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0344]

The flammability of the mixed refrigerant was evaluated as in Test Example 2-1. Burn rate tests are carried out as in Test Example 2-1.

[0345]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0346]

Table 9

[0347]

Test Example 2-5

The GWP of each blended refrigerant shown in Examples 2-25 to 2-30, Comparative Examples 2-37 to 2-45, and Reference Example 2-5 (R404A) is estimated based on the values of the fourth IPCC report.

[0348]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using NIST and Refprop 10.0, with the following conditions.

Evaporation temperature: 10°C

Condensing temperature: 40°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0349]

The definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0350]

Table 10 shows the results of Test Example 2-5. Table 10 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 10, the definitions of the terms are the same as the definitions of the terms in Test Example 2-1.

[0351]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0352]

The flammability of the mixed refrigerant was evaluated as in Test Example 2-1. Burn rate tests are carried out as in Test Example 2-1.

[0353]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0354]

Table 10

[0355]

Test Example 3

The GWP of each blended refrigerant shown in Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-5, and Reference Examples 3-1 (R134a) and 3-2 (R404A) is estimated based on the fourth report values IPCC.

[0356]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at saturated temperature of 45°C, condensing pressure and evaporation pressure of each of the mixed refrigerants are determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and database of thermodynamic and transport properties of reference liquids (Refprop 10.0) under the following conditions.

Evaporation temperature: -10°C

Condensing temperature: 45°C

Superheat temperature: 20K

Subcooling temperature: 0K

Compressor efficiency: 70%

[0357]

"Evaporation temperature -10°C" means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration unit is -10°C. In addition, "condensing temperature 45°C" means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration unit is 45°C.

[0358]

Table 11 shows the results of test example 3. Table 11 shows examples and comparative examples regarding Refrigerant 3 of the present invention. In Table 11, "HC ratio" and "cooling capacity ratio" mean the ratio (%) compared to R134a. In Table 11, "saturated pressure (45°C)" refers to the saturation pressure at a saturation temperature of 45°C. In Table 11, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0359]

The coefficient of performance (CC) is calculated according to the following equation:

XK \u003d (cooling capacity or heat capacity) / amount of electricity consumed.

[0360]

The critical temperature is determined by calculations using the National Institute of Science and Technology (NIST) and a database of thermodynamic and transport properties of reference fluids (Refprop 10.0).

[0361]

The flammability of the mixed refrigerant is determined by setting the fractionation of the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate between 0 cm/s and 10 cm/s is classified as Class 2L (flammable), a refrigerant with a burning rate greater than 10 cm/s is classified as Class 2 (low flammability), and a refrigerant with no flame spread is classified as Class 1 ( nonflammable). In Table 11, the ASHRAE Flammability Classification shows results based on these criteria.

[0362]

Burn rate tests are carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is subjected to deaeration by repeating the cycle of freezing, pumping and thawing until no traces of air are noted on the vacuum gauge. The burning rate is measured by a closed method. The starting temperature is the ambient temperature. Ignition is carried out by creating an electrical spark between the electrodes in the center of the sample cell. The duration of the discharge is from 1.0 to 9.9 ms and the ignition energy is typically about 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that allow light to pass through was used as the sample cell, and a xenon lamp was used as the light source. The schlieren image of the flame was recorded using a high speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0363]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0364]

More specifically, a 12 L spherical glass flask is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is built up in the glass bulb during combustion, the gas is allowed to leave the bulb through the top cap. Ignition is carried out using an electric discharge from electrodes placed one third of the distance from the bottom.

[0365]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio refrigerant composition/air: 1% vol. in steps of ±0.2% vol.

Refrigerant composition blend: ±0.1% wt.

Ignition method: AC discharge, voltage 15KV, electric current 30mA, neon transducer

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Criteria for evaluation

When the flame propagates at an angle greater than 90° from the ignition point, it is judged that flame propagation is present (flammable).

When the flame spreads at an angle of 90° or less from the ignition point, it is judged that there is no flame propagation (non-flammable).

[0366]

Table 11

[0367]

Test Example 4

The GWP of each blended refrigerant shown in Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-5 is estimated based on the values of the fourth IPCC report.

