JP2018104566A - Actuation media for refrigeration cycle and refrigeration cycle system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide actuation media for refrigeration cycle, capable of effectively suppressing or alleviating disproportionation reaction of 1,1,2-trifluoroethylene (HFO1123), and to provide a refrigeration cycle system using the same.SOLUTION: Actuation media for refrigeration cycle contain at least 1,1,2-trifluoroethylene as a refrigerant component, wherein a 2-5C saturated hydrocarbon and a 1-2C haloalkane (excluding, however, the case in which all of halogen atoms are F) are contained therein as a disproportionation inhibitor for inhibiting a disproportionation reaction of the 1,1,2-trifluoroethylene.SELECTED DRAWING: None

Description

  The present invention relates to a working medium for a refrigeration cycle capable of effectively suppressing or mitigating a disproportionation reaction of 1,1,2-trifluoroethylene, and a refrigeration cycle system using the same.

  As the working medium (refrigerant or heat medium) for the refrigeration cycle, HCFC (hydrochlorofluorocarbon) has been used before, but HCFC has a great influence on ozone layer destruction. In recent years, therefore, HFC (hydrofluorocarbon) having an ozone layer depletion coefficient (ODP) of 0 has been used. A typical HFC is R410A (refrigerant number based on Standard 34 standard of American Association of Heating, Refrigerating and Air-Conditioning (ASHRAE)) as a mixed refrigerant.

  However, since R410A has a large global warming potential (GWP), recently, the use of hydrofluoroolefin (HFO) having a smaller GWP has been proposed. For example, Patent Document 1 discloses using 1,1,2-trifluoroethylene (HFO1123) as HFO. Patent Document 1 discloses the combined use of HFC such as difluoromethane (HFC32, R32) together with 1,1,2-trifluoroethylene.

  Since 1,1,2-trifluoroethylene is less stable than conventional HFCs and the like, it is difficult to remain in the atmosphere, and therefore, ODP and GWP are small. However, as suggested in Patent Document 2, due to the low stability of 1,1,2-trifluoroethylene, self-polymerization reaction called disproportionation reaction (hereinafter referred to as disproportionation reaction) It is also known that this is likely to occur. The disproportionation reaction is likely to occur due to the heat generated during the use of the working medium for the refrigeration cycle, and the disproportionation reaction is accompanied by a large heat release. It is also known to occur. As a result, a large amount of soot may be generated, which may reduce the reliability of the refrigeration cycle system or the compressor constituting the system.

International Publication No. 2012/157774 International Publication No. 2015/141679 Pamphlet

  There are many unclear parts regarding the disproportionation reaction of 1,1,2-trifluoroethylene. As will be described later, the disproportionation reaction is a reaction including a self-decomposition reaction of 1,1,2-trifluoroethylene and a polymerization reaction subsequent to the self-decomposition reaction. Only “self-polymerization reaction” is described, and no specific examination on the disproportionation reaction is described. Therefore, in Patent Document 2, rather than suppressing the occurrence of the disproportionation reaction itself, difluoromethane is mixed to reduce the content of 1,1,2-trifluoroethylene in the total amount of the working medium. This is considered to reduce the frequency of occurrence of the “self-polymerization reaction”.

  Specifically, in Patent Document 2, the ratio of the total amount of 1,1,2-trifluoroethylene and difluoromethane to the total amount of the working medium is set to be more than 90% by mass to 100% by mass, It is disclosed that the mass ratio of 2-trifluoroethylene / difluoromethane is limited to a range of 21/79 to 39/61. However, in other words, if the content of 1,1,2-trifluoroethylene in the total amount of the working medium exceeds 39% by mass, the “self-polymerization reaction” cannot be effectively suppressed.

  The present invention has been made to solve such problems, and even when the content of 1,1,2-trifluoroethylene is relatively high, the disproportionation reaction is effectively prevented. It is an object of the present invention to provide a working medium for a refrigeration cycle that can be suppressed or alleviated and a refrigeration cycle system using the working medium.

  In order to solve the above-mentioned problem, the working medium for the refrigeration cycle according to the present invention contains at least 1,1,2-trifluoroethylene as a refrigerant component, and the 1,1,2-trifluoroethylene As a disproportionation inhibitor that suppresses the disproportionation reaction, it contains a saturated hydrocarbon having 2 to 5 carbon atoms and a haloalkane having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine. is there.

  According to the above configuration, a saturated hydrocarbon and a haloalkane are combined and added as a disproportionation inhibitor to a refrigerant component mainly composed of 1,1,2-trifluoroethylene (HFO1123). In the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as a fluorine radical, a fluoromethyl radical, and a fluoromethylene radical cause a chain branching reaction, and both saturated hydrocarbons and haloalkanes are free from these radicals. Can be captured well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, or the rapid progress of the disproportionation reaction can be reduced. In addition, it is possible to achieve suppression of the disproportionation reaction or relaxation of the progress with a smaller amount than when adding saturated hydrocarbon alone or haloalkane alone as a disproportionation inhibitor. As a result, it is possible to improve the reliability of the refrigeration cycle working medium and the refrigeration cycle system using the same.

  In the present invention, with the above configuration, a refrigeration cycle capable of effectively suppressing or mitigating the disproportionation reaction even when the content of 1,1,2-trifluoroethylene is relatively large. The working medium and the refrigeration cycle system using the same can be provided.

(A) * (B) is a typical block diagram which shows an example of the refrigerating-cycle system concerning one Embodiment of this indication.

  The working medium for a refrigeration cycle according to the present disclosure contains at least 1,1,2-trifluoroethylene as a refrigerant component and suppresses disproportionation reaction of the 1,1,2-trifluoroethylene. It is the structure containing a C2-C5 saturated hydrocarbon and a haloalkane which is C1-C2 and a halogen atom except the case where all the halogen atoms are fluorine as a oxidization inhibitor.

  According to the above configuration, a saturated hydrocarbon and a haloalkane are combined and added as a disproportionation inhibitor to a refrigerant component mainly composed of 1,1,2-trifluoroethylene (HFO1123). In the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as a fluorine radical, a fluoromethyl radical, and a fluoromethylene radical cause a chain branching reaction, and both saturated hydrocarbons and haloalkanes are free from these radicals. Can be captured well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, or the rapid progress of the disproportionation reaction can be reduced. In addition, it is possible to achieve suppression of the disproportionation reaction or relaxation of the progress with a smaller amount than when adding saturated hydrocarbon alone or haloalkane alone as a disproportionation inhibitor. As a result, it is possible to improve the reliability of the refrigeration cycle working medium and the refrigeration cycle system using the same.

