JP6979564B2 - Refrigeration cycle device - Google Patents

Description

The present invention relates to a refrigeration cycle device using a working medium containing HFO1123.

Generally, a refrigerating cycle device constitutes a refrigerating cycle by connecting a compressor, a four-way valve, a radiator (or a condenser), a decompressor such as a capillary tube or an expansion valve, an evaporator, etc., if necessary, by piping. A cooling or heating action is performed by circulating a refrigerating cycle working medium (refrigerant or heat medium) inside.

As the working medium for the refrigeration cycle in these refrigeration cycle devices, fluorocarbons (fluorocarbons are described as R ○○ or R ○○○ are specified by the US ASHRAE34 standard. Hereinafter, R ○○ or R ○ A halogenated hydrocarbon derived from methane or ethane called (shown as XX) is known.

R410A is often used as the refrigerant for the refrigeration cycle as described above, but the global warming potential (GWP) of the R410A refrigerant is as large as 2090, which is problematic from the viewpoint of preventing global warming.

Therefore, from the viewpoint of preventing global warming, for example, HFO1123 (1,1,2-trifluoroethylene) and HFO1132 (1,2-difluoroethylene) are attracting attention as small refrigerants for GWP (for example, 1,2-difluoroethylene). See Patent Document 1 or Patent Document 2).

International Publication No. 2012/157964 International Publication No. 2012/157765

However, HFO1123 (1,1,2-trifluoroethylene) and HFO1132 (1,2-difluoroethylene) are less stable than conventional refrigerants such as R410A, which causes disproportionation. An autolysis reaction called a reaction and a polymerization reaction following this autolysis reaction (hereinafter referred to as a disproportionation reaction) are likely to occur. The disproportionation reaction is only an autolysis reaction in a narrow sense, and is a self-decomposition reaction and a polymerization reaction following this autolysis reaction in a broad sense.

Since the disproportionation reaction increases in pressure with a large heat release, it may reduce the reliability of the compressor or refrigeration cycle device. Therefore, when HFO1123 or HFO1132 is used in a compressor or a refrigeration cycle device, it is necessary to suppress this disproportionation reaction.

Such a disproportionation reaction occurs as a starting point when high energy is applied in a refrigerant atmosphere where the temperature and pressure are excessively high.

For example, when a compressor is started, if a large amount of liquefied refrigerant is sucked in immediately after the compressor is started, a large load is applied to the motor unit, an excessive current flows, and the temperature of the motor unit suddenly rises. Rise. And if the current continues to be supplied as it is, it causes a phenomenon called layer short between the conductors of the stator windings that make up the stator of the motor, which becomes a high energy source and induces a disproportionation reaction. Become.

When the disproportionation reaction occurs, the pressure inside the compressor rises abnormally, which may reduce the reliability of the compressor and the refrigeration cycle device.

Therefore, the applicant proposes a working medium to which an disproportionation inhibitor such as HFO1123 (1,1,2-trifluoroethylene) or HFO1132 (1,2-difluoroethylene) is added to suppress or alleviate the disproportionation reaction. is doing.

The working medium to which the disproportionation inhibitor is added can suppress the disproportionation reaction and can improve the reliability of the refrigeration cycle apparatus. On the other hand, if the amount added to the working medium is large, the influence on the working medium becomes large and the performance of the refrigeration cycle is deteriorated.

Therefore, it is necessary to ensure that the effect is exhibited by adding the minimum necessary disproportionation inhibitor.

INDUSTRIAL APPLICABILITY The present invention has been made in view of such a point, and provides a refrigerating cycle apparatus having improved reliability without deteriorating the performance by effectively exerting the disproportionation suppressing effect of the disproportionation inhibitor. The purpose is.

In order to achieve the above object, the present invention comprises a refrigerating cycle circuit including a compression mechanism unit, an electric structure unit, a sealed compressor containing lubricating oil, a condenser, an expansion means, and an evaporator. In the refrigeration cycle apparatus in which the working medium containing trifluoroethylene is enclosed, the disproportioning inhibitor that suppresses the disproportionation reaction of 1,1,2-trifluoroethylene is added to the working medium, and the disproportionation is performed. The solubilization inhibitor has solubility in the lubricating oil, and the compatibility density when the disproportionation inhibitor is dissolved in the lubricating oil is the compatibility density when the refrigerant is dissolved in the lubricating oil. As a smaller refrigeration cycle device.