[0368]

The coefficient of performance (COP), cooling capacity, discharge temperature and saturation pressure at -10°C saturation temperature of each of the mixed refrigerants is determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and the thermodynamic and transport database. properties of reference liquids (Refprop 10.0) under the following conditions.

Evaporation temperature: 5°C

Condensing temperature: 45°C

Superheat temperature: 5K

Subcooling temperature: 5K

Compressor efficiency: 70%

[0369]

"Evaporation temperature 5°C" means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration unit is 5°C. In addition, "condensing temperature 45°C" means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration unit is 45°C.

[0370]

Table 12 shows the results of test example 4. Table 12 shows examples and comparative examples regarding Refrigerant 4 of the present invention. In Table 12, "HC ratio" and "cooling capacity ratio" mean the ratio (%) compared to R1234yf. In Table 12, "saturated pressure (-10°C)" refers to the saturation pressure at a saturation temperature of -10°C, which is a typical evaporating temperature under refrigeration conditions. In Table 12, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0371]

The coefficient of performance (CC) is calculated according to the following equation:

XK \u003d (cooling capacity or heat capacity) / amount of electricity consumed.

[0372]

The critical temperature is determined by calculations using the National Institute of Science and Technology (NIST) and a database of thermodynamic and transport properties of reference fluids (Refprop 10.0).

[0373]

The flammability of the mixed refrigerant is determined by setting the fractionation of the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate between 0 and 10 cm/s is classified as Class 2L (flammable), a refrigerant with a burning rate greater than 10 cm/s is classified as Class 2 (low flammable), and a refrigerant with no flame propagation is classified as Class 1 (non-flammable). In Table 12, the ASHRAE Flammability Classification shows results based on these criteria.

[0374]

Burn rate tests are carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is subjected to deaeration by repeating the cycle of freezing, pumping and thawing until no traces of air are noted on the vacuum gauge. The burning rate is measured by a closed method. The starting temperature is the ambient temperature. Ignition is carried out by creating an electrical spark between the electrodes in the center of the sample cell. The duration of the discharge is from 1.0 to 9.9 ms and the ignition energy is typically about 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light was used as the sample cell, and a xenon lamp was used as the light source. The schlieren image of the flame was recorded using a high speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0375]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0376]

More specifically, a 12 L spherical glass flask is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is built up in the glass bulb during combustion, the gas is allowed to leave the bulb through the top cap. Ignition is carried out using an electric discharge from electrodes placed one third of the distance from the bottom.

[0377]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio refrigerant composition/air: 1% vol. in steps of ±0.2% vol.

Refrigerant composition blend: ±0.1% wt.

Ignition method: AC discharge, voltage 15KV, electric current 30mA, neon transducer

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Criteria for evaluation

When the flame propagates at an angle greater than 90° from the ignition point, it is judged that flame propagation is present (flammable).

When the flame spreads at an angle of 90° or less from the ignition point, it is judged that there is no flame propagation (non-flammable).

[0378]

Table 12

[0379]

Test Example 5

The GWP of each blended refrigerant shown in Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-3, and Reference Example 5-1 (R134a) is estimated based on the values of the fourth IPCC report.

[0380]

The coefficient of performance (COP), the cooling capacity, of each of the mixed refrigerants is determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and the database of thermodynamic and transport properties of reference fluids (Refprop 10.0) under the following conditions .

Evaporation temperature: -30°C

Condensing temperature: 30°C

Superheat temperature: 5K

Subcooling temperature: 5K

Compressor efficiency: 70%

[0381]

"Evaporation temperature -30°C" means that the evaporation temperature of the mixed refrigerant in the evaporator provided in the refrigeration unit is -30°C. In addition, "condensing temperature 30°C" means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration unit is 30°C.

