JP2017145380A - Actuation medium for refrigeration cycle and refrigeration cycle system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actuation medium for refrigeration cycle capable of effectively suppressing or alleviating a disproportionation reaction of 1,1,2-trifluoroethylene (HFO1123) and a refrigeration cycle system using the same.SOLUTION: An actuation medium for refrigeration cycle has a coolant component at least constituted by 1,1,2-trifluoroethylene and halomethane having a structure represented by CHX, where X is a halogen atom selected from a group consisting of F, Cl, Br, I, m is an integer of 0 or more and n is an integer of 1 or more and further the sum of n and m is 4 and X is same or different kind of halogen atom when n is 2, excluding the case that X is only F, added.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 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 disclosed in Patent Document 2, due to the low stability of 1,1,2-trifluoroethylene, self-decomposition reaction called disproportionation reaction and polymerization following this self-decomposition reaction It is also known that a reaction (hereinafter referred to as disproportionation reaction) tends 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 Japanese Patent Application Laid-Open No. 2015-200480

  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 lubricant (refrigeration machine oil) used in combination with a flame retardant. And a method is disclosed.

  However, since there are many unknown parts about the disproportionation reaction of 1,1,2-trifluoroethylene, an additive (disproportionation inhibitor) that can effectively suppress or alleviate the disproportionation reaction. Not particularly known.

  The present invention has been made to solve such a problem, and is a working medium for a refrigeration cycle capable of effectively suppressing or mitigating a disproportionation reaction of 1,1,2-trifluoroethylene. An object of the present invention is to provide a refrigeration cycle system using the same.

In order to solve the above-mentioned problem, the working medium for the refrigeration cycle according to the present invention is composed of at least 1,1,2-trifluoroethylene as a refrigerant component and has the following formula (1) as a disproportionation inhibitor. )
CH _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 n And the sum of m is 4 and when n is 2 or more, X is the same or different kind of halogen atom.)
A halomethane having a structure shown in (excluding the case where X is only F) is added.

  According to the said structure, the halomethane shown to the said Formula (1) is added as a disproportionation inhibitor with respect to the refrigerant | coolant component which has 1,1, 2- trifluoroethylene (HFO1123) as a main component. This halomethane can well trap 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, or the rapid progress of the disproportionation reaction can be reduced. As a result, it is possible to improve the reliability of the refrigeration cycle working medium and the refrigeration cycle system using the same.

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

  In the present invention, with the above configuration, a working medium for a refrigeration cycle capable of effectively suppressing or mitigating the disproportionation reaction of 1,1,2-trifluoroethylene, and a refrigeration cycle system using the same. There is an effect that it can be provided.

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

  The working medium for a refrigeration cycle according to the present invention includes a refrigerant component composed of at least 1,1,2-trifluoroethylene, and has a structure represented by the following formula (1) as a disproportionation inhibitor (X Except for the case where only F is added).

CH _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 n And the sum of m is 4 and when n is 2 or more, X is the same or different kind of halogen atom.)
According to the said structure, the halomethane shown to the said Formula (1) is added as a disproportionation inhibitor with respect to the refrigerant | coolant component which has 1,1, 2- trifluoroethylene (HFO1123) as a main component. This halomethane can well trap 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, or the rapid progress of the disproportionation reaction can be reduced. 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 amount of the halomethane added may be 10 mol% or less when the total amount of the refrigerant component and the disproportionation inhibitor is 100 mol%. .

  According to the said structure, since the addition amount of the halomethane which is a disproportionation inhibitor is restrict | limited, it is effectively avoided that the property of the refrigerant | coolant component (refrigeration cycle working medium) by the excessive addition of halomethane is influenced. be able to.

  In the refrigeration cycle working medium having the above-described configuration, the halomethane may have a configuration in which bromine is contained in the halogen atom X.

  According to the said structure, since the halomethane which is a disproportionation inhibitor contains a bromine, the disproportionation reaction of 1,1, 2- trifluoroethylene can be suppressed or relieve | moderated still more favorably.

  Further, the refrigeration cycle working medium having the above configuration may be configured such that the halomethane is dibromomethane, bromomethane, dibromodichloromethane, or trifluoroiodomethane.

