JP6877998B2 - Working medium for refrigeration cycle and refrigeration cycle system - Google Patents

Description

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

Previously, HCFC (hydrochlorofluorocarbon) was used as the working medium (refrigerant or heat medium) for the refrigeration cycle, but HCFC has a great influence on ozone layer depletion. Therefore, in recent years, HFCs (hydrofluorocarbons) having an ozone depletion potential (ODP) of 0 have been used. A typical HFC is R410A (refrigerant number based on the Standard 34 standard of the American Society for Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE)) as a mixed refrigerant.

However, since R410A has a large global warming potential (GWP), the use of hydrofluoroolefins (HFOs) having a smaller GWP has recently been proposed. For example, Patent Document 1 discloses that 1,1,2-trifluoroethylene (HFO1123) is used as the HFO. Patent Document 1 also discloses a combination of HFCs such as difluoromethanes (HFC32, R32) together with 1,1,2-trifluoroethylene.

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

International Publication No. 2012/15776 Pamphlet JP-A-2015-2000800

In Patent Document 2, in order to suppress the disproportionation reaction of 1,1,2-trifluoroethylene, another refrigerant component is mixed at a constant ratio, or a flame retardant is added to the lubricating oil (refrigerator oil) used in combination. Is disclosed.

However, since there are many unclear points about the disproportionation reaction of 1,1,2-trifluoroethylene, additives (disproportionation inhibitors) that can effectively suppress or alleviate the disproportionation reaction are used. Not particularly known.

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

In order to solve the above-mentioned problems, the working medium for a refrigeration cycle according to the present invention contains at least 1,1,2-trifluoroethylene as a refrigerant component and contains 1,1,2-trifluoroethylene. As an disproportionation inhibitor that suppresses the disproportionation reaction, the following equation (1)
C ₂ H _m X _n ... (1)
(However, X in the formula (1) 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 further. 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.)
It is a configuration to which haloethane having the structure shown in (excluding the case where X is only F) is added.

According to the above configuration, haloethane represented by the above formula (1) is added as a disproportionation inhibitor to the refrigerant component containing 1,1,2-trifluoroethylene (HFO1123) as a main component. This haloethane can satisfactorily capture radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals that cause a chain branching reaction of the disproportionation reaction. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, and the rapid progress of the disproportionation reaction can be alleviated. As a result, the reliability of the working medium for the refrigeration cycle and the refrigeration cycle system using the working medium can be improved.

The present invention also includes a refrigeration cycle system configured using the refrigeration cycle actuating medium having the above configuration.

In the present invention, with the above configuration, even when the content of 1,1,2-trifluoroethylene is relatively high, the disproportionation reaction can be effectively suppressed or alleviated. It has the effect of being able to provide a working medium and a refrigeration cycle system using the working medium.

(A) and (B) are schematic block diagrams showing an example of a refrigeration cycle system according to an embodiment of the present disclosure.

The working medium for a refrigeration cycle according to the present disclosure contains at least 1,1,2-trifluoroethylene as a refrigerant component, and disproportionation that suppresses the disproportionation reaction of the 1,1,2-trifluoroethylene. As an inhibitor of chemical conversion, the following formula (1)
C ₂ H _m X _n ... (1)
(However, X in the formula (1) 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 further. 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.)
It is a configuration to which haloethane having the structure shown in (excluding the case where X is only F) is added.

According to the above configuration, haloethane represented by the above formula (1) is added as a disproportionation inhibitor to the refrigerant component containing 1,1,2-trifluoroethylene (HFO1123) as a main component. This haloethane can satisfactorily capture radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals that cause a chain branching reaction of the disproportionation reaction. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, and the rapid progress of the disproportionation reaction can be alleviated. As a result, the reliability of the working medium for the refrigeration cycle and the refrigeration cycle system using the working medium can be improved.

In the refrigeration cycle working medium having the above configuration, the haloethane may have a configuration in which the halogen atom X is at least one of F and I.

According to the above configuration, haloethane, which is not easily restricted in availability or handleability, can be used.

