WO2018052000A1 - Heat-cycle working medium composition and heat cycle system - Google Patents

Abstract

The present invention provides a heat-cycle working medium composition, the working medium composition having excellent refrigerant performance and being usable as a substitute for various existing refrigerants, and a heat cycle system using the composition. The heat-cycle working medium composition according to the present invention comprises a refrigerant containing 3,3,3-trifluoropropyne, and at least one compound selected from difluoromethane, pentafluoroethane, and 1,1,1,2-tetrafluoroethane, and satisfies (1) or (2) as follows: (1) the 3,3,3-trifluoropropyne content is 1 mass% or more with respect to the total mass of the compound and 3,3,3-trifluoropropyne; (2) the refrigerant is an azeotropic or azeotropic-like mixture.

Description

Working medium composition for heat cycle and heat cycle system

The present invention relates to a working medium composition for heat cycle and a heat cycle system.

中 While global warming has been discussed as a serious problem all over the world, the development of heat cycle systems such as air conditioners and refrigeration systems that have less burden on the environment has become increasingly important. Refrigerants are greatly involved in the performance of thermal cycle systems such as refrigeration equipment, in addition to their impact on global warming. Therefore, the selection of the refrigerant plays an important role in reducing the amount of carbon dioxide generated that contributes to global warming.

Recently, various refrigerants having a low global warming potential (GWP) have been proposed as compared with conventionally known chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC). As such a refrigerant, hydrofluoroolefin (HFO) is known, and for example, 2,3,3,3-tetrafluoropropene (HFO-1234yf) has been proposed (Patent Documents 1, 2, etc.). Patent Document 3 proposes fluorinated propyne (Patent Document 3 and the like). In addition, the use of hydrocarbons, carbon dioxide or the like as a refrigerant for reducing GWP has been proposed.

International Publication No. 2005/105947 International Publication No. 2006/0943303 JP 2011-38054 A

However, since various HFO refrigerants have limitations in refrigerant capacity and low combustibility, further improvements are required. In addition, natural refrigerants such as hydrocarbons have problems from the viewpoint of safety and the like because they have high refrigerant capacity but high combustibility.

The present invention has been made in view of the above, has an excellent refrigerant performance, and can be used as a substitute for various existing refrigerants, and a heat cycle working medium composition and a heat cycle using this composition The purpose is to provide a system.

As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by using a specific refrigerant, and has completed the present invention.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1
Containing a refrigerant containing at least one compound selected from difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane, and 3,3,3-trifluoropropyne;
(1) or (2) below
(1) The content of 3,3,3-trifluoropropyne is 1% by mass or more based on the total mass of the compound and 3,3,3-trifluoropropyne.
(2) the refrigerant is an azeotropic or azeotrope-like mixture;
A working medium composition for heat cycle that satisfies
Item 2
A refrigerant comprising difluoromethane and 3,3,3-trifluoropropyne, wherein the refrigerant has a 3,3,3-trifluoropropyne content of difluoromethane and 3,3,3-trifluoropropyne. Item 2. The working medium composition for heat cycle according to Item 1, wherein the content is 32 to 99% by mass with respect to the total mass.
Item 3
Item 3. The heat according to Item 2, wherein the refrigerant has a content of 3,3,3-trifluoropropyne of 33 to 95% by mass with respect to the total mass of difluoromethane and 3,3,3-trifluoropropyne. Cycle working medium composition.
Item 4
Item 4. The refrigerant according to Item 2 or 3, wherein the content of 3,3,3-trifluoropropyne is 57% by mass or more based on the total mass of difluoromethane and 3,3,3-trifluoropropyne. Working medium composition for heat cycle.
Item 5
Item 2. The refrigerant according to any one of Items 2 to 4, wherein the content of 3,3,3-trifluoropropyne is 79% by mass or more based on the total mass of difluoromethane and 3,3,3-trifluoropropyne. 2. The working medium composition for heat cycle according to item 1.
Item 6
Containing a refrigerant comprising difluoromethane and 3,3,3-trifluoropropyne;
Item 6. The working medium composition for heat cycle according to any one of Items 2 to 5, wherein the refrigerant is an azeotrope-like mixture.
Item 7
Item 7. The working medium composition for heat cycle according to any one of Items 1 to 6, wherein the refrigerant comprises only difluoromethane and 3,3,3-trifluoropropyne.
Item 8
Containing a refrigerant comprising pentafluoroethane and 3,3,3-trifluoropropyne;
Item 2. The working medium composition for heat cycle according to Item 1, wherein the refrigerant is an azeotropic or azeotrope-like mixture.
Item 9
Item 9. The refrigerant according to Item 8, wherein the content of 3,3,3-trifluoropropyne is 1 to 52% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. Working medium composition for heat cycle.
Item 10
Item 9. The refrigerant according to Item 8, wherein the content of 3,3,3-trifluoropropyne is 20 to 90% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. Working medium composition for heat cycle.
Item 11
Item 9. The refrigerant according to Item 8, wherein the content of 3,3,3-trifluoropropyne is 70 to 99% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. Working medium composition for heat cycle.
Item 12
Item 2. The working medium composition for heat cycle according to Item 1, comprising a refrigerant comprising pentafluoroethane, 3,3,3-trifluoropropyne and difluoromethane.
Item 13
The refrigerant is based on the total mass of pentafluoroethane, 3,3,3-trifluoropropyne and difluoromethane.
30 to 98% by mass of pentafluoroethane,
1 to 52% by weight of 3,3,3-trifluoropropyne, and
1 to 63% by mass of difluoromethane,
Item 13. The working medium composition for heat cycle according to Item 12.
Item 14
Containing a refrigerant comprising 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne;
In the refrigerant, the content of 3,3,3-trifluoropropyne is 5 to 99 mass% with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 1, wherein
Item 15
The refrigerant has a 3,3,3-trifluoropropyne content of 5 to 40% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. Item 15. The working medium composition for heat cycle according to Item 14, wherein
Item 16
The refrigerant has a content of 3,3,3-trifluoropropyne of 20 to 90% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. Item 15. The working medium composition for heat cycle according to Item 14, wherein
Item 17
The refrigerant has a 3,3,3-trifluoropropyne content of 70 to 99% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. Item 15. The working medium composition for heat cycle according to Item 14, wherein
Item 18
The refrigerant further includes difluoromethane,
For the total mass of 1,1,1,2-tetrafluoroethane, 3,3,3-trifluoropropyne and difluoromethane,
1,1,1,2-tetrafluoroethane is 50 to 98% by mass,
1 to 40% by weight of 3,3,3-trifluoropropyne, and
Item 15. The working medium composition for heat cycle according to Item 14, wherein difluoromethane is 1 to 43% by mass.
Item 19
Hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon as a third component other than pentafluoroethane, difluoromethane, 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne The item 1 to 18, comprising at least one selected from the group consisting of (HCFC), chlorofluorocarbon (CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), trifluoromethane iodide and carbon dioxide. A working medium composition for heat cycle.
Item 20
Item 20. A thermal cycle system comprising the thermal cycle working medium composition according to any one of Items 1 to 19.
Item 21
Item 20. Use of the composition according to any one of Items 1 to 19 as a substitute for a working medium for heat cycle including the refrigerant of any of R22, R410A, R404A, R134a, and R1234yf.