In the refrigeration cycle working medium having the above configuration, the haloalkane is represented by the following formula (1):
C ₂ H _m X _n (1)
(In the formula (1), X is a halogen atom selected from the group consisting of F, Cl, Br, and I, m is an integer of 0 or more, n is an integer of 1 or more, and The sum of m and n is 6, and when n is 2 or more, X is the same or different type of halogen atom.)
Or a haloethane having the structure shown below (excluding the case where X is only F), or the following formula (2)
CH _p X _q (2)
(In the formula (2), X is a halogen atom selected from the group consisting of F, Cl, Br, and I, p is an integer of 0 or more, q is an integer of 1 or more, and p And the sum of q is 4, and when q is 2 or more, X is the same or different kind of halogen atom.)
The structure which is halomethane (except when X is only F) having the structure shown in FIG.

  According to the above configuration, since the haloethane represented by the formula (1) or the halomethane represented by the formula (2) is used as the haloalkane, it is possible to satisfactorily suppress the disproportionation reaction or moderate the progress. it can.

  The refrigeration cycle working medium having the above-described configuration may include the saturated hydrocarbon and at least one of the haloethane and the halomethane as the disproportionation inhibitor.

  According to the above configuration, as the combination of the disproportionation inhibitor, [1] three kinds of combinations of saturated hydrocarbon, haloethane and halomethane, [2] two kinds of combinations of saturated hydrocarbon and haloethane, or [3] Since any combination of two types of saturated hydrocarbons and halomethanes is used, the disproportionation reaction can be suppressed or the progress can be satisfactorily achieved.

  In the refrigeration cycle working medium having the above configuration, the haloethane has a configuration in which the halogen atom X is at least one of F and I, and the halomethane has a configuration in which the halogen atom X contains bromine. May be.

  According to the said structure, what can implement | achieve the effect of suppression of a disproportionation reaction or the improvement of progress more satisfactorily as a haloalkane, or the thing which cannot receive a restriction | limiting to availability or handleability can be used.

In the working fluid for a refrigeration cycle having the above-described configuration, the saturated hydrocarbon is n-propane, the haloethane is 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I), The halomethane may be trifluoroiodomethane (CF ₃ I).

  According to the said structure, suppression of a disproportionation reaction or relaxation of progress can be implement | achieved more favorably by using each said compound as a saturated hydrocarbon and haloalkane.

  In the refrigeration cycle working medium having the above-described configuration, difluoromethane is further contained as a refrigerant component, and the content of the difluoromethane in the total amount of the refrigerant component and the disproportionation inhibitor is less than 60% by mass. The structure which is may be sufficient.

  According to the said structure, since there is little influence on an environment like 1,1,2- trifluoroethylene and difluoromethane which is a favorable refrigerant | coolant component is contained, a favorable property is implement | achieved as a working medium for refrigeration cycles. be able to.

  In the refrigeration cycle working medium having the above configuration, when the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass, the content of the disproportionation inhibitor is 3% by mass or less. It may be a configuration.

  According to the above configuration, even when the total amount of the saturated hydrocarbon and the haloalkane is suppressed to 3% by mass or less, it is possible to satisfactorily suppress the disproportionation reaction or moderate the progress. Therefore, even a small content (added amount) can be used as a good disproportionation inhibitor.

  Moreover, in the working medium for a refrigeration cycle having the above configuration, the content of the disproportionation inhibitor may be 1.2% by mass or more.

  According to the said structure, if the total amount of a saturated hydrocarbon and haloalkane is 1.2 mass% or more, especially suppression of disproportionation reaction or relaxation of progress can be implement | achieved satisfactorily. Therefore, even a small content (added amount) can be used as a good disproportionation inhibitor.

  Furthermore, the present disclosure includes a refrigeration cycle system configured using the refrigeration cycle working medium having the above-described configuration.

  According to the above configuration, since the refrigeration cycle system is configured using the above-described working medium for the refrigeration cycle, an efficient refrigeration cycle system can be realized and the reliability of the refrigeration cycle system can be improved.

  Hereinafter, a typical embodiment of the present disclosure will be specifically described. The working medium for a refrigeration cycle according to the present disclosure contains at least 1,1,2-trifluoroethylene as a refrigerant component and disproportionately suppresses the disproportionation reaction of the 1,1,2-trifluoroethylene. It is the structure containing a C2-C5 saturated hydrocarbon and a haloalkane which is C1-C2 and a halogen atom except the case where all the halogen atoms are fluorine as a oxidization inhibitor.

  Note that the refrigeration cycle working medium according to the present disclosure may include a compound other than 1,1,2-trifluoroethylene as a refrigerant component. In addition, the refrigeration cycle working medium according to the present disclosure only needs to be configured with at least a refrigerant component and a disproportionation inhibitor, but may include other components.

[Refrigerant component]
In the working medium for the refrigeration cycle according to the present disclosure, at least 1,1,2-trifluoroethylene (HFO1123) is used as a refrigerant component. 1,1,2-trifluoroethylene has the structure of the following formula (3), and two hydrogen atoms (H) bonded to the carbon atom (C) at the 1-position of ethylene are fluorine (F And one of the two hydrogen atoms bonded to the carbon atom at the 2-position is substituted with fluorine.

  1,1,2-trifluoroethylene contains a carbon-carbon double bond. Although ozone in the atmosphere generates hydroxyl radicals (OH radicals) by photochemical reaction, double bonds are easily decomposed by the hydroxyl radicals. Therefore, 1,1,2-trifluoroethylene has little influence on ozone layer destruction and global temperature.

  However, 1,1,2-trifluoroethylene is also known to cause a rapid disproportionation reaction due to this good decomposability. In this disproportionation reaction, a self-decomposition reaction occurs in which 1,1,2-trifluoroethylene molecules are decomposed, and subsequent to this self-decomposition reaction, carbon generated by decomposition is polymerized to become a soot. Reaction occurs. When an active radical is generated due to heat generation in a high temperature and high pressure state, this active radical reacts with 1,1,2-trifluoroethylene to generate the above-mentioned disproportionation reaction. Since this disproportionation reaction is accompanied by heat generation, an active radical is generated by this heat generation, and further, the disproportionation reaction is induced by this active radical. As described above, the generation of active radicals and the generation of the disproportionation reaction are linked, so that the disproportionation reaction proceeds rapidly.

