JP2018177966A - Refrigeration cycle device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a refrigeration cycle device the safety of which is enhanced by reliably inhibiting a disproportionation reaction of a working medium containing HFO1123.SOLUTION: A disproportionation inhibitor of 1, 1, 2-trifluoroethylene is added to a working medium for a refrigeration cycle, so that surface tension when the disproportionation inhibitor is dissolved in lubricant is smaller than surface tension when a refrigerant is dissolved in the lubricant. As a result, a large amount of the disproportionation inhibitor adheres to the surface of a motor part occupying a large surface area in a hermetic type compressor. Namely, the disproportionation inhibitor for the motor part where an event inducing a disproportionation reaction such as layer short-circuit occurs, is increased to reliably exert an effect of the disproportionation inhibitor. Consequently, the disproportionation reaction can be reliably and efficiently inhibited with a small amount of the disproportionation inhibitor.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a refrigeration cycle apparatus using a working medium containing HFO 1123.

  In general, the refrigeration cycle apparatus comprises a compressor, and optionally a four-way valve, a radiator (or a condenser), a pressure reducing device such as a capillary tube or an expansion valve, an evaporator, etc. Cooling or heating is performed by circulating a working medium for the refrigeration cycle (refrigerant or heat medium) therein.

  As a working medium for a refrigeration cycle in these refrigeration cycle apparatuses, it is prescribed by the US ASHRAE 34 standard that fluorocarbons (fluorocarbons are described as R OO or R OO). Hereinafter, R OO or R OO Halogenated hydrocarbons derived from methane or ethane, designated as ○), are known.

  R410A is often used as the above refrigerant for refrigerant cycle, but the global warming potential (GWP) of the R410A refrigerant is as large as 2090, and there is a problem from the viewpoint of global warming prevention.

  Therefore, from the viewpoint of preventing global warming, for example, HFO 1123 (1,1,2-trifluoroethylene) and HFO 1132 (1,2-difluoroethylene) are attracting attention as refrigerants having a small GWP (for example, See Patent Document 1 or Patent Document 2).

International Publication No. 2012/157764 International Publication No. 2012/157765

  However, HFO 1123 (1,1,2-trifluoroethylene) and HFO 1132 (1,2-difluoroethylene) have lower stability than conventional refrigerants such as R410A, and as a result, disproportionation A self-decomposition reaction called a reaction and a polymerization reaction (hereinafter referred to as a disproportionation reaction) following this auto-degradation reaction tend to occur. The disproportionation reaction is, in a narrow sense, only an autolysis reaction, and in a broad sense is an autolysis reaction and a polymerization reaction following this autolysis reaction.

  The disproportionation reaction causes a pressure rise with a large heat release, which may lower the reliability of the compressor or the refrigeration cycle apparatus. For this reason, when using HFO1123 or HFO1132 for a compressor or a refrigeration cycle apparatus, it is necessary to suppress this disproportionation reaction.

  Such disproportionation reaction occurs as a starting point when high energy is added under an excessively high temperature and high pressure refrigerant atmosphere, particularly in a compressor.

  For example, in an example, the discharge pressure (the high pressure side of the refrigeration cycle) rises excessively if the operation is not under normal operating conditions, that is, if the blower fan on the condenser side stops or the refrigeration cycle circuit is blocked. .

  Under such a condition, a lock failure of the compressor occurs. Even under the lock failure, if the power supply to the compressor is continued, the power of the motor of the compressor is excessively supplied, and the motor generates heat abnormally. As a result, a phenomenon called a layer short occurs between the conductors of the stator winding which constitutes the stator of the motor, which becomes a high energy source and induces disproportionation reaction.

  And if disproportionation reaction generate | occur | produces, the pressure in a compressor will raise abnormally and there exists a possibility of reducing the reliability of a compressor or a refrigerating-cycle apparatus.

  Therefore, the applicant proposes a working medium to which a disproportionation inhibitor such as HFO 1123 (1,1,2-trifluoroethylene) or HFO 1132 (1,2-difluoroethylene) is added to suppress or mitigate disproportionation reaction. 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 will be large and the performance of the refrigeration cycle will be degraded.

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

  The present invention has been made in view of such a point, and is a refrigeration cycle apparatus having a disproportionation suppressing effect of a disproportionation inhibitor effectively exhibited to enhance reliability without reducing performance. It is intended to be provided.