The working medium composition for heat cycle of the present invention has excellent refrigerant performance and can be used as a substitute for various existing refrigerants.

It is a graph which shows the vapor pressure curve of the mixed system of TFP and R125. It is the schematic of the experimental apparatus used by the combustion test 1 of an Example. It is the schematic of the experimental apparatus used in the combustion test 2 of an Example.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the expressions “containing” and “including” include the concepts of “containing”, “including”, “consisting essentially of”, and “consisting only of”.

Hereinafter, embodiments of the working medium composition for heat cycle according to the present invention will be described in detail. Hereinafter, the working medium composition for heat cycle is abbreviated as “working medium composition”.

The working fluid composition for heat cycle of the present invention comprises at least one compound selected from difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane, and 3,3,3-trifluoropropyne. Containing refrigerant,
(1) or (2) below
(1) The content of 3,3,3-trifluoropropyne is 1% by mass or more based on the total mass of the compound and 3,3,3-trifluoropropyne.
(2) the refrigerant is an azeotropic or azeotrope-like mixture;
Meet.

The “first embodiment” of the working medium composition of the present invention contains a refrigerant containing difluoromethane and 3,3,3-trifluoropropyne, and the content of 3,3,3-trifluoropropyne is It is 32-99 mass% with respect to the total mass of difluoromethane and 3,3,3-trifluoropropyne.

The “second embodiment” of the working medium composition of the present invention contains a refrigerant containing difluoromethane and 3,3,3-trifluoropropyne, and the refrigerant is an azeotrope-like mixture.

The “third embodiment” of the working medium composition of the present invention contains a refrigerant containing pentafluoroethane and 3,3,3-trifluoropropyne, and the refrigerant is an azeotropic or azeotrope-like mixture.

The “fourth embodiment” of the working medium composition of the present invention contains a refrigerant containing pentafluoroethane and 3,3,3-trifluoropropyne, and the refrigerant includes pentafluoroethane and 3,3,3. -Hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO) as a third component other than trifluoropropyne And at least one compound selected from the group consisting of trifluoromethane iodide and carbon dioxide.

The “fifth embodiment” of the working medium composition of the present invention contains a refrigerant containing 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne, and 3,3,3 -The content of trifluoropropyne is 5 to 99 mass% with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne.

In the following, difluoromethane is “HFC-32”, 3,3,3-trifluoropropyne is “TFP”, pentafluoroethane is “R125”, 1,1,1,2-tetrafluoroethane. May be written as “R134a”.

In this specification, the temperature glide 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 working medium composition in the components of the refrigerant system.

(First embodiment and second embodiment)
In the working medium composition of the first embodiment, the refrigerant has a content of 3,3,3-trifluoropropyne of 32 to 99 mass with respect to the total mass of difluoromethane and 3,3,3-trifluoropropyne. %, The combustibility tends to be equal to or less than that of TFP, the temperature glide can be further reduced, and a high COP (coefficient of performance) is likely to be obtained.

In the working medium composition of the second embodiment, the azeotrope-like mixture means that the composition fluctuation of the mixture is small even when the cycle of distilling and condensing the mixture is repeated. It means a composition that fits. Hereinafter, also in other embodiments, the definition of an azeotrope-like mixture is the same.

In the working medium composition of the second embodiment, the refrigerant is likely to be an azeotrope-like mixture, for example, when the TFP content is 0.01 to 40% by mass with respect to the total mass of HFC-32 and TFP. .

In the working medium composition of the second embodiment, the temperature glide can be 5K or less.

The working medium composition of the first embodiment and the working medium composition of the second embodiment are collectively referred to as “the working medium composition of the first and second embodiments”.

In the working medium compositions of the first and second embodiments, the refrigerant preferably has a TFP content of 33 to 95% by mass with respect to the total mass of HFC-32 and TFP. In this case, the combustibility tends to be lower, and the temperature glide can be smaller. In particular, this working medium composition can be less combustible than HFC-32 alone or TFP alone.

It is particularly effective to reduce the combustibility of the working medium composition that the upper limit of the TFP content is 95% by mass with respect to the total mass of HFC-32 and TFP.

The TFP content is preferably 57% by mass or more based on the total mass of HFC-32 and TFP. In this case, GWP tends to be low in addition to low combustibility and low temperature glide, and can be, for example, a GWP of 300 or less. In this case, the upper limit of the TFP content may be 99% by mass or 95% by mass with respect to the total mass of HFC-32 and TFP.

The content of TFP is preferably 79% by mass or more based on the total mass of HFC-32 and TFP. In this case, in addition to the low flammability and the low temperature glide, the GWP tends to be low, and for example, the GWP can be 150 or less. In this case, the upper limit of the TFP content may be 99% by mass or 95% by mass with respect to the total mass of HFC-32 and TFP.

In another aspect, in the working medium compositions of the first and second embodiments, in addition to low flammability and low temperature glide, both COP (coefficient of performance) and refrigeration capacity are, for example, R410A, which is an existing refrigerant. It tends to be higher than In this case, the content of TFP is particularly preferably 32 to 40% by mass with respect to the total mass of HFC-32 and TFP.

In yet another aspect, in the working medium compositions of the first and second embodiments, in addition to low flammability and low temperature glide, both COP (coefficient of performance) and refrigeration capacity are, for example, existing refrigerants. Compared to R404A, it tends to be higher, and the discharge temperature and discharge pressure can be equivalent to R404A. Therefore, the working medium composition is particularly suitable for freezing and refrigeration applications. In this case, the content of TFP is particularly preferably 85 to 99% by mass with respect to the total mass of HFC-32 and TFP.

In the working medium compositions of the first and second embodiments, the refrigerant can contain other components having a refrigerant function (hereinafter referred to as “third component”) as necessary in addition to HFC-32 and TFP. Appropriate selection of the third component can further reduce GWP, reduce combustibility, make it nonflammable, and improve performance. When using refrigerating machine oil, the compatibility between the refrigerating machine oil and the working medium composition Adjustment is easy. In addition, various objects can be achieved by selecting the third component.

The third component is a component having a refrigerant function and is not particularly limited as long as it is a component other than HFC-32 and TFP. An example of such a third component is a hydrocarbon having a fluorine group. Specific examples of the hydrocarbon having a fluorine group include hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO). ), And compounds such as iodinated trifluoromethane. In addition, the third component may be carbon dioxide.