Further, in the working medium for the refrigeration cycle having the above configuration, the haloethane may have a configuration of _{1,1,1-trifluoro-2-iodoethane (CF 3} CH _{2 I).}

According to the above configuration, since the haloethane which is the disproportionation inhibitor is 1,1,1-trifluoro-2-iodoethane, the disproportionation reaction of 1,1,2-trifluoroethylene is further improved. Can be suppressed or alleviated.

In the working medium for a refrigeration cycle having the above configuration, the content of the haloethane is in the range of 0.1% by mass or more and 10% by mass or less when the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass. It may be an internal configuration.

According to the above configuration, in order to limit the amount of haloethane, which is a disproportionation inhibitor, to a more preferable range, the disproportionation reaction of 1,1,2-trifluoroethylene by haloethane can be further suppressed. The progress can be slowed down.

Further, in the working medium for the refrigeration cycle having the above structure, the following formula (2) is further used as a disproportionation inhibitor.
CH _p X _q・ ・ ・ (2)
(However, X in the 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 q is the sum of 4, and when q is 2 or more, X is the same or different kind of halogen atom.)
Halomethane having the structure shown in (excluding the case where X is only F) may be added.

According to the above configuration, in addition to the haloethane represented by the formula (1), the halomethane represented by the formula (2) is used in combination as the disproportionation inhibitor, so that the disproportionation of 1,1,2-trifluoroethylene is used. The chemical reaction can be suppressed more satisfactorily or the progress can be alleviated.

Further, in the working medium for the refrigeration cycle having the above configuration, the halomethane may be trifluoroiodomethane (CF ₃ I).

According to the above configuration, trifluoroiodomethane is used in combination with haloethane represented by the formula (1) as a disproportionation inhibitor, so that the disproportionation reaction of 1,1,2-trifluoroethylene can be carried out. It can be better suppressed or slowed down.

Further, the working medium for the refrigeration cycle having the above structure further contains difluoromethane 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. It may be configured to be.

According to the above configuration, as with 1,1,2-trifluoroethylene, it has little impact on the environment and contains difluoromethane, which is a good refrigerant component, so that it realizes good properties as an operating medium for a refrigeration cycle. be able to.

Further, the present disclosure also includes a refrigeration cycle system configured by using the refrigeration cycle working medium having the above configuration.

According to the above configuration, since the refrigeration cycle system is configured by using the above-mentioned 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, typical embodiments 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 (HFO1123) as a refrigerant component and suppresses the disproportionation reaction of the 1,1,2-trifluoroethylene. As a disproportionation inhibitor, haloethane (ethane halide) satisfying specific conditions is added.

The refrigeration cycle operating medium according to the present disclosure may contain a compound other than 1,1,2-trifluoroethylene as a refrigerant component. Further, the working medium for the refrigeration cycle according to the present disclosure may be composed of at least a refrigerant component and a disproportionation inhibitor, but may contain components other than these.

[Refrigerant component]
At least 1,1,2-trifluoroethylene (HFO1123) is used as the refrigerant component in the working medium for the refrigeration cycle according to the present disclosure. 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. Ozone in the atmosphere generates hydroxyl radicals (OH radicals) by a photochemical reaction, and the double bonds are easily decomposed by these hydroxyl radicals. Therefore, 1,1,2-trifluoroethylene has little effect on ozone layer depletion and global temperature.

However, 1,1,2-trifluoroethylene is also known to cause a rapid disproportionation reaction due to its good degradability. In this disproportionation reaction, a self-decomposition reaction in which molecules of 1,1,2-trifluoroethylene are decomposed occurs, and following this self-decomposition reaction, carbon generated by the decomposition is polymerized to form soot. Reactions and the like occur. When an active radical is generated due to heat generation or the like in a high temperature and high pressure state, the active radical reacts with 1,1,2-trifluoroethylene to generate the above-mentioned disproportionation reaction. Since this disproportionation reaction is accompanied by heat generation, active radicals are generated by this heat generation, and further, the disproportionation reaction is induced by the active radicals. In this way, 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 diligent studies by the present inventors, the active radicals that induce the disproportionation reaction of 1,1,2-trifluoroethylene are mainly fluorine radicals (F radicals) and trifluoromethyl radicals (CF ₃ radicals). , Difluoromethylene radical (CF ₂ radical) and other radicals were revealed. Therefore, 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, a rapid disproportionation reaction is suppressed. Or tried to alleviate. As a result, it was independently found that haloethane (halogenated ethane) satisfying a specific condition as described later can be a suitable disproportionation inhibitor.