  In order to achieve the above object, the present invention is directed to a refrigeration cycle circuit having a compressor, a motor, an enclosed unit containing a lubricating oil, a condenser, an expansion means, and an evaporator. In a refrigeration cycle apparatus enclosing a working medium containing trifluoroethylene, a disproportionation inhibitor for suppressing the disproportionation reaction of the 1,1,2-trifluoroethylene is added to the working medium, and the disproportionation inhibitor is used. Inhibitor is soluble in the lubricating oil, and the surface tension when the disproportionation inhibitor is dissolved in the lubricating oil is determined by the surface tension when the working medium is dissolved in the lubricating oil Also as a small refrigeration cycle device.

  According to the above configuration, since the surface tension is low when the disproportionation inhibitor is dissolved in the lubricating oil, the liquid having a small surface tension, that is, the lubricating oil in which the disproportionation inhibitor is dissolved has high wettability, and the closed type Much adheres to the surface of the motor part which occupies a large surface area in the compressor. That is, the disproportionation inhibitor of the motor part in which the event which induces disproportionation reaction, such as layer short, occurs increases. Thereby, the disproportionation inhibitor can reliably exhibit its effect. Therefore, disproportionation reaction can be reliably suppressed, and the reliability of the refrigeration cycle apparatus can be enhanced.

  ADVANTAGE OF THE INVENTION this invention can exhibit the effect of a disproportionation inhibitor reliably by the said structure, and can provide a highly reliable refrigerating-cycle apparatus using the working medium containing HFO1123.

The schematic block diagram which shows the air conditioner as a refrigerating-cycle apparatus which concerns on Embodiment 1 of this invention The schematic block diagram which shows the closed type compressor of the air conditioner concerning the Embodiment 1

  According to a first aspect of the present invention, a refrigeration cycle circuit having a hermetic compressor, a condenser, an expansion means, and an evaporator including a compression mechanism part, an electric structure part, and a lubricating oil includes 1,1,2-trifluoroethylene. A refrigeration cycle apparatus in which a working medium is enclosed, wherein a disproportionation inhibitor for suppressing disproportionation reaction of the 1,1,2-trifluoroethylene is added to the working medium, and the disproportionation inhibitor Is soluble in the lubricating oil, and the surface tension when the disproportionation inhibitor is dissolved in the lubricating oil is smaller than the surface tension when the working medium is dissolved in the lubricating oil As a cycle device.

  According to the above configuration, since the surface tension is low when the disproportionation inhibitor is dissolved in the lubricating oil, the liquid having a small surface tension, that is, the lubricating oil in which the disproportionation inhibitor is dissolved has high wettability, and the closed type Much adheres to the surface of the motor part which occupies a large surface area in the compressor. That is, the disproportionation inhibitor of the motor part in which the event which induces disproportionation reaction, such as layer short, occurs increases. Thereby, the disproportionation inhibitor can reliably exhibit its effect. Therefore, disproportionation reaction can be reliably suppressed, and the reliability of the refrigeration cycle apparatus can be enhanced.

2nd invention is 1st invention, The said disproportionation inhibitor is following Formula (1)
CH _m X _n ... (1)
(Wherein 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 and n is an integer of 1 or more, and further n And the sum of m is 4, and when n is 2 or more, X is a halogen atom of the same or different types.)
Halomethane having the structure shown in (except in the case where X is only F).

  According to the above configuration, the halomethane serving as a disproportionation inhibitor well captures radicals such as a fluorine radical, a fluoromethyl radical, and a fluoromethylene radical which 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 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.

  In a third invention according to the first invention, the disproportionation inhibitor contains a saturated hydrocarbon having 2 to 5 carbon atoms, and the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass. Sometimes, 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 to 10% by mass. It is.

  According to the above configuration, the saturated hydrocarbon within the predetermined range effectively suppresses the disproportionation reaction or mitigates the rapid progress of the disproportionation reaction. That is, in the disproportionation reaction of 1,1,2-trifluoroethylene, a chain branching reaction is caused by radicals such as fluorine radical, fluoromethyl radical, and fluoromethylene radical, but the saturated hydrocarbon is good for these radicals. It can be captured. Therefore, even if the content of 1,1,2-trifluoroethylene is increased in all the refrigerant components, the disproportionation reaction can be effectively suppressed or the rapid progress of the disproportionation reaction can be mitigated. it can. As a result, the reliability of the working medium and the refrigeration cycle apparatus using the same can be improved.