Examples of HFC include hydrofluoroethanes represented by molecular formulas C ₂ H _x F _(6-x) (where x = 1 to 5) such as HFC-134a and HFC-125, and molecular formulas C ₃ such as HFC-245fa. Hydrofluoropropanes represented by H _y F _(8-y) (where y = 1 to 7), molecular formulas such as HFC-365mfc C ₄ H _z F _(8-z) (where z = 1 to 9) The hydrofluorobutane etc. which are represented by these are illustrated.

Examples of HFO include haloolefins having 2 or more carbon atoms having a fluorine group, preferably haloolefins having 3 or more carbon atoms having a fluorine group. In any of these compounds, the type of isomer is not particularly limited. Specific examples of HFO include fluoroethylene (HFO-1141), trans-1,2-difluoroethylene (HFO-1132E), cis-1,2-difluoroethylene (HFO-1132Z), 1,1-difluoroethylene ( HFO-1132a), trifluoroethylene (HFO-1123), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1, 2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye) 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3, , 3-trifluoropropene (-HFO 1243zf), 1,1,1,4,4,4- hexafluoro-2-butene (HFO-1336mzz) and the like.

The third component can contain one or more compounds.

In the working medium compositions of the first and second embodiments, when the refrigerant contains a third component in addition to HFC-32 and TFP, each content of the third component is as long as the effect of the present invention is not hindered. There is no particular limitation.

In the working medium compositions of the first and second embodiments, it is also preferable that the refrigerant consists of only HFC-32 and TFP. In other words, in the working medium composition of the present embodiment, the total amount of HFC-32 and TFP is also preferably 100% by mass with respect to the total mass of the refrigerant. It is also preferred that the refrigerant consists essentially of HFC-32 and TFP. Furthermore, in the working medium compositions of the first and second embodiments, when the refrigerant contains a third component in addition to HFC-32 and TFP, each of the third components is contained unless the effect of the present invention is inhibited. Although the amount is not particularly limited, the content of the third component in the refrigerant is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. In this case, the working medium composition tends to have a higher COP (coefficient of performance) than, for example, HFC-32 alone, in addition to low combustibility and low temperature glide, and is suitable as an alternative to R410A and the like.

The working medium composition of the first and second embodiments can have a combustion rate of, for example, 3.9 cm / sec or less. When the combustion speed is within this range, excellent low combustibility is ensured. The burning rate is preferably 3.6 cm / sec or less, more preferably 2.0 cm / sec or less, and particularly preferably 1.0 cm / sec or less.

The burning rate referred to here is a value measured by an apparatus and method according to ASHRAE Standard 34-2013 and ASHRAE Standard 34-2013 Appendix B2.

In the working medium compositions of the first and second embodiments, the refrigerant contains HFC-32 and TFP as essential components. As a result, the working medium composition has an excellent refrigerant capacity, low combustibility, low GWP, and low temperature glide. Therefore, according to the working medium composition of the present embodiment, the environmental load can be further reduced, and it can be applied as an alternative to the existing refrigerant. For example, the working medium composition of the present embodiment can be used as an alternative to the existing refrigerants R410A, R404A, R22, and the like.

The method for preparing the working medium composition of the first and second embodiments is not particularly limited. For example, the working medium composition can be prepared by mixing HFC-32 and TFP at a predetermined ratio. Moreover, you may add a predetermined amount of 3rd components and additives as needed.

The production method of HFC-32 and TFP is not particularly limited, and for example, HFC-32 and TFP can be produced by a known production method, and these can be applied to the working medium composition.

(Third and fourth embodiments)
As shown in the vapor pressure curve of FIG. 1, in the working medium composition of the third embodiment, TFP and R125 (pentafluoroethane) can form an azeotrope-like composition at an arbitrary composition ratio. Therefore, the working medium composition of the third embodiment has a small temperature glide at an arbitrary composition ratio and lower combustibility than TFP alone.

In the working medium composition of the third embodiment, the temperature glide can be 5K or less.

In the working medium composition of the third embodiment, the refrigerant preferably has a TFP content of 1 to 52 mass% with respect to the total mass of R125 and TFP. In this case, combustibility tends to be lower, and in particular, an incombustible composition tends to be obtained. Moreover, when content of TFP is the said range, a temperature glide can also become smaller. In particular, this working medium composition can be less combustible than R125 alone or TFP alone.

It is particularly effective for the upper limit of the TFP content to be 52% by mass with respect to the total mass of R125 and TFP in order to reduce the combustibility of the working medium composition.

In another aspect of the working medium composition of the third embodiment, the refrigerant preferably has a TFP content of 20 to 90% by mass with respect to the total mass of R125 and TFP. In this case, the working medium composition of the third embodiment can be used as an alternative refrigerant such as R410A, R404A, R22, and R407 because the GWP becomes small in addition to low combustibility and low temperature glide.

In the working medium composition of the third embodiment, the refrigerant has a GWP value of 1500 or less when the content of TFP is 58% by mass or more with respect to the total mass of R125 and TFP, compared to R125 alone. It can be a refrigerant with low environmental impact.

In the working medium composition of the third embodiment, the refrigerant preferably has a TFP content of 70 to 99% by mass with respect to the total mass of R125 and TFP. In this case, the working medium composition of the third embodiment has a particularly low GWP in addition to low flammability and low temperature glide, and therefore can be used as an alternative refrigerant such as R134a and R1234yf. Furthermore, in this case, both the refrigerating capacity and the heating capacity are likely to be significantly higher than, for example, the existing refrigerants R134a and R1234yf, and the discharge temperature can be equal to R134a and R1234yf. Therefore, the working medium composition having a TFP content of 70 to 99% by mass with respect to the total mass of R125 and TFP is particularly suitable for car air-conditioner applications, and particularly has a high heating capacity. It is suitable for car air-conditioner applications where it has been difficult to use the heat of an internal combustion engine for heating, such as a plug-in hybrid vehicle. It is particularly preferable that the content of TFP is 90 to 99% by mass with respect to the total mass of R125 and TFP.

In the working medium composition of the third embodiment, the refrigerant can be a GWP of 750 or less when the TFP content is 79% by mass or more with respect to the total mass of R125 and TFP. In the working medium composition of the third embodiment, the refrigerant can be a GWP of 300 or less when the TFP content is 92% by mass or more with respect to the total mass of R125 and TFP. When the content of TFP is 96% by mass or more with respect to the total mass of R125 and TFP, the working medium composition of the third embodiment can have a GWP of 150 or less.

In another aspect, in the working medium composition of the third embodiment, in addition to low flammability and low temperature glide, one or both of COP (coefficient of performance) and refrigeration capacity is, for example, R410A which is an existing refrigerant. It tends to be higher than In this case, the content of TFP can be 50 to 80% by mass with respect to the total mass of R125 and TFP.