As a result of intensive studies by the present inventors, active radicals that induce the disproportionation reaction of 1,1,2-trifluoroethylene are mainly fluorine radicals (F radicals) and trifluoromethyl radicals (CF ₃ radicals). And a radical such as a difluoromethylene radical (CF ₂ radical). Therefore, the rapid disproportionation reaction is suppressed by adding a substance (disproportionation inhibitor) capable of efficiently capturing F radicals, CF ₃ radicals, CF ₂ radicals, etc. to the working medium for the refrigeration cycle. Or tried to alleviate. As a result, as will be described later, it was originally found that a suitable disproportionation inhibitor can be obtained by adding a combination of a saturated hydrocarbon and a haloalkane.

  Here, the working medium for the refrigeration cycle according to the present disclosure may include a compound (other refrigerant component) other than 1,1,2-trifluoroethylene as the refrigerant component. Typical other refrigerant components include hydrofluorocarbons such as difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane and heptafluorocyclopentane. Fluorocarbon (HFC); monofluoropropene, trifluoropropene, tetrafluoropropene, pentafluoropropene, hydrofluoroolefin (HFO) such as hexafluorobutene, and the like can be mentioned, but are not particularly limited.

  Since these HFCs or HFOs are known to have little influence on ozone layer destruction and global warming, they can be used together with 1,1,2-trifluoroethylene as a refrigerant component. The other refrigerant components described above may be used alone or in combination of two or more. Among these, difluoromethane (HFC32, R32) can be mentioned as a particularly preferred example.

  The content of 1,1,2-trifluoroethylene in the refrigeration cycle working medium is not particularly limited, but among the components constituting the refrigeration cycle working medium, the total amount of refrigerant components and disproportionation inhibitor described later ( For convenience of explanation, it is assumed that “the total amount of refrigerant-related components” is 100% by mass, and the content of 1,1,2-trifluoroethylene may be 40% by mass or more. The content of trifluoroethylene may be 40% by mass as described above, but is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. preferable.

  If the content of 1,1,2-trifluoroethylene is less than 40% by mass of the total amount of refrigerant-related components, the content of 1,1,2-trifluoroethylene in the refrigeration cycle working medium becomes too low, A lot of other refrigerant components are contained. Therefore, in the working medium for the refrigeration cycle, the advantage of using 1,1,2-trifluoroethylene having a small GWP cannot be obtained sufficiently.

  Moreover, the upper limit of the content of 1,1,2-trifluoroethylene is not particularly limited, but may be 98.8% by mass or less of the total amount of refrigerant-related components. As will be described later, since the preferable lower limit of the disproportionation inhibitor is 1.2% by mass, only 1,1,2-trifluoroethylene is used as the refrigerant component, and no other refrigerant component is used ( Assuming that 1,1,2-trifluoroethylene is 100% by mass as the refrigerant component), the upper limit of the content of 1,1,2-trifluoroethylene in the total amount of refrigerant-related components is necessarily 98.8. It becomes mass%.

  When a refrigerant component other than 1,1,2-trifluoroethylene is contained as the refrigerant component, the content of the other refrigerant component is not particularly limited. For example, preferred examples of other refrigerant components include difluoromethane as described above, but the preferable upper limit of the content of 1,1,2-trifluoroethylene, which is an essential refrigerant component, is a refrigerant-related component. Since the total amount is 40% by mass, the content of difluoromethane may be less than 60% by mass of the total amount of refrigerant-related components. In addition, when other refrigerant components are included, an example of a particularly preferable content of 1,1,2-trifluoroethylene can be within a range of 70% by mass to 80% by mass, but is not limited thereto. Not.

[Disproportionation inhibitor]
The working medium for a refrigeration cycle according to the present disclosure includes a saturated hydrocarbon having 2 to 5 carbon atoms and a carbon number as a disproportionation inhibitor that suppresses the disproportionation reaction of 1,1,2-trifluoroethylene described above. 1 or 2, and a haloalkane excluding the case where all the halogen atoms are fluorine. By using these disproportionation inhibitors in combination, it becomes possible to achieve suppression of disproportionation reaction or relaxation of progress even with a smaller amount.

  First, saturated hydrocarbons will be described. In the present disclosure, the saturated hydrocarbon having 2 to 5 carbon atoms used as the disproportionation inhibitor is not particularly limited, and specifically, for example, ethane, n-propane, cyclopropane, n-butane, cyclobutane, and isobutane. (2-methylpropane), methylcyclopropane, n-pentane, isopentane (2-methylbutane), neopentane (2,2-dimethylpropane), methylcyclobutane and the like. Only one kind of these saturated hydrocarbons may be used, or two or more kinds may be used in appropriate combination. Of these saturated hydrocarbons, n-propane is particularly preferable.

  These saturated hydrocarbons are all gases at room temperature (the boiling points of n-pentane and methylcyclobutane are the highest at about 36 ° C., and the boiling points of other hydrocarbons are less than 36 ° C.). Can be mixed well. A saturated hydrocarbon having 6 or more carbon atoms is not preferable because it is liquid at room temperature and is difficult to mix as a component of a working medium for a refrigeration cycle. In addition, saturated hydrocarbons having 1 carbon atom, that is, methane are not preferable because of their large global warming potential (GWP). Of the saturated hydrocarbons having 2 to 5 carbon atoms, cyclopentane has a boiling point of 49 ° C. and is a liquid at room temperature, but can be used as a disproportionation inhibitor depending on conditions.

  Next, haloalkane (halogenated alkane) will be described. The haloalkane used as a disproportionation inhibitor in the present disclosure may be any one having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine. More specifically, a haloalkane having 2 carbon atoms, that is, haloethane (halogenated ethane), and a haloalkane having 1 carbon atom, that is, halomethane (halogenated methane) can be exemplified. As the disproportionation inhibitor, either haloethane or halomethane may be used in combination with the saturated hydrocarbon described above, but both haloethane and halomethane may be used in combination.

  Specifically, the haloethane in the haloalkane used as the disproportionation inhibitor may be one having the following formula (1) structure.

C ₂ H _m X _n (1)
However, X in Formula (1) is a halogen atom selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), and m is an integer of 0 or more. n is an integer of 1 or more, and the sum of m and n is 6. When n is 2 or more, X is the same or different kind of halogen atom.