  In a fourth invention according to the first invention, the disproportionation inhibitor is a saturated hydrocarbon having 2 to 5 carbon atoms, and a haloalkane having 1 or 2 carbon atoms and excluding all halogen atoms of fluorine. And.

According to the above configuration, the saturated hydrocarbon and haloalkane serving as the disproportionation inhibitor 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, a chain branching reaction is caused by radicals such as fluorine radical, fluoromethyl radical, and fluoromethylene radical, but both saturated hydrocarbon and haloalkane are These radicals can be trapped well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, or the rapid progress of the disproportionation reaction can be alleviated. In addition, it is also possible to realize suppression or disproportionation of the disproportionation reaction in a smaller amount than when a saturated hydrocarbon alone or a haloalkane alone is added as a disproportionation inhibitor. As a result, the reliability of the working medium and the refrigeration cycle apparatus using the same can be improved.

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

Embodiment 1
FIG. 1 is a schematic block diagram of an air conditioner according to Embodiment 1 of the present invention, and FIG. 2 is a schematic block diagram of a hermetic compressor used in the air conditioner.

  The air conditioner 10 of the present embodiment includes the indoor unit 11 and the outdoor unit 12 and the pipe 13 connecting them, the indoor unit 11 includes the heat exchanger 14, and the outdoor unit 12 includes the heat exchanger 15. , A compressor 16 and a pressure reducing device 17.

  The heat exchanger 14 of the indoor unit 11 and the heat exchanger 15 of the outdoor unit 12 are annularly connected by the pipe 13 to form 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 pressure reducing device 17 are annularly connected by the pipe 13. In addition, in the pipe 13 connecting the heat exchanger 14, the compressor 16 and the heat exchanger 15, a four-way valve 18 for switching between cooling and heating is provided. 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). Furthermore, the piping 13 is provided with various valve devices (including the four-way valve 18), a strainer, and the like (not shown).

  The heat exchanger 14 provided in the indoor unit 11 exchanges heat between room air sucked into the interior of the indoor unit 11 by the blower fan and the refrigerant (working medium for the refrigeration cycle) flowing inside the heat exchanger 14 Do. The indoor unit 11 blows the air warmed by heat exchange into the room at the time of heating and blows the air cooled by the heat exchange into the room at the time of cooling. The heat exchanger 15 provided in the outdoor unit 12 exchanges heat between the outside air sucked into the interior of the outdoor unit 12 by the blower and the refrigerant flowing in the heat exchanger 15.

  In the refrigeration cycle, a refrigerant (working medium for the refrigeration cycle) is enclosed, and the compressor 16 compresses the refrigerant and circulates it in the refrigeration cycle. The compressor 16 is a so-called hermetic rotary compressor, and lubricating oil is enclosed inside.

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

A three-phase stator winding is applied to the stator 162c, and a coil end is formed at the end in the vertical direction of the stator 162c. 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 feed terminal 166. The feed terminal 166 comprises three terminals, each of which is connected to the motor drive 115.

  The specific configurations of the indoor unit 11 and the outdoor unit 12, or the heat exchanger 14 or the heat exchanger 15, the compressor 16, the pressure reducing device 17, the four-way valve 18, the blower fan, the temperature sensor, the operation unit, the blower, The specific configuration of the accumulator, the other valve device, the strainer, etc. is not particularly limited, and a known configuration can be suitably used.

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

  The disproportionation inhibitor is soluble in the lubricating oil, and the surface tension when dissolved in the lubricating oil is smaller than the surface tension when the refrigerant is dissolved in the lubricating oil. is there.

For example, the following equation (1)
CH _m X _n ... (1)
(Wherein 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 and n is an integer of 1 or more, and further n And the sum of m is 4, and when n is 2 or more, X is a halogen atom of the same or different types.)
Halomethane having the structure shown in (except in the case where X is only F).

  The halomethane can well capture radicals such as fluorine radicals, fluoromethyl radicals, and fluoromethylene radicals that cause chain branching reaction of 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 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), four iodomethane (CI _4), carbon tetrabromide (CBr _4), bromotrichloromethane (CBrCl _3), dibromodichloromethane (CBr ₂ Cl _2), tribromofluoromethane (CBr ₃ F), fluoro iodomethane (CHFI _2), difluoro diiodo methane (CF ₂ I _2), dibromodifluoromethane (CBr ₂ F ₂ ), trifluoroiodomethane (CF ₃ I) and the like, but not particularly limited.