In another aspect, in the working medium composition of the third embodiment, in addition to low flammability and low temperature glide, one or both of COP (coefficient of performance) and refrigeration capacity are, for example, existing refrigerants. Compared to R404A, it tends to be higher, and the discharge temperature and discharge pressure can be equivalent to R404A. Therefore, the working medium composition is particularly suitable for freezing and refrigeration applications. In this case, the content of TFP can be 50 to 70% by mass with respect to the total mass of R125 and TFP.

The working medium composition of the third embodiment can contain, in addition to R125 and TFP, a third component as another component having a refrigerant function, if necessary. Appropriate selection of the third component can further reduce GWP, reduce combustibility, make it nonflammable, and improve performance. When using refrigerating machine oil, the compatibility between the refrigerating machine oil and the working medium composition Adjustment is easy. In addition, various objects can be achieved by selecting the third component.

The kind of the third component contained in the working medium composition of the third embodiment can be the same kind as the third component contained in the working medium composition of the first and second embodiments.

For example, in the working medium composition of the third embodiment, the refrigerant may be hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (third component other than R125 and TFP). CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), iodinated trifluoromethane, and at least one compound selected from the group consisting of carbon dioxide can be included. In the working medium composition of the third embodiment, when the refrigerant contains the third component, the working medium composition of the third embodiment is the same as that of the fourth embodiment.

In the working medium composition of the fourth embodiment, the content of 3,3,3-trifluoropropyne is 5 to 99% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. It can be. That is, in the working medium composition of the fourth embodiment, pentafluoroethane and 3,3,3-trifluoropropyne are not limited to azeotropic or azeotrope-like mixtures but can be non-azeotropic mixtures.

In the working medium composition according to the fourth embodiment, the third component may include one or more compounds.

In the working medium composition of the fourth embodiment, each content of the third component is not particularly limited.

In the working medium composition of the fourth embodiment, the third component is preferably difluoromethane (HFC-32). In this case, in the working medium composition of the third embodiment, in addition to low combustibility and low temperature glide, one or both of COP (coefficient of performance) and refrigeration capacity are compared with, for example, R410A which is an existing refrigerant. The discharge temperature and discharge pressure can be equivalent to R410A. Therefore, the working medium composition of the third embodiment containing HFC-32 as the third component has a lower GWP than R410A and is suitable for use as an alternative to R410A.

In the working medium composition of the fourth embodiment containing HFC-32, the refrigerant is 30 to 98% by mass of R125, 1 to 60% by mass of TFP, and 1 to 60% by mass of the total mass of R125, TFP and HFC-32. HFC-32 can be 1 to 69% by mass, and from the viewpoint of easily becoming an incombustible composition, R125 is 30 to 98% by mass, TFP is 1 to 52% by mass, and HFC-32 is 1 to 63% by mass. R125 is 37 to 98% by mass, TFP is 1 to 40% by mass, and HFC-32 is more preferably 1 to 50% by mass, R125 is 40 to 98% by mass, TFP Is 1 to 40% by mass, and HFC-32 is particularly preferably 1 to 50% by mass.

From the viewpoint that GWP tends to be 1600 or less, R125 is 37 to 70% by mass, TFP is 1 to 30% by mass, and HFC-32 is 1 to 33% with respect to the total mass of R125, TFP and HFC-32. It is preferable that it is mass%.

The working medium composition of the fourth embodiment containing HFC-32 is low in flammability, has a low GWP, and has a low temperature glide, with respect to the total mass of R125, TFP and HFC-32. R125 is preferably 30 to 98% by mass, TFP is 1 to 51% by mass, and HFC-32 is preferably 1 to 63% by mass, R125 is 48 to 98% by mass, TFP is 1 to 51% by mass, and More preferably, HFC-32 is 1 to 51% by mass.

The working medium compositions of the third embodiment and the fourth embodiment can have a combustion rate of, for example, 3.9 cm / sec or less. When the combustion speed is within this range, excellent low combustibility is ensured. The burning rate is preferably 3.6 cm / sec or less, more preferably 2.0 cm / sec or less, and particularly preferably 1.0 cm / sec or less.

In the working medium composition of the third embodiment and the fourth embodiment, the refrigerant includes R125 and TFP as essential components. As a result, the working medium composition has an excellent refrigerant capacity, low combustibility, low GWP, and low temperature glide. Therefore, according to the working-medium composition of 3rd Embodiment, while being able to reduce an environmental load more, it can apply as a substitute of the existing refrigerant | coolant. For example, the working medium composition of the present embodiment can be used as an alternative to the existing refrigerants R410A, R404A, R22, R134a, R1234yf, and the like.

The method for preparing the working medium composition of the third embodiment and the fourth embodiment is not particularly limited. For example, a working medium composition can be prepared by mixing R125 and TFP at a predetermined ratio. Moreover, you may add a predetermined amount of 3rd components and additives as needed.

The production method of R125 and TFP is not particularly limited, and for example, R125 and TFP can be produced by a known production method.

(Fifth embodiment)
In the working medium composition of the fifth embodiment, the refrigerant has a TFP content of 5 to 99% by mass with respect to the total mass of R134a and TFP. Further, the temperature glide can be made smaller, and a high COP (coefficient of performance) tends to be obtained.

In the working medium composition of the fifth embodiment, the refrigerant preferably has a TFP content of 5 to 40% by mass with respect to the total mass of R134a and TFP. In this case, combustibility tends to be lower, and in particular, an incombustible composition tends to be obtained. Moreover, when content of TFP is the said range, a temperature glide can also become smaller. In particular, this working medium composition can be less combustible than R134a alone or TFP alone.

In another aspect of the working medium composition of the fifth embodiment, the refrigerant preferably has a TFP content of 20 to 90% by mass with respect to the total mass of R134a and TFP. In this case, the working medium composition of the fifth embodiment can be used as an alternative refrigerant such as R410A, R404A, R22, and R407 because the GWP becomes small in addition to low combustibility and low temperature glide.

In the working medium composition of the fifth embodiment, the refrigerant has a GWP value of 1000 or less when the TFP content is 70% by mass or more with respect to the total mass of R134a and TFP, compared to R134a alone. It can be a refrigerant with low environmental impact.

In the working medium composition of the fifth embodiment, the refrigerant preferably has a TFP content of 70 to 99% by mass with respect to the total mass of R134a and TFP. In this case, the working medium composition of the fifth embodiment has a particularly low GWP in addition to low combustibility and low temperature glide, and therefore can be used as an alternative refrigerant such as R134a and R1234yf. Furthermore, in this case, one or both of the COP and the refrigerating capacity tends to be higher than R134a or HFO-1234yf. Therefore, a working medium composition having a TFP content of 70 to 99% by mass with respect to the total mass of R134a and TFP is particularly suitable for car air-conditioner applications, and particularly has a high heating capacity. It is suitable for car air-conditioner applications where it has been difficult to use the heat of an internal combustion engine for heating, such as a plug-in hybrid vehicle. It is particularly preferable that the content of TFP is 90 to 99% by mass with respect to the total mass of R134a and TFP.