According to the above configuration, when the operation is stopped, more disproportionation inhibitor is accumulated on the liquid level of the lubricating oil accumulated in the compressor. Therefore, at the start of operation, the lubricating oil accumulated in the oil storage section is sequentially blown up from the surface and supplied into the working medium as small droplets, so that more disproportionation inhibitor is supplied to the vicinity of the motor section. be able to. Therefore, in the case where a large amount of the liquefaction actuating medium is sucked into the compressor immediately after the start-up and a large current flows through the motor unit to cause a layer short, the effect of the disproportionation inhibitor can be surely exerted. .. Therefore, the disproportionation reaction can be effectively suppressed, and the reliability of the refrigeration cycle apparatus can be improved.

According to the above configuration, the present invention can surely exert the effect of the disproportionation inhibitor, and can provide a highly reliable refrigeration cycle apparatus using a working medium containing HFO1123.

Schematic configuration diagram showing an air conditioner as a refrigeration cycle device according to the first embodiment of the present invention. Schematic configuration diagram showing a closed compressor of the air conditioner according to the first embodiment.

The first invention comprises 1,1,2-trifluoroethylene in a refrigeration cycle circuit including a compression mechanism, an electric structure, a closed compressor containing lubricating oil, a condenser, expansion means, and an evaporator. A refrigeration cycle apparatus in which a working medium is enclosed, in which a disproportionation inhibitor that suppresses the disproportionation reaction of 1,1,2-trifluoroethylene is added to the working medium, and the disproportionation inhibitor is added. Has solubility in the lubricating oil, and the compatibility density when the disproportionation inhibitor is dissolved in the lubricating oil is higher than the compatibility density when the working medium is dissolved in the lubricating oil. It is a substance that becomes smaller.

According to the above configuration, when the operation is stopped, more disproportionation inhibitor is accumulated on the liquid level of the lubricating oil accumulated in the compressor. Therefore, at the start of operation, the lubricating oil accumulated in the oil storage section is sequentially blown up from the surface and supplied into the working medium as small droplets, so that more disproportionation inhibitor is supplied to the vicinity of the motor section. be able to. Therefore, in the case where a large amount of the liquefaction actuating medium is sucked into the compressor immediately after the start-up and a large current flows through the motor unit to cause a layer short, the effect of the disproportionation inhibitor can be surely exerted. .. Therefore, the disproportionation reaction can be effectively suppressed, and the reliability of the refrigeration cycle apparatus can be improved.

In the second invention, the disproportionation inhibitor is the following formula (1).
CH _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, n. And m is the sum of 4, and when n is 2 or more, X is the same or different kind of halogen atom.)
Halomethane having the structure shown in (Except when X is only F) is added.

According to the above configuration, 1 halomethane as a disproportionation inhibitor satisfactorily captures 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 same can be improved.

According to the third aspect of the invention, in the first invention, the unsaturated hydrocarbon contains a saturated hydrocarbon having 2 to 5 carbon atoms, and the total amount of the refrigerant component and the unsaturated hydrocarbon is 100% by mass. Occasionally, the content of the 1,1,2-trifluoroethylene is 40% by mass or more, and the content of the saturated hydrocarbon is in the range of 0.6% by mass or more and 10% by mass or less. Is.

According to the above configuration, the saturated hydrocarbon within a predetermined range effectively suppresses the disproportionation reaction or alleviates the rapid progress of the disproportionation reaction. That is, in the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals cause a chain branching reaction, and saturated hydrocarbons favor these radicals. Can be captured. Therefore, even if the content of 1,1,2-trifluoroethylene in all the refrigerant components is increased, the disproportionation reaction can be effectively suppressed or the rapid progress of the disproportionation reaction can be alleviated. can. As a result, the reliability of the working medium for the refrigeration cycle and the refrigeration cycle system using the same can be improved.