  Only one type of these disproportionation inhibitors may be used, or two or more types may be used in appropriate combination.

Among these, as preferable halomethane as a disproportionation inhibitor, for example, one containing bromine in a halogen atom X can be mentioned, and as more preferable halomethane, dibromomethane (CH ₂ Br ₂ ), bromomethane Mention may be made of (CH ₃ Br) or dibromodichloromethane (CBr ₂ Cl ₂ ).

Here, the addition amount of the halomethane is 10% of the total amount of the refrigerant component and the disproportionation inhibitor.
When it is 0 mol%, it is 10 mol% or less. Thereby, it is possible to effectively avoid affecting the properties of the refrigerant component (working medium for refrigeration cycle) due to the excessive addition of halomethane which is a disproportionation inhibitor.

  In the working medium for a refrigeration cycle of the above configuration, the halomethane may have a configuration in which the halogen atom X contains bromine. Since the disproportionation inhibitor halomethane contains bromine, the disproportionation reaction of 1,1,2-trifluoroethylene can be suppressed or mitigated better.

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

  Furthermore, in the working medium for a refrigeration cycle having the above-described configuration, difluoromethane may be contained as a refrigerant component. Similar to 1,1,2-trifluoroethylene, difluoromethane has less influence on the environment, so it can realize good properties as a working medium for a refrigeration cycle.

  Next, the effect of the air conditioner 10 comprised as mentioned above is demonstrated below.

  First, the basic operation of the air conditioner will be briefly described. 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 delivered to the heat exchanger 15 of the outdoor unit 12 through 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 is sent to the heat exchanger 14 of the indoor unit 11. In the heat exchanger 14, the liquid refrigerant evaporates by heat exchange with indoor air to be a gas refrigerant. The 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 to the heat exchanger 15 again via the four-way valve 18.

  In the heating operation, the compressor 16 of the outdoor unit 12 compresses and discharges the gas refrigerant, whereby the gas refrigerant is delivered to the heat exchanger 14 of the indoor unit 11 through the four-way valve 18. In the heat exchanger 14, the gas refrigerant is condensed and liquefied by heat exchange with the room air. The liquefied liquid refrigerant is decompressed by the pressure reducing device 17 to be 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.

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

  During the above operation, the disproportionation inhibitor added to the refrigerant is partially dissolved in the lubricating oil, and is squeezed together with the lubricating oil into the closed container 161 of the compressor 16 by the compression operation of the compression mechanism section 163. ing.

  The surface tension of the disproportionation inhibitor when dissolved in the lubricating oil is smaller than the surface tension when the refrigerant is dissolved in the lubricating oil, so the wettability is high and it is provided inside the compressor 16 It adheres to the surface of the components constituting the compression mechanism section 163 and the motor section 162.

At this time, since the motor unit 162 has electric wires and laminated electromagnetic steel plates, its surface area is large, and as a result, a large amount of disproportionation inhibitor adheres to the surface of components such as electromagnetic steel plates constituting the motor unit 162. It will be. In addition, when the pressure in the refrigeration cycle increases and the temperature rises and the disproportionation reaction is likely to occur, disproportionation suppression adhering to the surface of parts such as electromagnetic steel plate constituting the motor part 162 is suppressed. The agent evaporates to increase the concentration of the disproportionation inhibitor near the motor portion 162.

  That is, the concentration of the disproportionation inhibitor in the vicinity of the motor portion 162 where the phenomenon causing the disproportionation reaction, such as layer shorting, is likely to occur increases intensively, and the disproportionation inhibitor can strongly exert its effect. Become.

  Therefore, disproportionation reaction can be reliably prevented even if pressure increases and layer shorting occurs in the compressor 16, and the reliability of the refrigeration cycle apparatus can be secured.

  In addition, since the disproportionation inhibitor is concentrated and held in the motor portion 162 in the compressor 16, the disproportionation suppressing effect can be efficiently exhibited even if the addition ratio to the refrigerant is reduced. .

  Therefore, the addition amount of the disproportionation inhibitor can be increased to avoid affecting the properties of the refrigerant component (working medium) composed of 1,1,2-trifluoroethylene, and the refrigeration cycle performance is also high. Can be maintained.

  In addition, although the halomethane (except for the case where X is only F) was illustrated in the present embodiment as the above disproportionation inhibitor, the following may be further added other than the halomethane (except when only X is for F) Can be mentioned.