In the working medium composition of the fifth embodiment, the refrigerant can be a GWP of 750 or less when the TFP content is 52% by mass or more with respect to the total mass of R134a and TFP. When the content of TFP is 90% by mass or more with respect to the total mass of R134a and TFP, the working medium composition of the fifth embodiment can be a GWP of 152 or less.

In another aspect, in the working medium composition of the fifth embodiment, in addition to low flammability and low temperature glide, both COP (coefficient of performance) and refrigeration capacity are, for example, compared to R410A, which is an existing refrigerant. It tends to be expensive. In this case, the content of TFP can be 20 to 90% by mass with respect to the total mass of R134a and TFP.

In still another aspect, in the working medium composition of the fifth embodiment, in addition to low flammability and low temperature glide, both COP (coefficient of performance) and refrigeration capacity are, for example, the existing refrigerant R404A and In comparison, the discharge temperature and discharge pressure are likely to be equivalent to R404A. Therefore, the working medium composition is particularly suitable for freezing and refrigeration applications. In this case, the TFP content can be 40 to 70% by mass with respect to the total mass of R134a and TFP.

In the working medium composition of the fifth embodiment, the refrigerant can include, in addition to R134a and TFP, a third component as another component having a refrigerant function, if necessary. Appropriate selection of the third component can further reduce GWP, reduce combustibility, make it nonflammable, and improve performance. When using refrigerating machine oil, the compatibility between the refrigerating machine oil and the working medium composition Adjustment is easy. In addition, various objects can be achieved by selecting the third component.

The kind of the third component contained in the working medium composition of the fifth embodiment can be the same kind as the third component contained in the working medium composition of the first and second embodiments.

That is, in the working medium composition of the fifth embodiment, the refrigerant is a hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (as a third component other than R134a and TFP). CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), iodinated trifluoromethane, and at least one compound selected from the group consisting of carbon dioxide can be included.

The third component can contain one or more compounds.

In the working medium composition of the fifth embodiment, when the refrigerant includes the third component in addition to R134a and TFP, the content of the third component is not particularly limited as long as the effect of the present invention is not inhibited.

In the working medium composition of the fifth embodiment, the third component is preferably difluoromethane (HFC-32). In this case, in the working medium composition of the fifth embodiment, in addition to low combustibility and low temperature glide, both COP (coefficient of performance) and refrigeration capacity are higher than, for example, the existing refrigerant R410A. In addition, the discharge temperature and the discharge pressure can be equivalent to R410A. Therefore, the working medium composition of the fifth embodiment containing HFC-32 as the third component has a lower GWP than R410A and is suitable for use as an alternative to R410A.

The working medium composition of the fifth embodiment containing HFC-32 has an R134a of 30 to 98% by mass, a TFP of 1 to 60% by mass, and an HFC- of the total mass of R134a, TFP and HFC-32. 32 may be 1 to 69 mass%.

The working medium composition of the fifth embodiment containing HFC-32 is low in flammability, has a low GWP, and has a low temperature glide, with respect to the total mass of R134a, TFP and HFC-32. Preferably, R134a is 50 to 98% by mass, TFP is 1 to 40% by mass, and HFC-32 is 1 to 43% by mass, R134a is 55 to 98% by mass, TFP is 1 to 30% by mass, and When HFC-32 is 1 to 25% by mass, the nonflammable composition is likely to be obtained.

The working medium composition of the fifth embodiment can have a combustion rate of, for example, 3.9 cm / sec or less. When the combustion speed is within this range, excellent low combustibility is ensured. The burning rate is preferably 3.6 cm / sec or less, more preferably 2.0 cm / sec or less, and particularly preferably 1.0 cm / sec or less.

The working medium composition of the fifth embodiment includes R134a and TFP as essential components. As a result, the working medium composition has an excellent refrigerant capacity, low combustibility, low GWP, and low temperature glide. Therefore, according to the working-medium composition of 5th Embodiment, while being able to reduce an environmental load more, it can apply as a substitute of the existing refrigerant | coolant. For example, the working medium composition of the present embodiment can be used as an alternative to the existing refrigerants R410A, R404A, R22, R134a, R1234yf, and the like.

The method for preparing the working medium composition of the fifth embodiment is not particularly limited. For example, a working medium composition can be prepared by mixing R134a and TFP at a predetermined ratio. Moreover, you may add a predetermined amount of 3rd components and additives as needed.

The production method of R134a and TFP is not particularly limited, and for example, R134a and TFP can be produced by a known production method.

(First to fifth embodiments)
The working medium composition of the first to fifth embodiments (hereinafter referred to as “this embodiment”) can contain additives other than the refrigerant as necessary. Examples of additives other than the refrigerant include stabilizers, refrigerating machine oils, rust inhibitors, corrosion inhibitors, lubricants, polymerization inhibitors, solvents, and moisture. Examples of the stabilizer include aliphatic nitro compounds such as nitromethane and nitroethane, ethers such as 1,4-dioxane, amines such as 2,2,3,3,3-pentafluoropropylamine and diphenylamine, butylhydroxy Examples include xylene and benzotriazole. One stabilizer can be used, or two or more stabilizers can be used in combination. Examples of the refrigerating machine oil include, but are not limited to, polyalkylene glycol, polyol ester, polyvinyl ether, alkylbenzene mineral oil, and the like. Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole. .

Although the content of additives other than the refrigerant is not particularly limited, for example, in the case of a polymerization inhibitor, it can be 0.01 to 5.0% by mass with respect to the total mass of the refrigerant. Of course, the working medium composition may not contain additives other than the refrigerant.

The working medium composition of the present embodiment can be suitably used for various heat cycle systems. The thermal cycle system can be a thermal cycle system with a high cooling capacity by including the working medium composition of the present embodiment. In addition, since the working medium composition has low combustibility and low GWP, it can impart higher safety to the heat cycle system compared to the case where an existing refrigerant is used. Moreover, since the working medium composition also has a low temperature clad, it is possible to provide a highly stable thermal cycle system.

The type of heat cycle system is not particularly limited. Examples of heat cycle systems include room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, separate air conditioners with one or more indoor units and outdoor units connected by refrigerant piping, window type air conditioners, and portable types. Air-conditioner, rooftop type or central type air conditioner that transports cool and warm air through ducts, gas engine heat pump, air conditioner for trains, air conditioner for automobile, built-in showcase, separate showcase, commercial refrigerator-freezer, ice machine, Examples include body refrigerators, vending machines, car air conditioners, maritime transport containers, refrigerators for cooling refrigerators, chiller units, turbo refrigerators, or heating cycle dedicated machines. Examples of the heating cycle dedicated machine include a hot water supply device, a floor heating device, and a snow melting device.