In the fourth invention, in the first invention, the unsaturated inhibitor is a saturated hydrocarbon having 2 to 5 carbon atoms and a haloalkane having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine. , Is a configuration containing.

According to the above configuration, saturated hydrocarbons and haloalkanes as leveling inhibitors effectively suppress the disproportionation reaction and alleviate the rapid progress of the disproportionation reaction. That is, in the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals cause a chain branching reaction, but saturated hydrocarbons and haloalkanes are both. These radicals can be captured well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, and the rapid progress of the disproportionation reaction can be alleviated. Moreover, it is possible to suppress the disproportionation reaction or alleviate the progress in a smaller amount than when saturated hydrocarbon alone or haloalkane alone is added as a disproportionation inhibitor. As a result, the reliability of the working medium and the refrigerating cycle device using the working medium can be improved.

Hereinafter, embodiments of the present invention will be described with reference to the drawings, taking an air conditioner as an example. The present invention is not limited to this embodiment.

(Embodiment 1)
FIG. 1 is a schematic configuration diagram of an air conditioner according to the first embodiment of the present invention, and FIG. 2 is a schematic configuration diagram of a closed-type compressor used in the air conditioner.

The air conditioner 10 of 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 has 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, 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 (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 (working medium for refrigeration cycle) flowing inside the heat exchanger 14. conduct. 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.

A refrigerant (working medium for the refrigeration cycle) is sealed in the refrigeration cycle, and the compressor 16 compresses the refrigerant and circulates it in the refrigeration cycle. The compressor 16 is a so-called closed rotary compressor in which lubricating oil is sealed.

As shown in FIG. 2, the compressor 16 has a motor unit 162 and a compression mechanism unit 163 housed inside a closed container 161 that is an outer shell thereof, and the inside is filled with a high-temperature and high-pressure discharge refrigerant and lubricating oil. The bottom is an oil storage section 164 for storing lubricating oil. The motor motor 162a is a so-called brushless motor. The motor unit 162 includes a rotor 162b connected to the compression mechanism unit 163 and a stator 162c provided around the rotor 162b.

A three-phase stator winding is applied to the stator 162c, and a coil end is formed at the end portion of the stator 162c in the vertical direction. The ends of the three-phase stator windings are lead wires 165, respectively. That is, the stator 162c includes three lead wires 165 extending from each of the three-phase stator windings. The other ends of the three lead wires 165 are connected to the power supply terminal 166. The power supply terminal 166 includes three terminals, each of which is connected to the motor drive device 115.

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 and the like is not particularly limited, and a known configuration can be preferably used.

Next, the refrigerant (working medium for the refrigeration cycle) enclosed in the refrigeration cycle circuit will be described. In the working medium enclosed in the air conditioner 10 of the present embodiment, the refrigerant component is composed of at least 1,1,2-trifluoroethylene, and a disproportionation inhibitor is added.

The disproportioning inhibitor has solubility in the lubricating oil, and the compatibility density when the disproportioning inhibitor is dissolved in the lubricating oil is when the refrigerant is dissolved in the lubricating oil. It is smaller than the compatibility density of. The solubility of the disproportionation inhibitor in the lubricating oil decreases as the temperature and / or pressure increases.

For example, the following equation (1)
CH _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, n. And m is the sum of 4, and when n is 2 or more, X is the same or different kind of halogen atom.)
Halomethane having the structure shown in (except when X is F only).

The halomethane can satisfactorily capture radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals that cause a chain branching reaction of a 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 same can be improved.

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), methane iodide (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 can be mentioned, but are not particularly limited.

Only one kind of these disproportionation inhibitors may be used, or two or more kinds thereof may be used in combination as appropriate.

Among these, examples of the preferred halomethane as the disproportioning inhibitor include those containing bromine in the halogen atom X, and more preferable halomethanes include dibromomethane (CH ₂ Br ₂ ) and bromomethane. (CH ₃ Br) or dibromodichloromethane (CBr ₂ Cl ₂ ) can be mentioned.

Here, the amount of the halomethane added is 10 mol% or less when the total amount of the refrigerant component and the disproportionation inhibitor is 100 mol%. As a result, it is possible to effectively prevent the property of the refrigerant component (working medium for refrigeration cycle) from being affected by the excessive addition of halomethane, which is a disproportionation inhibitor.