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

  In the case of this disproportionation inhibitor, disproportionation suppression action is as follows. That is, in the disproportionation reaction of 1,1,2-trifluoroethylene, a chain branching reaction is caused by radicals such as fluorine radical, fluoromethyl radical and fluoromethylene radical, but the saturated hydrocarbon captures these radicals well. can do. Therefore, even if the content of 1,1,2-trifluoroethylene is increased in all the refrigerant components, the disproportionation reaction can be effectively suppressed or the rapid progress of the disproportionation reaction can be mitigated. it 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 said structure, if a saturated hydrocarbon is n-propane, it will act as a still more favorable disproportionation reaction inhibitor.

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

According to the above configuration, the disproportionation reaction can be more effectively suppressed if it is mixed with 1,1,2-trifluoroethylene so that the content of saturated hydrocarbon is at least within the above range. Abrupt progress can be further mitigated.

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

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

  Further, as disproportionation inhibitors, there are the following. That is, it contains a saturated hydrocarbon having 2 to 5 carbon atoms and a haloalkane which has 1 or 2 carbon atoms and in which all the halogen atoms are fluorine.

  In the case of this disproportionation inhibitor, disproportionation suppression action is as follows. That is, according to the above configuration, a saturated hydrocarbon and a haloalkane are combined and added as a disproportionation inhibitor to a refrigerant component containing 1,1,2-trifluoroethylene (HFO 1123) as a main component. In the disproportionation reaction of 1,1,2-trifluoroethylene, chain branching reaction is caused by radicals such as fluorine radical, fluoromethyl radical and fluoromethylene radical, but both saturated hydrocarbon and haloalkane are these radicals. Can be captured well. Therefore, the disproportionation reaction of 1,1,2-trifluoroethylene can be effectively suppressed, or the rapid progress of the disproportionation reaction can be alleviated.

  In addition, it is also possible to realize suppression or disproportionation of the disproportionation reaction in a smaller amount than when a saturated hydrocarbon alone or a 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 a refrigeration cycle of the above configuration, the haloalkane is represented by the following formula (1)
C ₂ H _m X _n ... (1)
(Wherein 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 and 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 a halogen atom of the same or different types.)
A haloethane having the structure shown in (except in the case where X is only F), or the following formula (2)
CH _p X _q ... (2)
(Wherein 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 and q is an integer of 1 or more, and further p And the sum of q is 4, and when q is 2 or more, X is a halogen atom of the same or different types.)
The structure may be halomethane having the structure shown in (except in the case where X is only F).

  According to the above configuration, since haloethane shown in the above-mentioned formula (1) or halomethane shown in the above-mentioned formula (2) is used as the haloalkane, it is possible to well realize suppression of disproportionation reaction or relaxation it can.

  Moreover, in the working medium for a refrigeration cycle of the above configuration, the disproportionation inhibitor may include the saturated hydrocarbon and at least one of the haloethane and the halomethane.

  According to the above constitution, as the combination of disproportionation inhibitors, [1] combination of three kinds of saturated hydrocarbon, haloethane and halomethane, [2] combination of two kinds of saturated hydrocarbon and haloethane, or [3] The suppression of disproportionation reaction or the alleviation of the progress can be well realized because any combination of two kinds of combinations of saturated hydrocarbon and halomethane will be used.

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

  According to the above-mentioned configuration, as the haloalkane, one capable of realizing the effect of suppressing the disproportionation reaction or alleviating the progress better, or one which is not easily restricted in availability or handleability can be used.

Further, in the working medium for a refrigeration cycle of the above configuration, the saturated hydrocarbon is n-propane and the haloethane is 1,1,1-trifluoro-2-iodoethane (CF ₃ CH ₂ I), It may be configured that the halomethane is trifluoroiodomethane (CF ₃ I).

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

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

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

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

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

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

  According to the above configuration, if the total amount of saturated hydrocarbon and haloalkane is 1.2% by mass or more, suppression of disproportionation reaction or relaxation of progress can be realized particularly well. Therefore, even a small content (addition amount) can be used as a good disproportionation inhibitor.

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

  Here, the working medium for a refrigeration cycle according to the present invention may contain a compound other than 1,1,2-trifluoroethylene (other refrigerant component) as a refrigerant component in any case. Representative other refrigerant components include hydrofluorocarbons such as difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane, etc. Examples of the fluorocarbon (HFC) include hydrofluoroolefins (HFO) such as monofluoropropene, trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluorobutene and the like, but are not particularly limited.