As long as the thermal cycle system enumerated above includes the working medium composition of the present embodiment, the other configurations are not particularly limited, and for example, may be the same as a known configuration.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiments.

(Examples 1-1 to 1-6)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and working fluid compositions were prepared so as to have the composition ratios shown in Table 1 below.

Using the obtained working medium composition, COP, refrigerating capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The heat pump operating conditions are such that the refrigerant evaporation temperature in the evaporator is 15 ° C., the refrigerant condensation temperature in the condenser is 45 ° C., the compressor efficiency is 0.7, the degree of superheat and the degree of supercooling are 0 ° C. Drove. The results of each evaluation are shown in Table 1.
Evaporation temperature: 15 ° C
Inhalation temperature: 20 ° C
Compressor efficiency: 0.7
Condensation temperature: 45 ° C
Condenser outlet: 40 ° C

(Comparative Examples 1 to 3)
Working medium compositions were prepared as compositions of R410A alone (Comparative Example 1), HFC-32 alone (Comparative Example 2), and TFP alone (Comparative Example 3), and the same evaluations as in Examples 1-1 to 1-6 Went. The results are shown in Table 1.

From the results of Table 1, the working fluid composition for heat cycle containing difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) both had low GWP and excellent refrigeration. It can be seen that it has the capability and also has a low temperature clyde. Moreover, the working medium composition of each Example also had a high COP.

(Examples 1-7 to 1-9)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and a working medium composition was prepared so that they had the composition ratios shown in Table 2 below.

The obtained working medium composition was used, and COP, refrigeration capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The heat pump operating conditions are as follows: the refrigerant evaporating temperature in the evaporator is −10 ° C., the refrigerant condensing temperature in the condenser is 40 ° C., the compressor efficiency is 0.7, the superheat is 10 ° C., and the supercooling is 0 ° C. I drove like that. The results of each evaluation are shown in Table 2.

(Comparative Example 4)
A working medium composition was prepared as a composition of R404A alone (Comparative Example 4) and evaluated in the same manner as in Examples 1-7 to 1-9. The results are shown in Table 2.

From the results of Table 2, the working fluid composition for heat cycle containing difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) both had excellent GWP and low GWP. It can be seen that it has a refrigerating capacity and also has a low temperature clade. In addition, it can be seen that the working medium composition of each Example also has a COP of R404A or higher, and the discharge temperature and discharge pressure can be equal to those of R404A.

(Examples 1-10 to 1-12)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and working fluid compositions were prepared so as to have the composition ratios shown in Table 3 below.

The obtained working medium composition was used, and COP, refrigeration capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The heat pump operating conditions are as follows: the refrigerant evaporation temperature in the evaporator is −40 ° C., the refrigerant condensation temperature in the condenser is 40 ° C., the compressor efficiency is 0.7, the degree of superheat is 20 ° C., and the degree of supercooling is 0 ° C. I drove like that. The results of each evaluation are shown in Table 3.

(Comparative Example 5)
A working medium composition was prepared as a composition of R404A alone (Comparative Example 5) and evaluated in the same manner as in Examples 1-10 to 1-12. The results are shown in Table 3.

From the results in Table 3, the working fluid composition for heat cycle containing difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) both had excellent GWP and low GWP. It can be seen that it has a refrigerating capacity and also has a low temperature clade. In addition, it can be seen that the working medium composition of each Example also has a COP of R404A or higher, and the discharge temperature and discharge pressure can be equal to those of R404A.

(Examples 1-13 to 1-15)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and working fluid compositions were prepared so as to have the composition ratios shown in Table 4 below.

The obtained working medium composition was used, and COP, refrigeration capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The heat pump operating conditions are as follows: the refrigerant evaporation temperature in the evaporator is −65 ° C., the refrigerant condensation temperature in the condenser is 40 ° C., the compressor efficiency is 0.7, the degree of superheat is 20 ° C., and the degree of supercooling is 0 ° C. I drove like that. The results of each evaluation are shown in Table 4.

(Comparative Example 6)
A working medium composition was prepared as a composition of R404A alone (Comparative Example 6) and evaluated in the same manner as in Examples 1-13 to 1-15. The results are shown in Table 4.

From the results of Table 4, the working fluid composition for heat cycle containing difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) both had excellent GWP and low GWP. It can be seen that it has a refrigerating capacity and also has a low temperature clade. In addition, it can be seen that the working medium composition of each Example also has a COP of R404A or higher, and the discharge temperature and discharge pressure can be equal to those of R404A.

(Examples 1-16 to 1-21)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and working fluid compositions were prepared so as to have the composition ratios shown in Table 5 below.

<Combustion test 1>
About the obtained working-medium composition, the burning rate was measured by the sealing method. (In this specification, the test for measuring a burning rate was described as the burning test 1. In this measurement, experiment shown in FIG. 2 was carried out. In the measurement, the apparatus of FIG. It was used after confirming that it was able to measure 2.3 cm / sec.Using this apparatus, gas mixed with dry air was put in a closed cell (test cell) and ignited by electric spark at a temperature of 23 ° C. The spreading speed was taken and measured with a high speed camera (however, the acid It was set to 1.03 times the combustion stoichiometry concentrations of.

Table 5 shows the results of evaluating the GWP and the combustion rate (cm / sec) (BV value) for each gas composition ratio.

(Comparative Examples 7 to 10)
Difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) were prepared, and the working medium compositions were prepared so that the composition ratios shown in Table 5 below (Comparative Examples 7 to 9) were obtained. Alternatively, a working medium composition was prepared as a composition of TFP alone (Comparative Example 10) and evaluated in the same manner as in Examples 1-16 to 1-21. The results are shown in Table 5.

From the results shown in Table 5, the working fluid composition for heat cycle containing difluoromethane (HFC-32) and 3,3,3-trifluoropropyne (TFP) all have a low BV value and low combustibility. You can see that

(Examples 3-1 to 3-8)
Pentafluoroethane (R125) and 3,3,3-trifluoropropyne (TFP) were prepared, and working fluid compositions were prepared so as to have composition ratios shown in Tables 6 to 11 below.

Using the obtained working medium composition, COP, refrigeration capacity or heating capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. Measurement of refrigeration capacity or heating capacity includes the first cooling test (also referred to as MAC cooling test), the second cooling test (also referred to as cooling test such as R410A), the heating test (also referred to as MAC heating test), the refrigeration test, the freezing test, The test was performed in 6 patterns of the cryogenic test, and each was performed under the following heat pump operating conditions.