That is, the haloethane represented by the formula (1) includes a monohaloethane represented by the following formula (11), a dihaloethane represented by the following formula (12), a trihaloethane represented by the following formula (13), a tetrahaloethane represented by the following formula (14), What is necessary is just to be at least one of the pentahaloethane shown to Formula (15), and the hexahaloethane shown to following Formula (16). In the haloethane represented by the formulas (11) to (16), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ each independently represent one halogen atom. Therefore, X ^{1 to} X ⁶ may be different types of halogen atoms, or may be at least two of the same type and different types of halogen atoms, or all of the same type. It may be a halogen atom.

CH ₂ X ¹ CH ₃ (11)
CHX ¹ X ² CH ₃ (12)
CX ¹ X ² X ³ CH ₃ (13)
CX ¹ X ² X ³ CH ₂ X ⁴ (14)
CX ¹ X ² X ³ CHX ⁴ X ⁵ (15)
CX ¹ X ² X ³ CX ⁴ X ⁵ X ⁶ (16)
However, the haloethane represented by the formula (1) excludes those in which X is composed only of F. This is because haloethane in which X is composed only of F is a compound that can be used in combination as another refrigerant component as described above, and does not substantially function as a disproportionation inhibitor.

  In the haloethane represented by the formula (1), the halogen atom X may be at least one of F, Cl, Br, and I as described above, and among these, at least one of F and I is preferable. . When the haloethane represented by the formula (1) contains Cl and / or Br, the ozone depletion potential (ODP) tends to be high, which may limit availability or handling. Regardless of the type of halogen atom X, the haloethane represented by the formula (1) includes a compound having a relatively large ozone depletion coefficient (ODP) and / or global warming potential (GWP).

  However, as will be described later, in the working medium for the refrigeration cycle according to the present disclosure, even when the amount of haloethane added as a disproportionation inhibitor is small, the disproportionation reaction of 1,1,2-trifluoroethylene is performed. Can be effectively suppressed, or the rapid progress of the disproportionation reaction can be mitigated. Even when other disproportionation inhibitors described later are used in combination, the total amount of disproportionation inhibitor added is sufficiently smaller than that of the refrigerant component. Therefore, even if a haloethane having a relatively large ODP or GWP is used, the environment is not significantly affected.

Specific haloethane represented by the formula (1) is not particularly limited. For example, 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I), monoiodoethane (CH ₃ CH ₂ I), mono Examples thereof include bromoethane (CH ₃ CH ₂ Br), 1,1,1-triiodoethane (CH ₃ CI ₃ ) and the like. Only one kind of these haloethanes may be used, or two or more kinds may be used in appropriate combination. Among these, 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I) can be particularly preferably used in consideration of availability, ODP value, handleability, and the like.

  Of the haloalkanes used as the disproportionation inhibitor, halomethanes may be specifically those having the structure of the following formula (2).

CH _p X _q (2)
However, X in Formula (2) is a halogen atom selected from the group consisting of F, Cl, Br, and I, p is an integer of 0 or more, q is an integer of 1 or more, and p And the sum of q is 4, and when q is 2 or more, X is the same or different kind of halogen atom.

That is, the halomethane represented by the formula (2) is a monohalomethane represented by the following formula (21), a dihalomethane represented by the following formula (22), a trihalomethane represented by the following formula (23), and a tetrahalomethane represented by the following formula (24). It may be at least one. X ¹ , X ² , X ³ , and X ⁴ in the halomethanes represented by these formulas (21) to (24) each independently represent one halogen atom. Therefore, X ^{1 to} X ⁴ may be different types of halogen atoms, or may be at least two of the same type and different types of halogen atoms, or all of the same type. It may be a halogen atom.

CH ₃ X ¹ (21)
CH ₂ X ¹ X ² (22)
CHX ¹ X ² X ³ (23)
CX ¹ X ² X ³ X ⁴ (24)
However, the halomethane represented by the formula (2) excludes those in which X is composed of only F. This is because halomethane in which X is composed of only F is a compound that can be used in combination as another refrigerant component as described above, and does not substantially function as a disproportionation inhibitor.

Specific examples of the halomethane represented by the formula (2) include (mono) iodomethane (CH ₃ I), diiodomethane (CH ₂ I ₂ ), dibromomethane (CH ₂ Br ₂ ), and bromomethane (CH ₃ Br). , Dichloromethane (CH ₂ Cl ₂ ), chloroiodomethane (CH ₂ ClI), dibromochloromethane (CHBr ₂ Cl), tetraiodomethane (CI ₄ ), carbon tetrabromide (CBr ₄ ), bromotrichloromethane (CBrCl) ₃ ), dibromodichloromethane (CBr ₂ Cl ₂ ), tribromofluoromethane (CBr ₃ F), fluorodiiodomethane (CHFI ₂ ), difluorodiiodomethane (CF ₂ I ₂ ), dibromodifluoromethane (CBr ₂ F ₂₎ ), Trifluoroiodomethane (CF ₃ I) and the like, but are not particularly limited. Only one kind of these halomethanes may be used, or two or more kinds may be used in appropriate combination.

Among these, more preferable halomethanes include, for example, those in which bromine is contained in the halogen atom X, and more preferable halomethanes include dibromomethane (CH ₂ Br ₂ ) and bromomethane (CH ₃ Br). , Dibromodichloromethane (CBr ₂ Cl ₂ ), trifluoroiodomethane (CF ₃ I), and the like, and particularly preferred halomethanes include trifluoroiodomethane (CF ₃ I).

[Content of disproportionation inhibitor]
Next, the content (addition amount) of the above-described disproportionation inhibitor will be specifically described. In the working medium for the refrigeration cycle according to the present disclosure, as described above, the saturated hydrocarbon and the haloalkane are used in combination as the disproportionation inhibitor, but haloethane and halomethane can be used as the haloalkane.

  Therefore, in the working medium for the refrigeration cycle according to the present disclosure, the disproportionation inhibitor includes [1] three types of at least one saturated hydrocarbon, at least one haloethane, and at least one halomethane. A combination using compounds, or [2] a combination using two compounds, at least one saturated hydrocarbon and at least one haloethane, or [3] at least one saturated hydrocarbon and at least one halomethane. There are three combinations that use two types of compounds.