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

  In the working medium for a refrigeration cycle according to the present invention, when it contains another refrigerant component, half or more 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 constituted 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 suitably used. Specific examples of lubricating oils include ester-based lubricating oils, ether-based lubricating oils, glycol-based lubricating oils, alkylbenzene-based lubricating oils, fluorine-based lubricating oils, mineral oils, and hydrocarbon-based synthetic oils. It is not limited. These lubricating oils may be used alone or in combination of two or more.

  Moreover, well-known various additives other than a disproportionation inhibitor may be added to a working fluid containing composition. Specific additives include, but are not particularly limited to, antioxidants, water capture agents, metal deactivators, antiwear agents, antifoam agents and the like. Antioxidants are used to improve the thermal stability, oxidation resistance, chemical stability, etc. of the refrigerant component or lubricating oil. The water capturing agent is used to remove the water when the water intrudes into the refrigeration cycle system, and in particular, to suppress the change in the properties of the lubricating oil. Metal deactivators are used to inhibit or prevent the catalytic chemical reaction of metal components. Anti-wear agents are used to reduce wear on the sliding parts in the compressor, especially during high pressure operation. The antifoaming agent is used particularly to suppress the generation of air bubbles in the lubricating oil.

  The specific type of these additives is not particularly limited, and known compounds can be suitably used according to various conditions. In addition, as these additives, one kind of compound may be used, or two or more kinds of compounds may be appropriately combined and used. Furthermore, the addition amount of these additives is also not particularly limited, so long as the properties of the working medium for a refrigeration cycle according to the present invention or the working medium-containing composition containing the same are not impaired. Can.

There are various types of compressors, such as scroll type, rotary type, reciprocating type, sliding vane type, etc., but if it is a sealed type and lubricating oil is enclosed inside, it does not depend on the type of compressor. Similar effects can be exhibited. Further, parts such as an accumulator and a strainer may not be required depending on the type of compressor, but the same effect can be exhibited regardless of the presence or absence.

  As described above, in the present embodiment, the air conditioner has been described as an example of the refrigeration cycle apparatus, but this is a refrigeration system in which components such as a compressor, a condenser, an expansion means, and an evaporator are connected by piping The specific application example is not particularly limited as long as it is a cycle device, and for example, a refrigerator (for home use, for business use), a dehumidifier, a showcase, an ice making machine, a heat pump type water heater, a heat pump type washing / drying machine, a vending machine Etc. can be mentioned.

  As described above, the present invention can reliably exert the effect of the disproportionation inhibitor, and can improve the reliability of the refrigeration cycle apparatus using the working medium containing HFO 1123. Therefore, the present invention can be widely applied to applications such as air conditioners for residences and businesses, car air conditioners, water heaters, refrigerator-freezers, showcases, dehumidifiers and the like.

DESCRIPTION OF SYMBOLS 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 Electric motor part 163 Compression mechanism part 164 Oil storage part 165 Lead wire 166 Feeding terminal 162b Rotor 162c stator

Claims (4)

Refrigeration cycle in which a working medium containing 1,1,2-trifluoroethylene is enclosed in a refrigeration cycle circuit having a compressor, a motor, a sealed compressor containing a lubricating oil, a condenser, an expansion means, and an evaporator. A disproportionation inhibitor for suppressing disproportionation reaction of said 1,1,2-trifluoroethylene to said working medium, and said disproportionation inhibitor for said lubricating oil A refrigeration cycle apparatus having solubility, wherein a surface tension when the disproportionation inhibitor is dissolved in the lubricating oil is smaller than a surface tension when the working medium is dissolved in the lubricating oil. As said disproportionation inhibitor, following Formula (1)
CH _m X _n ... (1)
(Wherein 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 and n is an integer of 1 or more, and further n And the sum of m is 4, and when n is 2 or more, X is a halogen atom of the same or different types.)
The refrigeration cycle apparatus according to claim 1, wherein halomethane (except in the case where X is only F) having the structure shown in is added. The saturated hydrocarbon having 2 to 5 carbon atoms is added as the disproportionation inhibitor, and the total amount of the refrigerant component and the disproportionation inhibitor is 100% by mass. The refrigeration cycle apparatus according to claim 1, wherein the content of ethylene is 40% by mass or more, and the content of the saturated hydrocarbon is in the range of 0.6% by mass to 10% by mass. The disproportionation inhibitor according to 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 the halogen atoms are fluorine. Refrigeration cycle equipment.

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