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

Since these HFCs or HFOs are known to have little effect on ozone layer depletion and global warming, they can be used together with 1,1,2-trifluoroethylene as a refrigerant component. Only one type of the above-mentioned other refrigerant components may be used in combination, or two or more types may be used in combination as appropriate. Among these, a particularly preferable example is difluoromethane (HFC32, R32).

[Disproportionation inhibitor]
The disproportionation inhibitor added to the working medium for the refrigeration cycle according to the present disclosure may be haloethane having the structure of the following formula (1) (satisfying a specific condition).

C ₂ H _m X _n ... (1)
However, X in the 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, and 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) is monohaloethane represented by the following formula (11), dihaloethane represented by the following formula (12), trihaloethane represented by the following formula (13), tetrahaloethane represented by the following formula (14), and the following. It may be at least one of pentahaloethane represented by the formula (15) and hexahaloethane represented by the following formula (16). ^{X 1} , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ in the haloethane represented by these formulas (11) to (16) each independently represent one halogen atom. Therefore, X ^{1 to} X ⁶ may be different types of halogen atoms, at least two or more of the same type and other 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, from the haloethane represented by the above formula (1), those in which X is composed only of F are excluded. 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, but it is preferably at least one of F and I. .. 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 handleability. Further, regardless of the type of halogen atom X, the haloethane represented by the formula (1) includes a compound having a relatively large ozone depletion potential (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 if the amount of haloethane added as the disproportionation inhibitor is small, the disproportionation reaction of 1,1,2-trifluoroethylene. Can be effectively suppressed, and the rapid progress of the disproportionation reaction can be alleviated. Further, even when another disproportionation inhibitor described later is used in combination, the total amount of the disproportionation inhibitor added is sufficiently smaller than that of the refrigerant component. Therefore, even if haloethane having a relatively large ODP or GWP is used, it does not have a significant effect on the environment.

The specific haloethane represented by the formula (1) is not particularly limited, and 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) and 1,1,1-triiodoethane (CH ₃ CI _3). Only one type of these haloethanes may be used, or two or more types may be appropriately combined and used. 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.

[Other ingredients that can be used together]
Since the working medium for the refrigeration cycle according to the present disclosure is used in the refrigeration cycle system, it can be used in combination with the lubricating oil (refrigerator oil) for lubricating the compressor provided in the refrigeration cycle system. As described above, the working medium for the refrigeration cycle according to the present disclosure suppresses disproportionation composed of a refrigerant component containing 1,1,2-trifluoroethylene as a substantially "main component" and haloethane described above. It may be composed of at least an agent. Furthermore, when the working medium for the refrigeration cycle is used in combination with the lubricating oil, it can be considered that the working medium-containing composition is composed of the refrigerant component, the disproportionation inhibitor, the lubricating oil component, and other components. it can.

In the working medium for the refrigeration cycle according to the present disclosure, the disproportionation inhibitor haloethane may be mixed with the refrigerant component or the lubricating oil component. Since haloethane is usually a liquid at normal temperature and pressure, the gas phase portion of haloethane existing at the vapor pressure may be mixed with the refrigerant component, and the liquid phase portion may be mixed with the lubricating oil component.

As the lubricating oil component contained in the working medium-containing composition (used together with the working medium for the refrigeration cycle), various lubricating oils known in the refrigeration cycle system can be preferably used. Specific examples of the lubricating oil include ester-based lubricating oil, ether-based lubricating oil, glycol-based lubricating oil, alkylbenzene-based lubricating oil, fluorine-based lubricating oil, mineral oil, hydrocarbon-based synthetic oil, and the like. Not limited. Only one type of these lubricating oils may be used, or two or more types may be appropriately combined and used.