In the refrigeration cycle working medium having the above configuration, the halomethane may have a configuration in which bromine is contained in the halogen atom X. Since halomethane, which is a disproportionation inhibitor, contains bromine, the disproportionation reaction of 1,1,2-trifluoroethylene can be suppressed or alleviated even more satisfactorily.

Further, in the working medium for a refrigeration cycle having the above configuration, the halomethane may be dibromomethane, bromomethane, or dibromodichloromethane. Since the halomethane as the disproportionation inhibitor is dibromomethane or bromomethane, the disproportionation reaction of 1,1,2-trifluoroethylene can be further suppressed or alleviated.

Furthermore, the refrigerating cycle operating medium having the above configuration may contain difluoromethane as a refrigerant component. Since difluoromethane has little impact on the environment like 1,1,2-trifluoroethylene, it can realize good properties as a working medium for a refrigeration cycle.

Next, the operation and effect of the air conditioner 10 configured as described above will be described below.

First, the basic operation of the air conditioner will be briefly explained. 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 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 due to heat exchange with the indoor air to become a gas refrigerant. 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 is condensed and liquefied by 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.

Next, the action and effect of the disproportionation inhibitor will be described.

During the above operation, the disproportionation inhibitor added to the refrigerant dissolves in the lubricating oil and stays as droplets in the closed container 161 of the compressor 16, and a part of the agent stays in the refrigerating cycle together with the refrigerant. Circulate.

Then, when the operation is stopped, the disproportionation inhibitor dissolves in the lubricating oil accumulated in the oil storage unit 164 of the compressor 16 and accumulates in the oil storage unit 164 together with the refrigerant. At this time, since the compatibility density when the disproportioning inhibitor is dissolved in the lubricating oil is smaller than the phase compatibility density when the refrigerant is dissolved in the lubricating oil, lubrication containing the disproportioning inhibitor Oil will be concentrated near the liquid level in the oil storage section.

As a result, at the start of operation, the lubricating oil accumulated in the oil storage unit 164 is sequentially blown up from the surface thereof, so that it becomes small droplets and is intensively supplied to the refrigerant. Then, a large amount of the disproportionation inhibitor stays in the vicinity of the motor unit 162.

Therefore, even if a large amount of liquefied refrigerant is sucked in immediately after the compressor 16 is started and a large current flows through the motor unit 162 to cause a layer short, disproportionation in the vicinity of the motor unit 162 may occur. The concentration of the inhibitor is high, and the disproportionation inhibitor effect is strongly exerted. Therefore, the disproportionation reaction that tends to occur immediately after activation can be reliably and effectively suppressed.

Further, since a large amount of the disproportionation inhibitor stays in the vicinity of the motor unit 162 when the disproportionation reaction is likely to occur in the motor unit 162, the disproportionation suppressing effect can be efficiently achieved even if the amount added is small. It can be demonstrated.

Therefore, it is possible to avoid affecting the thermal properties of the refrigerant component (working medium) composed of 1,1,2-trifluoroethylene by increasing the amount of the disproportionation inhibitor added, and the refrigerating cycle performance can be avoided. Can also be held high.

As the above-mentioned disproportionation inhibitor, halomethane (excluding the case where X is only F) is exemplified in the present embodiment, but in addition to halomethane (excluding the case where X is only F), the following substances are further used. Can be given.

One of them is a saturated hydrocarbon having 2 to 5 carbon atoms, which contains 1,1,2-trifluoroethylene when the total amount of the refrigerant component and the unsaturated inhibitor is 100% by mass. The amount is 40% by mass or more, and the content of the saturated hydrocarbon is within the range of 0.6% by mass or more and 10% by mass or less.

In the case of this disproportionation inhibitor, the disproportionation inhibitory action is as follows. That is, in the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals cause a chain branching reaction, and saturated hydrocarbons capture these radicals well. can do. Therefore, even if the content of 1,1,2-trifluoroethylene in all the refrigerant components is increased, the disproportionation reaction can be effectively suppressed or the rapid progress of the disproportionation reaction can be alleviated. can. As a result, the reliability of the working medium for the refrigeration cycle and the refrigeration cycle system using the same can be improved.