<First cooling test>
Evaporation temperature (intermediate): 5 ° C
Inhalation temperature: 10 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 45 ° C
Supercooling degree: 0 ℃
<Second cooling test>
Evaporation temperature (intermediate): 15 ° C
Inhalation temperature: 20 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 45 ° C
Condenser outlet: 40 ° C
<Heating test>
Evaporation temperature (intermediate): 0 ° C
Inhalation temperature: 5 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 35 ° C
Supercooling degree: 0 ℃
<Refrigeration test>
Evaporation temperature (intermediate): -10 ° C
Inhalation temperature: 0 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 40 ° C
Supercooling degree: 0 ℃
<Frozen test>
Evaporation temperature (intermediate): -40 ° C
Inhalation temperature: -25 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 40 ° C
Supercooling degree: 0 ℃
<Cryogenic test>
Evaporation temperature (intermediate): -65 ° C
Inhalation temperature: -45 ° C
Compressor efficiency: 0.7
Condensation temperature (intermediate): 40 ° C
Supercooling degree: 0 ℃

(Comparative Example 11)
A working medium composition was prepared as a composition of R125 alone and evaluated in the same manner as in Examples 3-1 to 3-8.

(Comparative Example 12)
A working medium composition was prepared as a composition of R134a alone and evaluated in the same manner as in Examples 3-1 to 3-8.

(Comparative Example 13)
A working medium composition was prepared as a composition of R1234yf alone and evaluated in the same manner as in Examples 3-1 to 3-8.

(Comparative Example 14)
A working medium composition was prepared as a composition of R404A alone and evaluated in the same manner as in Examples 3-1 to 3-8.

Tables 6 to 11 show the results of the first cooling test, the second cooling test, the heating test, the refrigeration test, the freezing test, and the cryogenic test, respectively. Tables 6 to 11 also show the evaluation results of the temperature glide. As comparative objects, Tables 6 to 11 show the results of the same evaluations as in Examples 3-1 to 3-8 for the compositions of Comparative Examples 1 and 3.

In the example of Table 6, GWP is remarkably low and COP is equal to or higher than R410A used in the past, and the temperature glide is sufficiently small. Further, it is also clear that the composition of Example 3-2 is nonflammable in the combustion range test described later. Thus, a thermal cycle working medium composition containing R125 and TFP can be an alternative working medium useful in applications where R410A is used.

In the example of Table 7, GWP is remarkably low and COP is equal to or higher than R134a used conventionally, and the refrigerating capacity is extremely large. In addition, compared with R1234yf, whose use will expand in the future, the refrigerating capacity is remarkably large while the COP is comparable. Thus, a working fluid composition for thermal cycling containing R125 and TFP can be an alternative working fluid useful in applications where R134a or R1234yf is used.

In the examples of Table 8, GWP is remarkably low and COP is equal to or higher than R134a that is conventionally used, and the heating capacity is extremely large. In addition, compared with R1234yf, which will be used in the future, the heating capacity is significantly large while the COP is comparable. Therefore, the working medium composition for heat cycle containing R125 and TFP is used for car air conditioners and the like that are difficult to use the heating function of the internal combustion engine, such as hybrid cars and plug-in hybrid cars that are increasingly used in the future. , R134a and R1234yf can be useful alternative working media in applications.

In the examples in Tables 9 to 11, the GWP is remarkably low, the COP is equal to or higher than the conventionally used R404A, the refrigerating capacity is also equal, and the temperature glide is sufficiently small. Further, it is clear that the composition of Example 3-1 is nonflammable in the combustion range test described later. Thus, a thermal cycle working medium composition containing R125 and TFP can be an alternative working medium useful in refrigeration applications where R404A is used. Further, from the results of Tables 9 to 11, the working fluid composition for heat cycle containing R125 and TFP is a refrigeration in which R22 (GWP = 1810, ozone depleting substance) still used in some regions is used. Since it was almost the same as refrigeration, it can be an alternative.

(Examples 4-1 to 4-6)
1,1,1,2-tetrafluoroethane (R134a) and 3,3,3-trifluoropropyne (TFP) were prepared, and the working medium composition was such that the composition ratios shown in Tables 12 to 14 below were obtained. Was prepared.

Using the obtained working medium composition, COP, refrigeration capacity or heating capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The refrigerating capacity or heating capacity was measured under the same conditions as the heat pump operating conditions of the first cooling test, the second cooling test, and the heating test.

(Comparative Example 15)
A working medium composition was prepared as a composition of R134a alone and evaluated in the same manner as in Examples 4-1 to 4-6.

(Comparative Example 16)
A working medium composition was prepared as a composition of R410A alone and evaluated in the same manner as in Examples 4-1 to 4-6.

Tables 12 to 14 show the results of the first cooling test, the second cooling test, and the heating test, respectively. Tables 12 to 14 also show the evaluation results of the temperature glide. As comparative objects, Tables 6 to 11 show the results of the same evaluations as in Examples 4-1 to 4-6 for the compositions of Comparative Example 3, Comparative Example 12, and Comparative Example 13.

It can be seen that the working medium composition for heat cycle containing R134a and TFP has a low GWP, an excellent refrigeration capacity, and a low temperature glide. In addition, the working medium compositions of Examples 4-1 to 4-6 also had a high COP.

In the example of Table 12, GWP is remarkably low and COP is equal to or higher than R410A used conventionally, and the temperature glide is sufficiently small. Further, it is clear that the compositions of Examples 4-1 and 4-2 are nonflammable in the combustion range test described later. Thus, a thermal cycle working medium composition containing R134a and TFP can be an alternative working medium useful in applications where R410A is used.

In the examples of Table 13, GWP is remarkably low and COP is equal to or higher than R134a that is conventionally used, and the refrigerating capacity is remarkably large. Moreover, in the Example of Table 13, COP is comparable and refrigerating capacity is remarkably large also with respect to R1234yf whose use will expand in the future. Therefore, the working medium composition for heat cycle containing R134a and TFP can be a useful working medium in applications where R134a alone or R1234yf is used.

In the example of Table 14, GWP is remarkably low and COP is equivalent as compared with R134a used in the past, and heating capability is remarkably large, and COP is comparable to R1234yf whose use will be expanded in the future. The heating capacity is remarkably large. Therefore, the working medium composition for heat cycle containing R134a and TFP is used for car air conditioners and the like that are difficult to use the heating function of an internal combustion engine such as hybrid cars and plug-in hybrid cars that are increasingly used in the future. It can be an alternative working medium useful in applications where R134a alone or R1234yf is used.

(Examples 5-1 and 5-2)
Pentafluoroethane (R125), 3,3,3-trifluoropropyne (TFP) 1,1,1,2-tetrafluoroethane (R134a) and difluoromethane (HFC-32) were prepared. The working medium composition was prepared so as to have the composition ratio shown in FIG.