In addition, various known additives other than the disproportionation inhibitor may be added to the working medium-containing composition. Specific examples of the additive include, but are not limited to, an antioxidant, a moisture scavenger, a metal inactivating agent, an anti-wear agent, an antifoaming agent, and the like. Antioxidants are used to improve the thermal stability, oxidation resistance, chemical stability, etc. of the refrigerant component or lubricating oil. Moisture scavengers are used to remove moisture when it enters the refrigeration cycle system, and in particular to suppress changes in the properties of the lubricating oil. The metal inactivating agent is used to suppress or prevent a chemical reaction caused by the catalytic action of a metal component. The anti-wear agent is used to reduce wear on sliding parts in the compressor, especially during high pressure operation. The defoaming agent is used especially for suppressing the generation of air bubbles in the lubricating oil.

The specific types of these additives are not particularly limited, and known compounds and the like can be preferably used depending on 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 appropriately combined and used. Further, the amount of these additives added is not particularly limited, and they should be added within a known range as long as the properties of the working medium for refrigeration cycle or the working medium-containing composition containing the same are not impaired. Can be done.

Further, in the working medium for a refrigeration cycle according to the present disclosure, as the disproportionation inhibitor, a compound other than the above-mentioned haloethane and capable of suppressing the disproportionation reaction can also be used in combination. Examples of such other disproportionation inhibitors include halomethane (methane halide) having the structure of the following formula (2).

CH _p X _q・ ・ ・ (2)
However, X in the 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. The sum of and q is 4, and when q is 2 or more, X is the same or different kind of halogen atom.

Specific examples of such halomethane include (mono) iodomethane (CH ₃ I), diiodomethane (CH ₂ I ₂ ), dibromomethane (CH ₂ Br ₂ ), bromomethane (CH ₃ Br), and dichloromethane ( CH ₂ Cl ₂ ), _{chloroiodomethane (CH 2} ClI), dibromochloromethane (CHBr ₂ Cl), methane iodide (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 ), tri Fluoroiodomethane (CF ₃ I) and the like can be mentioned, but are not particularly limited. Only one type of these halomethanes may be used, or two or more types may be appropriately combined and used.

Among these, more preferable halomethanes include, for example, dibromomethane (CH ₂ Br ₂ ), bromomethane (CH ₃ Br), dibromo dichloromethane (CBr ₂ Cl ₂ ), trifluoroiodomethane (CF ₃ I) and the like. As a particularly preferable halomethane, trifluoroiodomethane (CF ₃ I) can be mentioned.

[Composition of working medium for refrigeration cycle]
The composition of the working medium for a refrigeration cycle according to the present disclosure is particularly limited as long as it contains 1,1,2-trifluoroethylene as a refrigerant component and the above-mentioned haloethane as a disproportionation inhibitor. Not done.

The content of 1,1,2-trifluoroethylene, which is a refrigerant component, is not particularly limited, but the total amount of the refrigerant component and the disproportionation inhibitor among the components constituting the working medium for the refrigeration cycle (for convenience of explanation). When "total amount of refrigerant-related components") is 100% by mass, the content of 1,1,2-trifluoroethylene may be 40% by mass or more, and the content of 1,1,2-trifluoroethylene may be 40% by mass or more. As described above, the lower limit of the content may be 40% by mass, but it is preferably 45% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.

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

Further, the upper limit of the content of 1,1,2-trifluoroethylene is not particularly limited, but may be 99.9% by mass or less of the total amount of the refrigerant-related components. As will be described later, since the preferable lower limit of haloethane, which is an disproportion inhibitor, is 0.1% by mass, only 1,1,2-trifluoroethylene is used as the refrigerant component, and other refrigerant components are used. If not (100% by mass of 1,1,2-trifluoroethylene as the refrigerant component), the upper limit of the content of 1,1,2-trifluoroethylene in the total amount of the refrigerant-related components is inevitably high. It is 99.9% by 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, the above-mentioned difluoromethane is mentioned as a preferable example of other refrigerant components, and the preferable upper limit of the content of 1,1,2-trifluoroethylene, which is an essential refrigerant component, is 40 of the total amount of the refrigerant-related components. Since it is by mass%, the content of difluoromethane may be less than 60% by mass of the total amount of the refrigerant-related components. When other refrigerant components are contained, an example of a particularly preferable content of 1,1,2-trifluoroethylene may be in the range of 70% by mass to 80% by mass, but the content is limited to this. Not done.