In the refrigeration cycle working medium having the above configuration, the saturated hydrocarbon may be n-propane.

According to the above configuration, if the saturated hydrocarbon is n-propane, it acts as a better disproportionation reaction inhibitor.

Further, in the working medium for a refrigeration cycle having the above configuration, the content of the saturated hydrocarbon in the total amount of the refrigerant component and the disproportionation inhibitor is within the range of 1.0% by mass or more and 9.5% by mass or less. It may be configured to be.

According to the above configuration, so that the content of saturated hydrocarbons is at least within the above range 1,
When mixed with 1,2-trifluoroethylene, the disproportionation reaction can be more effectively suppressed and the rapid progress can be further alleviated.

Further, the working medium for the refrigeration cycle having the above configuration 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 a configuration that is.

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 a working medium for a refrigeration cycle. be able to.

Further, the disproportionation inhibitor includes the following. That is, it contains saturated hydrocarbons having 2 to 5 carbon atoms and haloalkanes having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine.

In the case of this disproportionation inhibitor, the disproportionation inhibitory action is as follows. That is, according to the above configuration, saturated hydrocarbons and haloalkanes are added in combination as disproportionation inhibitors to the refrigerant component containing 1,1,2-trifluoroethylene (HFO1123) as a main component. In the disproportionation reaction of 1,1,2-trifluoroethylene, radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals cause a chain branching reaction, and saturated hydrocarbons and haloalkanes both cause these radicals. Can be captured well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, and the rapid progress of the disproportionation reaction can be alleviated.

Moreover, it is possible to suppress the disproportionation reaction or alleviate the progress in a smaller amount than when saturated hydrocarbon alone or haloalkane alone is added as a disproportionation inhibitor. As a result, the reliability of the working medium for the refrigeration cycle and the refrigeration cycle system using the same can be improved.

In the working medium for the refrigeration cycle having the above configuration, the haloalkane is 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 kind of halogen atom.)
It is a haloethane having the structure shown in (except when X is only F), or it is 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 further, 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 may be a configuration of halomethane having the structure shown in (except when X is only F).

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

Further, the working medium for a refrigeration cycle having the above configuration may contain the saturated hydrocarbon and at least one of the haloethane and the halomethane as the disproportionation inhibitor.

According to the above configuration, as a combination of the disproportion inhibitor, [1] a combination of three types of saturated hydrocarbon, haloethane and halomethane, [2] a combination of two types of saturated hydrocarbon and halomethane, or [3]. Since any combination of two types of saturated hydrocarbons and halomethanes will be used, suppression of disproportionation reaction or relaxation of progress can be satisfactorily realized.

Further, in the working medium for a refrigeration cycle having the above configuration, the halogen atom X is at least one of F and I in the halogen atom X, and the halomethane has a configuration in which bromine is contained in the halogen atom X. You may.

According to the above configuration, as the haloalkane, one that can better realize the effect of suppressing the disproportionation reaction or alleviating the progress, or one that 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 saturated hydrocarbon is n-propane and the haloethane is 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I). The halomethane may be configured to be trifluoroiodomethane (CF _{3 I).}

According to the above configuration, by using each of the above compounds as the saturated hydrocarbon and the haloalkane, suppression of the disproportionation reaction or relaxation of the progress can be better realized.

Further, the working medium for the refrigeration cycle having the above configuration 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 a configuration that is.

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 a working medium for a refrigeration cycle. be able to.

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

According to the above configuration, even if the total amount of saturated hydrocarbons and haloalkanes is suppressed to 3% by mass or less, the suppression of the disproportionation reaction or the relaxation of the progress can be satisfactorily realized. Therefore, even a small content (addition amount) can be used as a good disproportionation inhibitor.

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

According to the above configuration, when the total amount of saturated hydrocarbons and haloalkanes is 1.2% by mass or more, the disproportionation reaction can be suppressed or the progress can be alleviated particularly well. Therefore, even a small content (addition amount) can be used as a good disproportionation inhibitor.