  As described in the content of the refrigerant component, when the refrigerant-related component total amount (total amount of the refrigerant component and the disproportionation inhibitor) is 100% by mass, the upper limit of the disproportionation inhibitor addition amount (content) Is not particularly limited, but may be 10% by mass or less of the total amount of refrigerant-related components, preferably 5% by mass or less, and more preferably 3% by mass or less. This is because when the content of the disproportionation inhibitor exceeds 10% by mass of the total amount of refrigerant-related components, the content of the disproportionation inhibitor increases excessively when viewed as a working medium for a refrigeration cycle. This is because good physical properties as a “refrigerant” may not be exhibited. Of course, it goes without saying that 10 mass% or more of the total amount of refrigerant-related components may be added depending on the composition of the working medium for the refrigeration cycle.

  As the disproportionation inhibitor, a saturated hydrocarbon and a haloalkane are used in combination, but the mixing ratio of the saturated hydrocarbon and the haloalkane is not particularly limited. As described above, the preferable content of the total amount of the disproportionation inhibitor can be 10% by mass or less, and it is sufficient that the saturated hydrocarbon and the haloalkane are used in an appropriate mixing ratio within this range.

  Here, the saturated hydrocarbon and the haloalkane can suppress the disproportionation reaction or alleviate the progress even when the addition amount is 10% by mass or less. Furthermore, as in the present disclosure, when a saturated hydrocarbon and a haloalkane are used in combination, the disproportionation reaction can be suppressed or the progress can be mitigated in a smaller amount than when added alone. More specifically, the upper limit of the total amount of disproportionation inhibitor may be 10% by mass or less, and may be 5% by mass or less, but when a saturated hydrocarbon and a haloalkane are combined, 3% by mass or less is more preferable. A preferable upper limit can be set.

  At this time, the mixing ratio of the saturated hydrocarbon and the haloalkane is not particularly limited, but when the addition amount is 3% by mass or less, as a representative example of the mixing ratio of the saturated hydrocarbon and the haloalkane, The range of 1: 0.5-1: 2 can be mentioned. As described above, there are three combinations of saturated hydrocarbons and haloalkanes. Therefore, when a typical mixing ratio is exemplified for each combination, [1] a combination of three types of combinations of saturated hydrocarbons, haloethanes and halomethanes. Can be included in the range of 1: 0.25: 0.25 to 1: 1: 1 by mass ratio. [2] In the combination of two types of combination of saturated hydrocarbon and haloethane, 1: 0.25 In the range of ˜1: 1, [3] In the case of a combination of two types of combined use of saturated hydrocarbon and halomethane, it can be in the range of 1: 0.25 to 1: 1.

  Moreover, although it does not specifically limit about the lower limit of content of disproportionation inhibitor, As a typical lower limit, 1.2 mass% or more of refrigerant | coolant related component whole quantity can be mentioned. Even if the total amount of the saturated hydrocarbon and the haloalkane is less than 1.2% by mass, it is possible to obtain an effect such as suppression of the disproportionation reaction. Effects such as suppression of reaction can be more suitably realized. Therefore, in the present disclosure, a more preferable range of the content of the disproportionation inhibitor may be a range of 1.2% by mass or more and 3% by mass or less of the total amount of refrigerant-related components.

  In general, in the working medium for the refrigeration cycle, impurities contained in the refrigerant component are often 2 to 3% by mass or less. For example, a commercially available 1,1,2-trifluoroethylene having a purity of about 97% by mass is known, and as impurities, the remainder of the synthetic raw material or by-products are contained in less than 3% by mass. . The disproportionation inhibitor in the present disclosure uses a saturated hydrocarbon and a haloalkane in combination to cause disproportionation reaction even when added to 1,1,2-trifluoroethylene at an impurity level (3% by mass or less). It can be effectively suppressed or progress can be mitigated. Therefore, the addition amount of the disproportionation inhibitor is not necessarily specified, and the upper limit value, the lower limit value, or the mixing ratio of the saturated hydrocarbon and the haloalkane described above is a typical preferable example. It is a thing.

[Other ingredients that can be used in combination]
Since the refrigeration cycle working medium according to the present disclosure is used in the refrigeration cycle system, it can be used in combination with a lubricating oil (refrigeration oil) that lubricates a compressor included in the refrigeration cycle system. As described above, the working medium for the refrigeration cycle according to the present disclosure is composed of a refrigerant component that is substantially “main component” of 1,1,2-trifluoroethylene, and the above-described saturated hydrocarbon and haloalkane. What is necessary is just to be comprised by the disproportionation inhibitor. Further, when the working fluid for the refrigeration cycle is used in combination with the lubricating oil, it may be considered that the working fluid-containing composition is composed of the refrigerant component, the disproportionation inhibitor, the lubricating oil component, and other components. it can.

  In the refrigeration cycle working medium according to the present disclosure, the disproportionation inhibitor may be mixed with a refrigerant component or a lubricating oil component. Of the disproportionation inhibitors, saturated hydrocarbons and halomethanes are usually gases at normal temperature and pressure, and therefore may be mixed with refrigerant components. In contrast, haloethane is normally a liquid at normal temperature and pressure, so the vapor phase portion of the haloethane present in the vapor pressure component may be mixed with the refrigerant component, and the liquid phase portion should be mixed with the lubricating oil component. Good. Even when a liquid saturated hydrocarbon or halomethane is used at room temperature and normal pressure, the liquid phase portion may be mixed with the lubricating oil component as in the case of haloethane.

  As the lubricating oil component contained in the working medium-containing composition (used together with the working medium for the refrigeration cycle), various known lubricating oils can be suitably used in the refrigeration cycle system. Specific lubricants include ester-based lubricants, ether-based lubricants, glycol-based lubricants, alkylbenzene-based lubricants, fluorine-based lubricants, mineral oils, hydrocarbon-based synthetic oils, etc. It is not limited. Only one type of these lubricating oils may be used, or two or more types may be used in appropriate combination.

  In addition, various known additives other than the disproportionation inhibitor may be added to the working medium-containing composition. Specific additives include, but are not limited to, antioxidants, moisture scavengers, metal deactivators, antiwear agents, antifoaming agents, and the like. Antioxidants are used to improve the thermal stability, oxidation resistance, chemical stability, etc. of refrigerant components or lubricating oils. The moisture scavenger is used to remove moisture when moisture enters the refrigeration cycle system, and in particular to suppress property changes of the lubricating oil. The metal deactivator is used for suppressing or preventing a chemical reaction caused by the catalytic action of the metal component. The antiwear agent is used to reduce wear at a sliding portion in the compressor, particularly wear during high pressure operation. The antifoaming agent is used in particular to suppress the generation of bubbles in the lubricating oil.