Using the obtained working medium composition, COP, refrigeration capacity or heating capacity (kJ / m ³ ), and temperature glide (K) were evaluated using a heat pump. The refrigerating capacity or the heating capacity was measured under the same conditions as the heat pump operating conditions of the first cooling test.

In the examples of Table 15, GWP is remarkably low and COP is equal to or higher than R410A used in the past, and temperature glide is sufficiently small. Thus, a working fluid composition for thermal cycling containing R32, R125, and TFP, and a working fluid composition for thermal cycling containing R32, R134a, and TFP are alternative working media useful in applications where R410A is used. It can be.

<Combustion test 2>
The flammability of the obtained working medium composition was evaluated according to the US ASHRAE 34-2013 standard. The combustion range was measured using a measuring device based on ASTM E681-09.

FIG. 3 shows an apparatus for performing the combustion test 2. In FIG. 3, reference numeral 1 is an ignition source, 2 is a sample inlet, 3 is a spring, 4 is a 12-liter spherical glass flask, 5 is an electrode, 6 is a stirring means, and 7 is a heat insulating chamber.

A spherical glass flask with an internal volume of 12 liters was used so that the state of combustion could be visually observed and recorded. When excessive pressure was generated by combustion, gas was released from the upper lid. The ignition method was generated by discharge from an electrode held at a height of 1/3 from the bottom.

<Test conditions>
・ Test container: 280mmφ spherical shape (internal volume: 12 liters)
・ Test temperature: 60 ℃ ± 3 ℃
・ Pressure: 101.3 kPa ± 0.7 kPa
・ Moisture: 0.0088g ± 0.0005g / g dry air
Composition / air mixing ratio: 1 vol.% Increments ± 0.2 vol.%
-Composition mixing: ± 0.1% by weight
・ Ignition method: AC discharge, voltage 15 kV, current 30 mA, neon transformer ・ Electrode spacing: 6.4 mm (1/4 inch)
-Spark: 0.4 seconds ± 0.05 seconds As a criterion, it was determined that the flame spread (propagated) when the flame spread 90 degrees or more around the ignition point.

Table 16 shows the results of the combustion test 2. In this combustion test 2, as a comparison, the compositions of Reference Examples 1 to 4 were also tested.

Claims (21)

1. Containing a refrigerant containing at least one compound selected from difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane, and 3,3,3-trifluoropropyne;
   (1) or (2) below
   (1) The content of 3,3,3-trifluoropropyne is 1% by mass or more based on the total mass of the compound and 3,3,3-trifluoropropyne.
   (2) the refrigerant is an azeotropic or azeotrope-like mixture;
   A working medium composition for heat cycle that satisfies
2. A refrigerant comprising difluoromethane and 3,3,3-trifluoropropyne, wherein the refrigerant has a 3,3,3-trifluoropropyne content of difluoromethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 1, wherein the content is 32 to 99% by mass relative to the total mass.
3. 3. The refrigerant according to claim 2, wherein the content of 3,3,3-trifluoropropyne is 33 to 95% by mass with respect to the total mass of difluoromethane and 3,3,3-trifluoropropyne. Working medium composition for heat cycle.
4. The content of 3,3,3-trifluoropropyne in the refrigerant is 57% by mass or more based on the total mass of difluoromethane and 3,3,3-trifluoropropyne. A working medium composition for heat cycle.
5. 5. The refrigerant according to claim 2, wherein the content of 3,3,3-trifluoropropyne is 79% by mass or more based on the total mass of difluoromethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycles according to claim 1.
6. Containing a refrigerant comprising difluoromethane and 3,3,3-trifluoropropyne;
   The working medium composition for heat cycle according to any one of claims 2 to 5, wherein the refrigerant is an azeotrope-like mixture.
7. The working medium composition for heat cycle according to any one of claims 1 to 6, wherein the refrigerant comprises only difluoromethane and 3,3,3-trifluoropropyne.
8. Containing a refrigerant comprising pentafluoroethane and 3,3,3-trifluoropropyne;
   The working medium composition for heat cycle according to claim 1, wherein the refrigerant is an azeotropic or azeotrope-like mixture.
9. 9. The refrigerant according to claim 8, wherein the content of 3,3,3-trifluoropropyne is 1 to 52 mass% with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. A working medium composition for heat cycle.
10. 9. The refrigerant according to claim 8, wherein the content of 3,3,3-trifluoropropyne is 20 to 90% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. A working medium composition for heat cycle.
11. 9. The refrigerant according to claim 8, wherein the content of 3,3,3-trifluoropropyne is 70 to 99% by mass with respect to the total mass of pentafluoroethane and 3,3,3-trifluoropropyne. A working medium composition for heat cycle.
12. The working medium composition for heat cycle according to claim 1, comprising a refrigerant containing pentafluoroethane, 3,3,3-trifluoropropyne and difluoromethane.
13. The refrigerant is based on the total mass of pentafluoroethane, 3,3,3-trifluoropropyne and difluoromethane.
    30 to 98% by mass of pentafluoroethane,
    1 to 52% by weight of 3,3,3-trifluoropropyne, and
    1 to 63% by mass of difluoromethane,
    The working medium composition for heat cycles according to claim 12.
14. Containing a refrigerant comprising 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne;
    In the refrigerant, the content of 3,3,3-trifluoropropyne is 5 to 99 mass% with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 1, wherein
15. The refrigerant has a 3,3,3-trifluoropropyne content of 5 to 40% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 14, wherein
16. The refrigerant has a content of 3,3,3-trifluoropropyne of 20 to 90% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 14, wherein
17. The refrigerant has a 3,3,3-trifluoropropyne content of 70 to 99% by mass with respect to the total mass of 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne. The working medium composition for heat cycle according to claim 14, wherein
18. The refrigerant further includes difluoromethane,
    For the total mass of 1,1,1,2-tetrafluoroethane, 3,3,3-trifluoropropyne and difluoromethane,
    1,1,1,2-tetrafluoroethane is 50 to 98% by mass,
    1 to 40% by weight of 3,3,3-trifluoropropyne, and
    The working medium composition for heat cycle according to claim 14, wherein difluoromethane is 1 to 43% by mass.
19. Hydrofluoroolefin (HFO), hydrofluorocarbon (HFC), hydrochlorofluorocarbon as a third component other than pentafluoroethane, difluoromethane, 1,1,1,2-tetrafluoroethane and 3,3,3-trifluoropropyne (HCFC), chlorofluorocarbon (CFC), chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), at least one selected from the group consisting of trifluoromethane iodide and carbon dioxide, The working medium composition for heat cycle as described.
20. A heat cycle system comprising the working medium composition for heat cycle according to any one of claims 1 to 19.
21. Use of the composition according to any one of claims 1 to 19 as an alternative to a working medium for heat cycle comprising a refrigerant of any of R22, R410A, R404A, R134a and R1234yf.

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