  According to the said structure, since the halomethane which is a disproportionation inhibitor is a dibromomethane or a bromomethane, the disproportionation reaction of 1,1, 2- trifluoroethylene can be suppressed or relieve | moderated still more favorably.

  Further, the refrigeration cycle working medium having the above-described configuration may further include difluoromethane as a refrigerant component.

  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.

  Furthermore, the present invention 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, typical embodiments of the present invention will be specifically described. The working medium for a refrigeration cycle according to the present invention uses at least 1,1,2-trifluoroethylene (HFO1123) as a refrigerant component, and suppresses or reduces disproportionation of 1,1,2-trifluoroethylene. As a disproportionation inhibitor, halomethane (halogenated methane) satisfying specific conditions is added.

  In addition, the refrigerant | coolant cycle working medium concerning this invention may contain compounds other than 1, 1, 2- trifluoroethylene as a refrigerant | coolant component. In addition, the working medium for the refrigeration cycle according to the present invention only needs to be composed of at least a refrigerant component and a disproportionation inhibitor, but may contain components other than these.

[Refrigerant component]
In the working medium for a refrigeration cycle according to the present invention, at least 1,1,2-trifluoroethylene (HFO1123) is used as a refrigerant component. 1,1,2-trifluoroethylene has the structure of the following formula (2), 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 generated active radicals are generated due to heat generation in a high temperature and high pressure state, the active radicals react with 1,1,2-trifluoroethylene to generate the disproportionation reaction described above. 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, it has been uniquely found that halomethane (halogenated methane) satisfying specific conditions as described later can be a suitable disproportionation inhibitor.

  Here, the working medium for the refrigeration cycle according to the present invention 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, a particularly preferred example is difluoromethane (R32).

  In the refrigeration cycle working medium according to the present invention, when other refrigerant components are contained, more than half of all the refrigerant components may be 1,1,2-trifluoroethylene. Therefore, in the present invention, it can be said that 1,1,2-trifluoroethylene is the main component of the refrigerant component. Of course, the refrigerant component may be composed only of 1,1,2-trifluoroethylene.

[Disproportionation inhibitor]
The disproportionation inhibitor added to the working medium for a refrigeration cycle according to the present invention may be halomethane having the following formula (1) structure (which satisfies a specific condition).

CH _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 n and m is 4. When n is 2 or more, X is the same or different type of halogen atom.

That is, the halomethane represented by the formula (1) is a monohalomethane represented by the following formula (11), a dihalomethane represented by the following formula (12), a trihalomethane represented by the following formula (13), and a tetrahalomethane represented by the following formula (14). It may be at least one. X ₁ , X ₂ , X ₃ , and X ₄ in the halomethanes represented by these formulas (11) to (14) 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.

  However, from the halomethane represented by the formula (1), those in which X is composed of only F are excluded. 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 (1) 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), fluoroiodomethane (CHFI ₂ ), difluorodiiodomethane (CF ₂ I ₂ ), dibromodifluoromethane (CBr ₂ F ₂ ) , Trifluoroiodomethane (CF ₃ I), and the like. Only one kind of these disproportionation inhibitors may be used, or two or more kinds may be used in appropriate combination.

Among these, preferable halomethanes as disproportionation inhibitors include, for example, those in which bromine is contained in the halogen atom X, and more preferable halomethanes include dibromomethane (CH ₂ Br ₂ ), bromomethane. (CH ₃ Br), dibromodichloromethane (CBr ₂ Cl ₂ ), trifluoroiodomethane (CF ₃ I), or the like can be given.

  In the working medium for the refrigeration cycle according to the present invention, the amount of the disproportionation inhibitor added to the refrigerant component is not particularly limited, but when the total amount of the refrigerant component and the disproportionation inhibitor is 100 mol%, the disproportionation occurs. The addition amount of halomethane represented by the formula (1) as an inhibitor is preferably 10 mol% or less. That is, the upper limit of the amount of disproportionation inhibitor added can be 10 mol%. When the addition amount of halomethane represented by the formula (1) exceeds 10 mol%, the addition amount of the disproportionation inhibitor with respect to the total amount of refrigerant components in the working medium for the refrigeration cycle becomes too large, May affect properties.