  Specific types of these additives are not particularly limited, and known compounds and the like can be suitably used according to various conditions. Further, as these additives, only one kind of compound or the like may be used, or two or more kinds of compounds or the like may be used in appropriate combination. Furthermore, the addition amount of these additives is not particularly limited, and should be added within a known range as long as the properties of the working medium for a refrigeration cycle according to the present disclosure or the working medium-containing composition containing the same are not impaired. Can do.

[Configuration example of refrigeration cycle system]
Next, an example of the refrigeration cycle system configured using the refrigeration cycle working medium according to the present disclosure will be described with reference to FIGS.

  The specific configuration of the refrigeration cycle system according to the present disclosure is not particularly limited as long as components such as a compressor, a condenser, an expansion unit, and an evaporator are connected by piping. Specific application examples of the refrigeration cycle system according to the present disclosure are also not particularly limited. For example, an air conditioner (air conditioner), a refrigerator (for home use, for business use), a dehumidifier, a showcase, an ice making machine, a heat pump hot water supply Machine, heat pump washer / dryer, vending machine and the like.

  As a typical application example of the refrigeration cycle system according to the present disclosure, an air conditioner will be described. Specifically, as schematically shown in the block diagram of FIG. 1A, the air conditioner 10 according to the present embodiment includes an indoor unit 11 and an outdoor unit 12, and a pipe 13 that connects these units. The indoor unit 11 includes a heat exchanger 14, and the outdoor unit 12 includes a heat exchanger 15, a compressor 16, and a decompression device 17.

  The heat exchanger 14 of the indoor unit 11 and the heat exchanger 15 of the outdoor unit 12 are connected in a ring shape by a pipe 13, thereby forming a refrigeration cycle. Specifically, the heat exchanger 14 of the indoor unit 11, the compressor 16, the heat exchanger 15 of the outdoor unit 12, and the decompression device 17 are connected in a ring shape through the pipe 13. The pipe 13 connecting the heat exchanger 14, the compressor 16, and the heat exchanger 15 is provided with a four-way valve 18 for switching between heating and cooling. The indoor unit 11 includes a blower fan, a temperature sensor, an operation unit, and the like (not shown), and the outdoor unit 12 includes a blower, an accumulator, and the like that are not shown. Further, the pipe 13 is provided with various valve devices (including the four-way valve 18), a strainer and the like (not shown).

  The heat exchanger 14 included in the indoor unit 11 exchanges heat between the indoor air sucked into the indoor unit 11 by the blower fan and the refrigerant flowing inside the heat exchanger 14. The indoor unit 11 blows air heated by heat exchange into the room during heating, and blows air cooled by heat exchange into the room during cooling. The heat exchanger 15 included in the outdoor unit 12 performs heat exchange between the outside air sucked into the outdoor unit 12 by the blower and the refrigerant flowing inside the heat exchanger 15.

  In addition, the specific structure of the indoor unit 11 and the outdoor unit 12, or the heat exchanger 14 or the heat exchanger 15, the compressor 16, the decompression device 17, the four-way valve 18, the blower fan, the temperature sensor, the operation unit, the blower, Specific configurations of the accumulator, other valve devices, strainers, and the like are not particularly limited, and known configurations can be suitably used.

  An example of the operation of the air conditioner 10 shown in FIG. 1A will be specifically described. First, in the cooling operation or the dehumidifying operation, the compressor 16 of the outdoor unit 12 compresses and discharges the gas refrigerant, whereby the gas refrigerant is sent to the heat exchanger 15 of the outdoor unit 12 via the four-way valve 18. Since the heat exchanger 15 exchanges heat between the outside air and the gas refrigerant, the gas refrigerant is condensed and liquefied. The liquefied liquid refrigerant is decompressed by the decompression device 17 and sent to the heat exchanger 14 of the indoor unit 11. In the heat exchanger 14, the liquid refrigerant evaporates by heat exchange with room air and becomes a gas refrigerant. This gas refrigerant returns to the compressor 16 of the outdoor unit 12 through the four-way valve 18. The compressor 16 compresses the gas refrigerant and discharges it again to the heat exchanger 15 via the four-way valve 18.

  Further, in the heating operation, the compressor 16 of the outdoor unit 12 compresses and discharges the gas refrigerant, whereby the gas refrigerant is sent to the heat exchanger 14 of the indoor unit 11 via the four-way valve 18. In the heat exchanger 14, the gas refrigerant is condensed and liquefied by heat exchange with room air. The liquefied liquid refrigerant is decompressed by the decompression device 17 to become a gas-liquid two-phase refrigerant, and is sent to the heat exchanger 15 of the outdoor unit 12. Since the heat exchanger 15 exchanges heat between the outside air and the gas-liquid two-phase refrigerant, the gas-liquid two-phase refrigerant evaporates to become a gas refrigerant and returns to the compressor 16. The compressor 16 compresses the gas refrigerant and discharges it again to the heat exchanger 14 of the indoor unit 11 through the four-way valve 18.

  Further, as another typical application example of the refrigeration cycle system according to the present disclosure, a refrigerator will be described as an example. Specifically, for example, as schematically shown in the block diagram of FIG. 1B, the refrigerator 20 according to the present embodiment includes the compressor 21, the condenser 22, the decompression device 23, and the evaporation shown in FIG. The container 24, the piping 25, etc. are provided. In addition, although not shown, the refrigerator 20 also includes a casing, a blower, an operation unit, a control unit, and the like serving as a main body.

  The compressor 21 compresses the refrigerant gas into a high-temperature and high-pressure gas refrigerant. The condenser 22 cools and liquefies the refrigerant. The decompression device 23 is composed of, for example, a capillary tube, and decompresses the liquefied refrigerant (liquid refrigerant). The evaporator 24 evaporates the refrigerant into a low-temperature and low-pressure gas refrigerant. The compressor 21, the condenser 22, the decompression device 23, and the evaporator 24 are annularly connected in this order by a pipe 25 through which the refrigerant gas is circulated, thereby constituting a refrigeration cycle.

  The configurations of the compressor 21, the condenser 22, the decompression device 23, the evaporator 24, the piping 25, the main body housing, the blower, the operation unit, the control unit, and the like are not particularly limited, and a known configuration is preferably used. it can. Moreover, the refrigerator 20 may be provided with well-known structures other than these.

