JPH09111230A - Mixed working fluid containing trifluoroiodomethane and refrigeration cycle apparatus using the same - Google Patents

Abstract

(57) [Abstract] [Problems] Halogenated hydrocarbons that have a problem in the environmental problem of global warming in the case of CFCs that have a problem of depleting the ozone layer in the stratosphere, and on the premise of using ester oil that is easily hydrolyzed It is an object of the present invention to provide a flame-retardant mixed working fluid that has almost no such influence in a similar type of refrigerant and can be used as it is in a conventional refrigeration cycle apparatus. A mixed working fluid comprising a lubricating oil other than an ester oil and a mixture, the mixture comprising 20-80 wt% trifluoroiodomethane and 20-80 wt% propylene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a mixed working fluid containing a lubricating oil other than ester oil, trifluoroiodomethane, hydrocarbons and a radical chain inhibitor, and a refrigerating machine such as an air conditioner and a refrigerator. The present invention relates to a cycle device.

[0002]

2. Description of the Related Art Generally, a refrigeration cycle device such as an air conditioner or a refrigerator is constructed by connecting a compressor, a condenser, an expansion mechanism (a throttle device such as a capillary tube or an expansion valve), an evaporator, an accumulator, etc. through piping. The cooling effect of the device is obtained by circulating the refrigerant inside the device. If a four-way valve is attached to the cycle device, not only a cooling effect but also a heating effect can be obtained. In these refrigeration cycle apparatuses, halogenated hydrocarbons derived from methane or ethane called fluorocarbons (hereinafter referred to as R ○○ or R ○○○) are used as a refrigerant.

In an air conditioner, a refrigerator, etc., the condensing temperature is about 50.degree. C. and the evaporation temperature is about 0.degree. Among them, chlorodifluoromethane (CHClF ₂ ,
R22, boiling point -40.8 ° C) is widely used as a refrigerant.

However, since this R22 has the ability to destroy ozone in the stratosphere, the restrictions on its use and production have already been determined by the International Convention on Montreal, and there is a movement to abolish its use and production in the future. is there.

In order to prevent such an influence from affecting the stratospheric ozone layer, it is a necessary condition that the molecular structure does not contain chlorine. Therefore, as this possibility, another chlorine-free alternative refrigerant of fluorohydrocarbons has been proposed.

[0006]

However, such a fluorohydrocarbon refrigerant has a problem in another environmental problem of global warming. The global warming potential (hereinafter referred to as G
WP), and GWP of fluorohydrocarbon refrigerants
Is said to have the same effect as R22. In other words, the 1994 IPCC (Intergovermental Panel on Climat)
According to the report of e Change, Intergovernmental Panel on Climate Change, when comparing the GWP of carbon dioxide (CO ₂ ) to 1, the GWP of R22 is 1700 when compared with the 100-year cumulative horizontal axis.
It is supposed to be. In addition, among fluorohydrocarbons that do not contain chlorine, GWP of difluoromethane (CH ₂ F ₂ , R32, boiling point -52 ° C) is 580, pentafluoroethane (CF ₃ -CHF ₂ , R125, boiling point -48 ° C). ) GWP is 32
00, 1,1,1-trifluoroethane (CF ₃ —CH ₃ , R
143a, boiling point -48 ° C) GWP is 4400, 1,
1,1,2-tetrafluoroethane (CF ₃ -CH ₂ F, R13
4a, boiling point −27 ° C.) has a GWP of 1300, 1,1-difluoroethane (CHF ₂ —CH ₃ , R152a, boiling point −25)
GWP of (° C.) is set to 140.

Further, the refrigerant of fluorohydrocarbons has poor compatibility with mineral oil and some synthetic oils which have been used as conventional lubricating oils for compressors, and therefore is discharged together with the refrigerant from the compressor. The lubricating oil may not return to the compressor from the low temperature evaporator. Therefore, when fluorocarbons are used as a refrigerant, it is considered that ester oil having good compatibility is used as a lubricating oil for a compressor. However, since ester oil is easily hydrolyzed, it is necessary to pay close attention to the reliability of chemical materials.

Therefore, the present invention has been tried in view of the above-mentioned problems, and can be used together with a conventional lubricating oil for a compressor, has almost no effect on the stratospheric ozone layer, and causes global warming. It is an object of the present invention to provide a mixed working fluid containing a refrigerant that is an alternative to R22 and has a small effect on

It is another object of the present invention to provide a mixed working fluid containing chlorine-free trifluoroiodomethane, hydrocarbons, a lubricating oil other than ester oil, and a radical chain inhibitor.

A further object of the present invention is to provide a refrigeration cycle apparatus which uses a lubricating oil other than ester oil, trifluoroiodomethane and hydrocarbons as a mixed working fluid.