The disproportionation inhibitor may be further composed of a substance containing any one of terpenes such as limonene, pican, camphene, cymene and terpinene, or terpenoids such as citronellol, tyrpineol and borneol.

Here, in any case, the working medium for the refrigeration cycle according to the present invention 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 (R32).

When the working medium for a refrigeration cycle according to the present invention contains other refrigerant components, it is sufficient that more than half of all the refrigerant components are 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 of only 1,1,2-trifluoroethylene.

Further, as the lubricating oil component used in combination 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 oils, ether-based lubricating oils, glycol-based lubricating oils, alkylbenzene-based lubricating oils, fluorine-based lubricating oils, mineral oils, hydrocarbon-based synthetic oils, 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.

Further, 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, antioxidants, moisture scavengers, metal deactivating agents, anti-wear agents, antifoaming agents 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 water when it has infiltrated into 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 due to the catalytic action of the 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 a refrigerating cycle according to the present invention or the working medium-containing composition containing the same are not impaired. Can be done.

There are various types of compressors such as scroll type, rotary type, reciprocating type, sliding vane type, etc., but if it is a closed type and the lubricating oil is sealed inside, it does not matter what type of compressor it is. The same effect can be achieved. Further, it may not be necessary to provide parts such as an accumulator and a strainer depending on the type of compressor, but the same effect can be exhibited regardless of the presence or absence.

In the present embodiment, an air conditioner has been described as an example of a refrigerating cycle device, but this is a refrigerating system in which components such as a compressor, a condenser, an expansion means, and an evaporator are connected by piping. If it is a cycle device, specific application examples are not particularly limited, and for example, a refrigerator (household or commercial use), a dehumidifier, a showcase, an ice maker, a heat pump type water heater, a heat pump type washer / dryer, and a vending machine. And so on.

As described above, the present invention can surely exert the effect of the disproportionation inhibitor, and can improve the reliability of the refrigeration cycle apparatus using the working medium containing HFO1123. Therefore, it can be widely applied to applications such as residential and commercial air conditioners, car air conditioners, water heaters, refrigerators / freezers, showcases, and dehumidifiers.

10 Air conditioner 11 Indoor unit 12 Outdoor unit 13 Piping 14, 15 Heat exchanger 16 Compressor 17 Decompression device 18 Four-way valve 161 Sealed container 162 Motor unit 163 Compression mechanism unit 164 Oil storage unit 165 Lead wire 166 Power supply terminal 162b Rotor 162c stator

Claims (3)

A refrigeration cycle in which a working medium containing 1,1,2-trifluoroethylene is enclosed in a refrigeration cycle circuit having a closed compressor containing a compression mechanism, a motor, and lubricating oil, a condenser, an expansion means, and an evaporator. In the apparatus, an disproportionation inhibitor that suppresses the disproportionation reaction of 1,1,2-trifluoroethylene is added to the working medium, and the disproportionation inhibitor is added.
As the disproportionation inhibitor, the following formula (1)
CHmXn ・ ・ ・ (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, n. And m is the sum of 4, and when n is 2 or more, X is the same or different kind of halogen atom.)
Halomethane having the structure shown in (except when X is only F) is added,
The disproportioning inhibitor has solubility in the lubricating oil, and the compatibility density when the disproportioning inhibitor is dissolved in the lubricating oil when the refrigeration cycle device is stopped is determined by the working medium. A refrigeration cycle device whose compatibility density is smaller than that when dissolved in the lubricating oil. When saturated hydrocarbons having 2 to 5 carbon atoms are added as the unsaturation inhibitor and the total amount of the refrigerant component and the unsaturation inhibitor is 100% by mass, the 1,1,2-trifluoro The refrigerating cycle apparatus according to claim 1, wherein the ethylene content is 40% by mass or more and the saturated hydrocarbon content is within the range of 0.6% by mass or more and 10% by mass or less. The first aspect of claim 1, wherein the disproportionation inhibitor contains a saturated hydrocarbon having 2 to 5 carbon atoms and a haloalkane having 1 or 2 carbon atoms and excluding the case where all halogen atoms are fluorine. Refrigeration cycle equipment.

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