  An example of the operation of the refrigerator 20 illustrated in FIG. The compressor 21 compresses the gas refrigerant and discharges it to the condenser 22. The condenser 22 cools the gas refrigerant into a liquid refrigerant. The liquid refrigerant is decompressed by passing through the decompression device 23 and sent to the evaporator 24. In the evaporator 24, the liquid refrigerant is vaporized by taking heat from the surroundings, and becomes a gas refrigerant and returns to the compressor 21. The compressor 21 compresses the gas refrigerant and discharges it to the condenser 22 again.

  Such an air conditioner 10 or the refrigerator 20 is a refrigeration cycle system configured by using the above-described refrigeration cycle working medium. 1,1,2-trifluoroethylene used for the working medium for the refrigeration cycle has good properties as a refrigerant component, and has small ODP and GWP. Therefore, an efficient refrigeration cycle system can be realized while reducing the influence on the environment.

  In addition, the working medium for the refrigeration cycle according to the present disclosure uses 1,1,2-trifluoroethylene as a refrigerant component, and as a disproportionation inhibitor, a saturated hydrocarbon having 2 to 5 carbon atoms and carbon And a haloalkane except that the halogen atoms are all fluorine. Therefore, even if heat generation or the like occurs during the operation of the refrigeration cycle, occurrence of a chain disproportionation reaction of 1,1,2-trifluoroethylene can be avoided, suppressed, or alleviated. As a result, generation of soot and the like due to a chain disproportionation reaction can be effectively avoided, so that the reliability of the refrigeration cycle working medium and the refrigeration cycle system using the same can be improved.

  The present disclosure will be described more specifically based on examples, comparative examples, and reference examples, but the present disclosure is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present disclosure.

(Experimental system of disproportionation reaction)
Pressure sensor (manufactured by VALCOM Co., Ltd.) that measures the internal pressure in the pressure-resistant container (Teflon inner cylinder sealed container TAF-SR [trade name], internal volume 50 mL) manufactured by Pressure Glass Industrial Co., Ltd.) VESVM10-2m [trade name]), thermocouple (PL thermocouple ground PL-18-KA 4-T [trade name] manufactured by Conax Technologies) for measuring the internal temperature in the pressure vessel, and the pressure vessel A discharge device (UH-1 series mini-mini welder [trade name] manufactured by AS ONE Co., Ltd.) is attached to the inside, and 1,1,2-trifluoroethylene (manufactured by SynQuest Laboratories, Hydras Chemical ( Co., Ltd., a gas cylinder of 5% limonene (contained in liquid phase) as a stabilizer, was connected so that the pressure could be adjusted. Furthermore, the pressure sensor and the thermometer were connected to a data logger (GL220 type [trade name] manufactured by Graphtec Co., Ltd., sampling interval minimum 10 milliseconds). Thus, an experimental system for disproportionation reaction was constructed. Since the upper limit of measurement of the thermocouple used in the experimental system is about 1000 ° C., the internal temperature of the pressure vessel in the following comparative example or implementation is handled as a reference value particularly when it exceeds 1000 ° C.

(Comparative example)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel. The internal pressure (1,1,2-trifluoroethylene pressure) at this time was 1.28 MPa.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated by a discharge device at an internal temperature of about 24 ° C. (297.65 K), and the internal pressure and internal temperature were measured by a data logger. . As a result, an internal pressure of 7.867 MPa and an internal temperature of about 884 ° C. (1157.45 K) were measured in 1 to 2 seconds after one discharge was generated. Thereafter, when the inside of the pressure vessel was checked after the internal pressure and the internal temperature were sufficiently reduced, generation of a considerable amount of soot was confirmed.

Example 1
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.97% by mass of n-propane, 1,1,1-trifluoro was used as a disproportionation inhibitor. -2-iodoethane was added in an amount of 0.26% by mass and trifluoroiodomethane was added in an amount of 0.25% by mass. In addition, the sum total of the addition amount of 3 types of disproportionation inhibitor is 1.48 mass%.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (about 300 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 5 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Example 2)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.97% by mass of n-propane, 1,1,1-trifluoro was used as a disproportionation inhibitor. 2-Iodoethane was added in an amount of 0.51% by mass and trifluoroiodomethane was added in an amount of 0.43% by mass. In addition, the sum total of the addition amount of 3 types of disproportionation inhibitor is 1.91 mass%.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (about 300 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 43 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Example 3)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.96% by mass of n-propane, 1,1,1-trifluoro was used as a disproportionation inhibitor. 2-iodoethane was added to 0.89% by mass, and trifluoroiodomethane was added to 0.74% by mass. In addition, the sum total of the addition amount of 3 types of disproportionation inhibitor is 2.59 mass%.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (about 300 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even after the discharge was repeated 36 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

Example 4
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.97% by mass of n-propane, 1,1,1-trifluoro was used as a disproportionation inhibitor. -2-Iodoethane was added so that the addition amount was 0.51% by mass. The total amount of the two disproportionation inhibitors added is 1.48% by mass.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 24 ° C. (about 297 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 5 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Example 5)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.97% by mass of n-propane, 1,1,1-trifluoro was used as a disproportionation inhibitor. -2-iodoethane was added so that the addition amount was 0.26% by mass. The total amount of the two disproportionation inhibitors added is 1.23% by mass.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 22 ° C. (about 295 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 5 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Example 6)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel, and 0.97% by mass of n-propane and 0.48 of trifluoroiodomethane were used as a disproportionation inhibitor. It added so that it might become the addition amount of the mass%. In addition, the sum total of the addition amount of 2 types of disproportionation inhibitors is 1.45 mass%.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (about 300 K), and the internal pressure and internal temperature were measured by a data logger. did. As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 18 times.

(Reference Example 1)
In the experimental system, 1,1,2-trifluoroethylene was introduced into the pressure vessel from the gas cylinder, and n-propane as a disproportionation inhibitor was added to an amount of 2.8% by mass. .

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (300 K), and the internal pressure and internal temperature were measured by a data logger. . As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 11 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Reference Example 2)
In the experimental system, 1,1,2-trifluoroethylene was introduced into the pressure vessel from the gas cylinder, and 1,1,1-trifluoro-2-iodoethane as a disproportionation inhibitor was 1.27% by mass. It added so that it might become the addition amount of.