  On the other hand, the lower limit of the addition amount of the disproportionation inhibitor varies depending on various conditions, and it is difficult to limit a suitable numerical value such as an upper limit value. For example, the amount of F radicals that can be assumed varies depending on the content of 1,1,2-trifluoroethylene in the refrigerant component. Specifically, when the refrigerant component is composed only of 1,1,2-trifluoroethylene, and when composed of 50 mol% 1,1,2-trifluoroethylene and 50 mol% difluoromethane. The amount of F radicals expected is clearly different. Therefore, the lower limit of the addition amount of the disproportionation inhibitor is not particularly limited.

  Needless to say, various conditions that may affect the amount of disproportionation inhibitor added are not limited to the content of 1,1,2-trifluoroethylene in the refrigerant component. For example, specific types of components constituting the refrigeration cycle system, components such as lubricating oil used in addition to the refrigerant components, and the like can also affect the amount of disproportionation inhibitor added. Moreover, depending on various conditions, the upper limit value is not necessarily limited to 10 mol%, and the disproportionation inhibitor (halomethane represented by the formula (1)) may be added in excess of 10 mol%.

  Here, the halomethane represented by the formula (1) includes a compound having a relatively large ozone depletion coefficient (ODP) and / or global warming potential (GWP). However, halomethane represented by the formula (1) is an additive added to the working medium for the refrigeration cycle as a disproportionation inhibitor, and as described above, the amount added is sufficiently smaller than the refrigerant component. Therefore, even if halomethane having a relatively large ODP or GWP is used, it does not significantly affect the environment.

  Thus, the working medium for a refrigeration cycle according to the present invention adds halomethane represented by the formula (1) as a disproportionation inhibitor to a refrigerant component mainly composed of 1,1,2-trifluoroethylene. doing. This halomethane can well capture F radicals generated during the chain progression of the disproportionation reaction. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, or the rapid progress of the disproportionation reaction can be reduced. As a result, it is possible to improve the reliability of the refrigeration cycle working medium and the refrigeration cycle system using the same.

[Other ingredients that can be used in combination]
Since the refrigeration cycle working medium according to the present invention is used in a refrigeration cycle system, it can be used in combination with a lubricating 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 invention is a disproportionation inhibitor composed of a refrigerant component mainly composed of 1,1,2-trifluoroethylene and halomethane represented by the formula (1). And at least it may be configured. 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.

  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 refrigeration cycle according to the present invention or the working medium-containing composition containing the same are not impaired. Can do.

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

  The specific configuration of the refrigeration cycle system according to the present invention 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 invention 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 invention, 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.

  Moreover, as another typical application example of the refrigeration cycle system according to the present invention, 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.

  Moreover, the working medium for a refrigeration cycle according to the present invention uses 1,1,2-trifluoroethylene as a refrigerant component and contains halomethane represented by the above formula (1) as a disproportionation inhibitor. Yes. 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 invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In addition, measurement / evaluation of various synthesis reactions and physical properties in the following examples were performed as follows.

(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.

(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 within 1 to 2 seconds after the discharge. Thereafter, when the inside of the pressure vessel was checked after the internal pressure and the internal temperature were sufficiently reduced, 1.0 g of soot was generated.

Example 1
In the experimental system, 1,1,2-trifluoroethylene was introduced into the pressure vessel from a gas cylinder, and 5.0 mol of dibromomethane (CH ₂ Br ₂ , manufactured by Kanto Chemical Co., Inc.) was used as a disproportionation inhibitor. % Addition amount. At this time, the partial pressure of 1,1,2-trifluoroethylene was 1.311 MPa, and the partial pressure of dibromomethane was 0.069 MPa.