[0382]

Table 13 shows the results of test example 5. Table 13 shows examples and comparative examples regarding Refrigerant 5 of the present invention. In Table 13, "HC ratio" and "cooling capacity ratio" mean the ratio (%) compared to R1234yf. In Table 13, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the theoretical calculation of the mixed refrigerant refrigeration cycle. In Table 13, "boiling point (°C)" means the temperature at which the liquid phase of the mixed refrigerant is at atmospheric pressure (101.33 kPa). In Table 13, "motor power input amount (%)" refers to the electrical energy used to run the electric vehicle and is expressed as a ratio compared to the power input amount when the refrigerant is HFO-1234yf. In Table 13, "heater power input amount (%)" refers to the electric power used to drive the heater and is expressed as a ratio compared to the power input amount when the refrigerant is HFO-1234yf. In Table 13, "walkable distance" refers to the distance that an electric vehicle equipped with a rechargeable battery having a constant electric capacity can travel when the heater is on, and is expressed as a ratio (%) compared to the distance that can be traveled (100%), when the vehicle is moving without the heater on (that is, the heater power input is 0).

[0383]

The coefficient of performance (CC) is calculated according to the following equation:

XK \u003d (cooling capacity or heat capacity) / amount of electricity consumed.

[0384]

The flammability of the mixed refrigerant is determined by setting the fractionation of the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. The burning rate is measured as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is subjected to deaeration by repeating the cycle of freezing, pumping and thawing until no traces of air are noted on the vacuum gauge. The burning rate is measured by a closed method. The starting temperature is the ambient temperature. Ignition is carried out by creating an electrical spark between the electrodes in the center of the sample cell. The duration of the discharge is from 1.0 to 9.9 ms and the ignition energy is typically about 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that allow light to pass through was used as the sample cell, and a xenon lamp was used as the light source. The schlieren image of the flame was recorded using a high speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0385]

Heating is carried out using an electric heater in the case of a refrigerant having a boiling point greater than -40°C, and using a heat pump in the case of a refrigerant having a boiling point of -40°C or less.

[0386]

The amount of power consumed when using the heater is calculated according to the following equation:

The amount of power consumed when using the heater = heat capacity / HC of the heater

The HC of the heater refers to the heat output.

[0387]

In terms of heat output, the heater efficiency is 1 in an electric heater, and the heater consumes an electrode equivalent to the motor power. That is, the power consumption of the heater is equal to E=E/(1+efficiency). In the case of a heat pump, heater efficiency is determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using the National Institute of Science and Technology (NIST) and the reference fluid thermodynamic and transport properties database (Refprop 10.0) under the following conditions.

Evaporation temperature: -30°C

Condensing temperature: 30°C

Superheat temperature: 5K

Subcooling temperature:5K

Compressor efficiency: 70%

[0388]

The distance traveled is calculated using the following equation:

Distance traveled = (battery capacity)/(motor power input+heater power input).

[0389]

Table 13 (EN - electric heater, HP - heat pump)

Position numbers

[0390]

1: Feed line

2: Sampling line

3: Thermometer

4: Vacuum gauge

5: Electrode

6: Stirring paddle (made of PTFE).

Claims (46)