  In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated several times by a discharge device at an internal temperature of about 27 ° C. (300 K), and the internal pressure and internal temperature were measured by a data logger. . As a result, no significant pressure increase or temperature increase was observed even when the discharge was repeated 30 times. Thereafter, the inside of the pressure vessel was checked after the internal pressure and temperature were sufficiently lowered, but no soot was found.

(Comparison of Comparative Examples, Examples and Reference Examples)
From the result of the comparative example, by generating a discharge in the pressure-resistant vessel in the experimental system, a disproportionation reaction occurs in 1,1,2-trifluoroethylene, and this disproportionation reaction is chained rapidly. You can see it going. During this disproportionation reaction, the internal pressure increased to 7.8 MPa, and the internal temperature increased to 880 ° C. (1157 K).

  On the other hand, from the results of Examples 1 to 6, by using a combination of a saturated hydrocarbon and a haloalkane as a disproportionation inhibitor, even if the addition amount is as small as 1.2% by mass or more and 3% by mass or less. It can be seen that the disproportionation reaction can be effectively suppressed. Further, as is clear from the results of Examples 1 to 3, the results of Examples 4 and 5, and the result of Example 6, [1] three kinds of combinations of saturated hydrocarbon, haloethane and halomethane (Examples) 1-3) [2] Two types of combinations of saturated hydrocarbons and haloethanes (Examples 4 and 5), [3] Two types of combinations of saturated hydrocarbons and halomethanes (Examples) 6), it can be seen that the disproportionation reaction can be effectively suppressed.

  Further, as is clear from the comparison between the results of Examples 1 to 6 and the results of Reference Examples 1 and 2, when a combination of a saturated hydrocarbon and a haloalkane was used as the disproportionation inhibitor, the saturated hydrocarbon alone It can also be seen that the disproportionation reaction can be effectively suppressed even if the addition amount (content) is relatively smaller than when haloalkane is used alone.

  Based on the results of these examples and reference examples, there is no difference in the mechanism of action between the suppression action of the disproportionation reaction by saturated hydrocarbons and the suppression action of the disproportionation reaction by haloalkanes. I guess that. If the inhibitory action by saturated hydrocarbons and haloalkanes is the same, it is considered that the addition amount (content) cannot be reduced even if these are simply combined and added. However, as described above, the amount added can be reduced by a combination of a saturated hydrocarbon and a haloalkane.

  Considering the results of these Examples and Reference Examples, in the case of saturated hydrocarbons, the active radicals extract hydrogen atoms from the saturated hydrocarbons before the active radicals that cause the disproportionation reaction react in a chain manner. It is presumed that the disproportionation reaction is suppressed. On the other hand, haloalkane is presumed to suppress the disproportionation reaction by reacting directly with the active radical and inactivating it. Based on these assumptions, when a saturated hydrocarbon hydrogen atom is extracted by an active radical, a saturated hydrocarbon radical is generated, but this saturated hydrocarbon radical is not rapidly inactivated by a haloalkane. I guess that. Thereby, it is conceivable that the disproportionation reaction can be effectively suppressed even with a smaller addition amount.

  It should be noted that the present invention is not limited to the description of the above-described embodiment, and various modifications are possible within the scope shown in the scope of the claims, and are disclosed in different embodiments and a plurality of modifications. Embodiments obtained by appropriately combining the technical means are also included in the technical scope of the present invention.

  INDUSTRIAL APPLICATION While this invention can be used suitably for the field | area of the working medium used for a refrigerating cycle, it is an air conditioning apparatus (air conditioner), a refrigerator (for home use, business use), a dehumidifier, a showcase, an ice making machine, a heat pump type. The present invention can also be suitably used in the field of refrigeration cycle systems such as hot water heaters, heat pump type washing / drying machines, vending machines and the like.

10 Air conditioner (refrigeration cycle system)
DESCRIPTION OF SYMBOLS 11 Indoor unit 12 Outdoor unit 13 Piping 14 Heat exchanger 15 Heat exchanger 16 Compressor 17 Pressure reducing device 18 Four-way valve 20 Refrigerator (refrigeration cycle system)
21 Compressor 22 Condenser 23 Pressure reducing device 24 Evaporator 25 Piping

Claims (9)

While containing at least 1,1,2-trifluoroethylene as a refrigerant component,
As a disproportionation inhibitor that suppresses the disproportionation reaction of the 1,1,2-trifluoroethylene,
A saturated hydrocarbon having 2 to 5 carbon atoms;
A haloalkane having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine, and
Working medium for refrigeration cycle. The haloalkane is represented by the following formula (1)
C ₂ H _m X _n (1)
(In the formula (1), X is a halogen atom selected from the group consisting of F, Cl, Br, and I, m is an integer of 0 or more, n is an integer of 1 or more, and The sum of m and n is 6, and when n is 2 or more, X is the same or different type of halogen atom.)
Or a haloethane having the structure shown below (excluding the case where X is only F), or the following formula (2)
CH _p X _q (2)
(In the formula (2), X is a halogen atom selected from the group consisting of F, Cl, Br, and I, p is an integer of 0 or more, q is an integer of 1 or more, and p And the sum of q is 4, and when q is 2 or more, X is the same or different kind of halogen atom.)
It is characterized by being a halomethane having a structure shown in (except when X is only F),
The working medium for a refrigeration cycle according to claim 1. The disproportionation inhibitor contains the saturated hydrocarbon and at least one of the haloethane and the halomethane,
The working medium for a refrigeration cycle according to claim 2. In the haloethane, the halogen atom X is at least one of F and I.
The halomethane is characterized in that the halogen atom X contains bromine.
The working medium for a refrigeration cycle according to claim 2 or 3. The saturated hydrocarbon is n-propane;
The haloethane is 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I);
The halomethane is trifluoroiodomethane (CF ₃ I),
The working medium for a refrigeration cycle according to any one of claims 2 to 4. Furthermore, while containing difluoromethane as a refrigerant component,
The difluoromethane content in the total amount of the refrigerant component and the disproportionation inhibitor is less than 60% by mass,
The working medium for a refrigeration cycle according to any one of claims 1 to 5. When the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass, the content of the disproportionation inhibitor is 3% by mass or less,
The working medium for a refrigeration cycle according to claim 1. The content of the disproportionation inhibitor is 1.2% by mass or more,
The working medium for a refrigeration cycle according to claim 7.   The refrigerating cycle system comprised using the working medium for refrigerating cycles of any one of Claim 1 to 8.

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