The content of haloethane, which is a disproportionation inhibitor, is not particularly limited, but the upper limit thereof may be 10% by mass or less of the total amount of the refrigerant-related components, preferably 5% by mass or less, and 3% by mass or less. More preferably. As shown in Examples described later, the haloethane in the present disclosure can satisfactorily suppress or alleviate the disproportionation reaction of 1,1,2-trifluoroethylene even if the content is 5% by mass or less. it can. On the other hand, if the content of haloethane exceeds 10% by mass, the content of the disproportionation inhibitor becomes too large when viewed as a working medium for a refrigeration cycle, and good physical properties as a "refrigerant" cannot be exhibited. there is a possibility. Of course, it goes without saying that 10% by mass or more of the total amount of the refrigerant-related components may be added depending on the composition of the working medium for the refrigeration cycle.

The lower limit of haloethane is also not particularly limited, but may be 0.1% by mass or more of the total amount of the refrigerant-related components, preferably 0.5% by mass or more, and 1% by mass or more. Is more preferable. Although it depends on the specific composition of the working medium for the refrigeration cycle, when the haloethane content is less than 0.1% by mass, the disproportionation reaction of 1,1,2-trifluoroethylene is effectively suppressed or mitigated. It may not be possible.

Therefore, in the present disclosure, the range of the preferable content of haloethane, which is a disproportionation inhibitor, may be in the range of 0.1% by mass or more and 10% by mass or less of the total amount of the refrigerant-related components.

In general, in the working medium for a refrigeration cycle, the amount of impurities contained in the refrigerant component is often 2 to 3% by mass or less. The haloethane in the present disclosure can effectively suppress or alleviate the disproportionation reaction even when added to 1,1,2-trifluoroethylene at the impurity level. Therefore, the lower limit of the amount of haloethane added cannot always be specified, and each of the above lower limits gives a typical preferable example until it gets tired.

The content of the disproportionation inhibitor is not particularly limited even when a component other than haloethane, for example, the above-mentioned halomethane (for example, trifluoroiodomethane) is used in combination. Since the above-mentioned 10% by mass or less is mentioned as a preferable upper limit value of haloethane, the total amount of the disproportionation inhibitor is 10% by mass or less of the total amount of the refrigerant-related components even when haloethane and halomethane are used in combination. As described above, halomethane may be added.

[Configuration example of refrigeration cycle system]
Next, an example of a refrigeration cycle system configured by using the refrigeration cycle working medium according to the present disclosure will be described with reference to FIGS. 1 (A) and 1 (B).

The specific configuration of the refrigeration cycle system according to the present disclosure is not particularly limited, and any component such as a compressor, a condenser, an expansion means, and an evaporator may be connected by piping. Specific application examples of the refrigeration cycle system according to the present disclosure are also not particularly limited, and for example, an air conditioner (air conditioner), a refrigerator (household or commercial use), a dehumidifier, a showcase, an ice maker, and a heat pump type hot water supply. Machines, heat pump type washer-dryers, vending machines, etc. can be mentioned.

An air conditioner will be described as a typical application example of the refrigeration cycle system according to the present disclosure. 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, an outdoor unit 12, and a pipe 13 connecting them. 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 an annular shape by a pipe 13, whereby a refrigeration cycle is formed. 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 an annular shape by the pipe 13 in this order. Further, a four-way valve 18 for switching air conditioning is provided in the pipe 13 connecting the heat exchanger 14, the compressor 16, and the heat exchanger 15. The indoor unit 11 is provided with a blower fan, a temperature sensor, an operation unit and the like (not shown), and the outdoor unit 12 is provided with a blower, an accumulator and the like (not shown). Further, the pipe 13 is provided with various valve devices (including a 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 warmed 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 exchanges heat between the outside air sucked into the outdoor unit 12 by the blower and the refrigerant flowing inside the heat exchanger 15.

The specific configuration of the indoor unit 11 and the outdoor unit 12, the heat exchanger 14, 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, and the like. The specific configuration of the accumulator, other valve device, strainer, etc. is not particularly limited, and a known configuration can be preferably 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 condenses and liquefies. The liquefied liquid refrigerant is depressurized 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 to become a gas refrigerant by heat exchange with the indoor air. This gas refrigerant returns to the compressor 16 of the outdoor unit 12 via the four-way valve 18. The compressor 16 compresses the gas refrigerant and discharges it to the heat exchanger 15 again 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 condenses and liquefies due to heat exchange with the indoor 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 to the heat exchanger 14 of the indoor unit 11 again via 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. It is provided with a vessel 24, a pipe 25, and the like. Although not shown, the refrigerator 20 also includes a housing as a main body, a blower, an operation unit, a control unit, and the like.