1. A refrigeration method, including operating a refrigeration cycle in which the evaporation temperature is -75 to -5°C, using a refrigerant composition containing a refrigerant, moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), and where HFO-1132 (E) is present in an amount of from 35.0 to 65.0% wt., and HFO-1234yf is present in an amount of from 65.0 to 35.0% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 2. The method according to p. 1, in which HFO-1132 (E) is present in an amount of from 41.3 to 53.5% wt., and HFO-1234yf is present in an amount of from 58.7 to 46.5% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 3. The method according to claim 1 or 2, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf. 4. The composition of the refrigerant containing the refrigerant, moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), where the refrigerant contains HFO-1132 (E) and HFO-1234yf in such quantities that the sum of HFO-1132 (E) and HFO-1234yf is 99.5% of the mass. or more, and where HFO-1132 (E) is present in an amount of from 40.5 to 49.2% wt., and HFO-1234yf is present in an amount of from 59.5 to 50.8% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 5. Composition according to claim 4, in which the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 6. Composition according to claim 4 or 5, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A . 7. Composition according to claim 4 or 5, containing at least one substance selected from the group consisting of water, tracer, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors. 8. A composition according to claim 4 or 5, wherein the composition further comprises a refrigeration oil and is intended for use as a working fluid in a refrigeration apparatus. 9. The composition of claim. 7, in which the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG (PAG)), complex polyol ether (POE (POE)) and simple polyvinyl ether (PVE ( PVE)). 10. The composition of the refrigerant containing the refrigerant, moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), where the refrigerant contains HFO-1132 (E) and HFO-1234yf in such quantities that the sum of HFO-1132 (E) and HFO-1234yf is 99.5% of the mass. or more, and where HFO-1132 (E) is present in an amount of from 31.1 to 39.8% wt., and HFO-1234yf is present in an amount of from 68.9 to 60.2% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 11. The composition according to p. 10, in which HFO-1132 (E) is present in an amount of from 31.1 to 37.9% wt., and HFO-1234yf is present in an amount of from 68.9 to 62.1% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 12. Composition according to claim 10 or 11, in which the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 13. Composition according to claim 10 or 11, which is intended for use as an alternative refrigerant for R134a, R1234yf or CO ₂ . 14. The composition according to claim 10 or 11, containing at least one substance selected from the group consisting of water, a tracer, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors. 15. The composition according to claim 10 or 11, where the composition additionally contains a refrigeration oil and is intended for use as a working fluid in a refrigeration apparatus. 16. The composition of claim. 15, in which the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG (PAG)), complex polyol ether (POE (POE)) and simple polyvinyl ether (PVE ( PVE)). 17. The composition of the refrigerant containing the refrigerant, moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), where the refrigerant contains HFO-1132 (E) and HFO-1234yf in such quantities that the sum of HFO-1132 (E) and HFO-1234yf is 99.5% of the mass. or more, and where HFO-1132 (E) is present in an amount of from 21.0 to 28.4% wt., and HFO-1234yf is present in an amount of from 79.0 to 71.6% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 18. Composition according to claim 17, in which the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 19. Composition according to claim 17 or 18, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A , R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R532fze4 or R132f 20. The composition according to claim 17 or 18, containing at least one substance selected from the group consisting of water, a tracer, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors. 21. A composition according to claim 17 or 18, wherein the composition further comprises a refrigerant oil and is intended for use as a working fluid in a refrigeration apparatus. 22. The composition of claim. 21, in which the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG (PAG)), complex polyol ether (POE (POE)) and simple polyvinyl ether (PVE ( PVE)). 23. The composition of the refrigerant containing the refrigerant, moreover, the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), where the refrigerant contains HFO-1132 (E) and HFO-1234yf in such quantities that the sum of HFO-1132 (E) and HFO-1234yf is 99.7% of the mass. or more, and where HFO-1132 (E) is present in an amount of from 12.1 to 45.0% wt., and HFO-1234yf is present in an amount of from 87.9 to 55.0% of the mass. based on the total weight of HFO-1132 (E) and HFO-1234yf. 24. Composition according to claim 23, in which the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 25. Composition according to claim 23 or 24, which is intended for use as an alternative refrigerant for R12, R134a or R1234yf. 26. The composition according to claim 23 or 24, containing at least one substance selected from the group consisting of water, a tracer, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors. 27. A composition according to claim 23 or 24, wherein the composition further comprises a refrigerant oil and is intended for use as a working fluid in a refrigeration apparatus. 28. The composition of claim. 27, in which the refrigeration oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG (PAG)), complex polyol ether (POE (POE)) and simple polyvinyl ether (PVE ( PVE)). 29. The method of cooling, including the operation of the refrigeration cycle using the refrigerant composition according to any one of paragraphs. 4-28. 30. The method of operation of the refrigeration apparatus, configured to implement the refrigeration cycle using the refrigerant composition according to any one of paragraphs. 4-28. 31. Refrigerator containing the refrigerant composition according to any one of paragraphs. 4-28 as a working fluid. 32. Apparatus according to claim 31, which is an air conditioning system, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a freezer showcase, a freezer and refrigeration unit, a refrigeration unit for freezing and refrigerated warehouses, an air conditioning system for vehicles , turbo chiller or screw chiller.

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