  In order to induce a disproportionation reaction of 1,1,2-trifluoroethylene, discharge was generated by a discharge device at an internal temperature of about 27 ° C. (300 K), and an internal pressure and an internal temperature were measured by a data logger. As a result, no significant pressure increase or temperature increase was observed. 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 the pressure vessel, and dibromomethane, which is a disproportionation inhibitor, was added so as to have an addition amount of 9.0 mol%. At this time, the partial pressure of 1,1,2-trifluoroethylene was 1.1648 MPa, and the partial pressure of dibromomethane was 0.1152 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 22 ° C. (295.65 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. Thereafter, after the internal pressure and internal temperature were sufficiently reduced, the inside of the pressure vessel was confirmed, but no generation of soot was observed.

(Example 3)
In the experimental system, 1,1,2-trifluoroethylene was introduced from a gas cylinder into a pressure vessel and 1.0 mol of dibromodichloromethane (CBr ₂ Cl ₂ , manufactured by Wako Chemical Co., Ltd.) was used as a disproportionation inhibitor. % Addition amount. At this time, the partial pressure of 1,1,2-trifluoroethylene was 1.16 MPa, and the partial pressure of dibromodichloromethane was 0.0117 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 23 ° C. (296.75 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 after one discharge.

Example 4
In the experimental system, 1,1,2-trifluoroethylene was introduced into the pressure vessel from the gas cylinder, and 1.0 mol% of trifluoroiodomethane (CF ₃ I, manufactured by SynQuest Laboratories) was used as a disproportionation inhibitor. It added so that it might become the addition amount of. At this time, the partial pressure of 1,1,2-trifluoroethylene was 1.1880 MPa, and the partial pressure of trifluoroiodomethane was 0.0120 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 21 ° C. (294.25 K), and the internal pressure and internal temperature were measured by a data logger. . As a result, although the temperature rose to 1.5 MPa for a moment after the discharge, the temperature rise was hardly seen.

(Example 5)
In the experimental system, 1,1,2-trifluoroethylene was introduced into the pressure vessel from the gas cylinder, and trifluoroiodomethane, which is a disproportionation inhibitor, was added to an addition amount of 5.0 mol%. did. At this time, the partial pressure of 1,1,2-trifluoroethylene was 1.1780 MPa, and the partial pressure of trifluoroiodomethane was 0.0620 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 22 ° C. (295.25 K), and the internal pressure and internal temperature were measured by a data logger. . As a result, although it rose to 1.5 MPa and 61 ° C. (334 K) for a moment after discharge, no extreme pressure increase or temperature increase was observed.

(Comparison between Comparative Example and Example)
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 5, by adding dibromomethane, dibromodichloromethane, or trifluoroiodomethane corresponding to the halomethane represented by the formula (1), 1,1,2-trifluoroethylene It can be seen that the leveling reaction is effectively suppressed.

  The results of Examples 1, 2 and 5 also show that the halomethane represented by the formula (1) can effectively suppress the disproportionation reaction with an addition amount of 10 mol% or less. Furthermore, from the results of Examples 3 and 4, the halomethanes represented by the above formula (1), for example, dibromodichloromethane or trifluoroiodomethane, exhibited a disproportionation reaction even when the addition amount was as small as 1.0 mol%. It turns out that a chain | strand can be suppressed effectively.

  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 (6)

The refrigerant component is composed of at least 1,1,2-trifluoroethylene,
The following formula (1)
CH _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 n And the sum of m is 4 and when n is 2 or more, X is the same or different kind of halogen atom.)
Halomethane having a structure shown in (except when X is only F) is added,
Working medium for refrigeration cycle. The addition amount of the halomethane is 10 mol% or less when the total amount of the refrigerant component and the halomethane is 100 mol%,
The working medium for a refrigeration cycle according to claim 1. The halomethane is characterized in that the halogen atom X contains bromine.
The working medium for a refrigeration cycle according to claim 1 or 2. Wherein the halomethane is dibromomethane, bromomethane, dibromodichloromethane, or trifluoroiodomethane,
The working medium for a refrigeration cycle according to claim 3. Furthermore, it contains difluoromethane as a refrigerant component,
The working medium for a refrigeration cycle according to any one of claims 1 to 4.   The refrigerating cycle system comprised using the working medium for refrigerating cycles of any one of Claim 1 to 5.

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