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 low-pressure gas refrigerant. The compressor 21, the condenser 22, the decompression device 23, and the evaporator 24 are connected in a ring shape in this order by a pipe 25 for circulating the refrigerant gas, thereby forming 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 known configurations can be preferably used. it can. Further, the refrigerator 20 may have a known configuration other than these.

An example of the operation of the refrigerator 20 shown in FIG. 1B will be specifically described. 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 depressurized by passing through the depressurizing device 23 and sent to the evaporator 24. In the evaporator 24, the liquid refrigerant takes heat from the surroundings and vaporizes, 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 a refrigerator 20 is a refrigeration cycle system configured by using the above-mentioned refrigeration cycle operating medium. 1,1,2-trifluoroethylene used as a working medium for a refrigeration cycle has good properties as a refrigerant component and has a small ODP and GWP. Therefore, it is possible to realize an efficient refrigeration cycle system while reducing the impact on the environment.

Moreover, the working medium for the refrigeration cycle according to the present disclosure uses 1,1,2-trifluoroethylene as a refrigerant component and contains haloethane represented by the above formula (1) as a disproportionation inhibitor. There is. Therefore, even if heat is generated during the operation of the refrigeration cycle, the occurrence of a chain disproportionation reaction of 1,1,2-trifluoroethylene can be avoided, suppressed or mitigated. As a result, it is possible to effectively avoid the generation of soot due to the chain disproportionation reaction, 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 in more detail based on Examples and Comparative Examples, but the present disclosure is not limited thereto. Those skilled in the art may make various changes, modifications, and modifications without departing from the scope of the present disclosure.

(Experimental system of disproportionation reaction)
A pressure sensor (manufactured by Balcom Co., Ltd.) that measures the internal pressure inside a closed pressure-resistant container (Teflon inner cylinder closed container TAF-SR [trade name], internal volume 50 mL) manufactured by Pressure-Resistant Glass Industry Co., Ltd. VESVM10-2m [trade name]), thermocouple for measuring the internal temperature inside the pressure-resistant container (PL thermocouple ground PL-18-KA 4-T [trade name] manufactured by Conax Technologies), and the pressure-resistant container. A discharge device (UH-1 series mini mini welder [trade name] manufactured by AS ONE Co., Ltd.) for generating a discharge inside is installed, and 1,1,2-trifluoroethylene (manufactured by SynQuest Laboratories, Hydras Chemical), which is a refrigerant component, is installed. Sold by Co., Ltd., a gas cylinder containing 5% limonene (liquid phase) as a stabilizer) was connected so that the pressure could be adjusted. Further, the pressure sensor and the thermometer were connected to a data logger (GL220 type [trade name] manufactured by Graphtec Corporation, sampling interval of 10 milliseconds at the minimum). As a result, an experimental system for the 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-resistant container in the following comparative example or implementation is treated as a reference value especially when it exceeds 1000 ° C.

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

In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, a 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 within 1 to 2 seconds after one discharge was generated. After that, when the inside of the pressure-resistant container was checked after the internal pressure and the internal temperature were sufficiently lowered, it was confirmed that a considerable amount of soot was generated.

(Example 1)
In the above experimental system, 1,1,2-trifluoroethylene was introduced from the gas cylinder into the pressure-resistant container, and 1,1,1-trifluoro-2-iodoethane as a disproportionation inhibitor was added in an amount of 0.51% by mass. Was added so as to be the amount of addition.

In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharges were generated multiple 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 increase or decrease in temperature was observed even when the discharge was repeated twice.

(Example 2)
In the above experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure-resistant container, and 1,1,1-trifluoro-2-iodoethane as a disproportionation inhibitor was added in an amount of 1.27% by mass. Was added so as to be the amount of addition.

In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharges were generated multiple 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 increase or decrease in temperature was observed even after repeating the discharge 30 times. After that, the inside of the pressure-resistant container was checked after the internal pressure and the internal temperature were sufficiently lowered, but no soot was generated.

(Example 3)
In the above experimental system, 1,1,2-trifluoroethylene was introduced from the gas cylinder into the pressure-resistant container, and 1,1,1-trifluoro-2-iodoethane as a disproportionation inhibitor was added in an amount of 2.51% by mass. Was added so as to be the amount of addition.

In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharges were generated multiple 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 increase or decrease in temperature was observed even when the discharge was repeated twice. After that, the inside of the pressure-resistant container was checked after the internal pressure and the internal temperature were sufficiently lowered, but no soot was generated.

(Example 4)
In the above experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure-resistant container, and 1,1,1-trifluoro-2-iodoethane as a disproportionation inhibitor was added in an amount of 11.87% by mass. Was added so as to be the amount of addition.

In order to induce the disproportionation reaction of 1,1,2-trifluoroethylene, discharges were generated multiple 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 increase or decrease in temperature was observed even after the discharge was repeated 44 times. After that, the inside of the pressure-resistant container was checked after the internal pressure and the internal temperature were sufficiently lowered, but no soot was generated.

(Comparison of Comparative Example and Example)
From the results of the comparative example, by generating an electric discharge in the pressure-resistant container in the experimental system, a disproportionation reaction occurs in 1,1,2-trifluoroethylene, and this disproportionation reaction is chained and rapidly. You can see that it progresses. During this disproportionation reaction, the internal pressure rose to 7.8 MPa and the internal temperature rose to 880 ° C. (1157K).

On the other hand, from the results of Examples 1 to 4, by adding 1,1,1-trifluoro-2-iodoethane corresponding to the haloethane represented by the above formula (1), 1,1,2-trifluoroethylene can be obtained. It can be seen that the disproportionation reaction is effectively suppressed.

Further, from the results of Examples 1 to 3, the disproportionation reaction can be effectively suppressed by adding 10% by mass or less (more specifically, 3% by mass or less) of the haloethane represented by the formula (1). Understand. In particular, from the results of Example 1, it can be seen that the haloethane represented by the formula (1) can effectively suppress the chain of disproportionation reaction even with a small addition amount of 1.0% by mass or less.

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

The present invention can be suitably used in the field of working media used in refrigeration cycles, and is also an air conditioner (air conditioner), a refrigerator (household or commercial use), a dehumidifier, a showcase, an ice maker, and a heat pump type. It can be widely and suitably used in the field of refrigeration cycle systems such as water heaters, heat pump type washer / dryers, and vending machines.

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

Claims (7)

It contains at least 1,1,2-trifluoroethylene as a refrigerant component and
As a disproportionation inhibitor that suppresses the disproportionation reaction of 1,1,2-trifluoroethylene.
The following equation (1)
C ₂ H _m X _n ... (1)
(However, X in the formula (1) is Ri Ah with a halogen atom F, or I, m with is an integer of 1 or more n is an integer of 2 or more, further, the sum of m and n is 6 der Ri, X unless the only F, and the X Ru contains at least one I.)
It is characterized in that haloethane having the structure shown in is added.
Working medium for refrigeration cycle. The haloethane is characterized by being 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I).
The working medium for a refrigeration cycle according to claim 1. When the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass, the content of the haloethane is in the range of 0.1% by mass or more and 10% by mass or less.
The working medium for a refrigeration cycle according to claim 1 or 2. Further, as a disproportionation inhibitor, the following equation (2)
CH _p X _q・ ・ ・ (2)
(However, X in the 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 q is the sum of 4, and when q is 2 or more, X is the same or different kind of halogen atom.)
It is characterized in that halomethane having the structure shown in (except when X is only F) is added.
The working medium for a refrigeration cycle according to any one of claims 1 to 3. The halomethane is trifluoroiodomethane (CF ₃ I).
The working medium for a refrigeration cycle according to claim 4. Furthermore, it contains difluoromethane as a refrigerant component and also contains difluoromethane.
The content of the difluoromethane 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. A refrigeration cycle system configured by using the working medium for a refrigeration cycle according to any one of claims 1 to 6.

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