[0011]

[Means for Solving the Problems] Hydrocarbons are
Since it has almost no effect on the stratospheric ozone layer and almost no effect on global warming, it has been proposed as an alternative refrigerant for fluorohydrocarbons such as R22 that can be used as it is.

For example, propane (C ₃ H ₈ , R290, boiling point -42.1 ° C) has a boiling point close to that of R22, and thus R
22 have been proposed as alternative refrigerants. Further, since the vapor pressure with respect to temperature of propane (R290) is similar to that of R22, the vapor pressure of R22 at a temperature of 0 ° C. or higher is R22.
It is lower than that of R22 and the refrigerating capacity is reduced by about 20%.

Hydrocarbons have a good chemical compatibility with mineral oils and some synthetic oils because they have similar chemical structures. For this reason, it becomes possible to use hydrocarbons together with conventional compressor lubricating oils other than ester oils.

However, hydrocarbons have explosive flammability as the biggest drawback. For this reason,
In order to use these as refrigerants for refrigeration cycle devices such as air conditioners and refrigerators, strict explosion-proof measures are required, resulting in excessive equipment costs and poor usability.

By the way, trifluoroiodomethane (CF
₃ I, boiling point −22.7 ° C.), also known as iodotrifluoromethane or trifluoromethyl iodide, consists of only 1 carbon atom, 3 fluorine atoms and 1 iodine atom,
Since chlorine is not contained in the molecular structure, it has almost no effect on stratospheric ozone depletion. The GWP of trifluoroiodomethane is considerably smaller than that of fluorohydrocarbons, and is almost the same as carbon dioxide (CO ₂ ). In addition, trifluoroiodomethane has been attracting attention as a non-combustible substance having a negative catalytic effect, and can reduce the flammability of hydrocarbons and make them incombustible depending on the amount mixed. Further, it can be used together with a lubricating oil for a compressor other than the ester oil without inhibiting the compatibility of the hydrocarbons with the mineral oil and some synthetic oils.

Therefore, propylene (R1270) is used as a hydrocarbon in the mixed working fluid of the present invention. Propylene (C ₃ H _6, R1270, boiling -4
7.7 ° C.) are hydrocarbons having a double bond having a lower boiling point than R22.

In the present invention, trifluoroiodomethane is mixed with propylene (R1270) and the composition range is specified to form a mixture having a boiling point equivalent to that of R22 and to make it incombustible. The mixed working fluid can be used as an alternative refrigerant for R22.

Further, in the present invention, a mixture of trifluoroiodomethane and propylene (R1270) is further added with propane (C ₃ H ₈ , R290, boiling point -42.1 ° C.) or cyclopropane (C ₃ H ₆ , RC270). , Boiling point −33 ° C.) or isobutane (iC ₄ H ₈ , R600a, boiling point −11.7)
C) and specify the composition range, R2
By forming a mixture having a boiling point equivalent to 2 and making it incombustible, the mixed working fluid can be used as a substitute refrigerant for R22.

Further, the inclusion of a radical chain inhibitor in these refrigerants can contribute to the stabilization of trifluoroiodomethane.

Therefore, the present invention is a mixed working fluid containing a lubricating oil other than ester oil, chlorine-free trifluoroiodomethane and hydrocarbons, the hardrocarbons being the main components of propylene ( R1
270), and further propane (R290) or cyclopropane (RC270) or isobutane (R60)
0a) is included.

The present invention also specifies the composition range of trifluoroiodomethane so that it can be flame retarded as a mixture.

Further, the present invention specifies the composition range of the mixture of trifluoroiodomethane and hydrocarbons so that the vapor pressure of the mixture becomes almost equal to R22.

The present invention also stabilizes trifluoroiodomethane by including a radical chain inhibitor.

Further, the present invention is a refrigeration cycle apparatus using these mixed working fluids.

The present invention makes it possible to make almost no influence on the stratospheric ozone layer by forming the refrigerant as a mixture of chlorine-free trifluoroiodomethane and hydrocarbons by the above combination. The ODP in the specified composition range is also expected to be 0.

Further, such a mixture is much smaller than the GWP of R22 and may be almost as carbon dioxide (CO ₂ ) as trifluoroiodomethane and GW.
Propylene with almost no P (R1270), propane with little GWP (R290) or cyclopropane (RC270) or isobutane (R600)
Since it is composed of only one of a), the refrigerant mixed with these has almost no effect on global warming.

Further, since trifluoroiodomethane is a nonflammable substance having a negative catalytic effect, propylene (R12
70) or a mixture of propane (R290) or cyclopropane (RC270) or isobutane (R600a) with a composition range further limited to a flame-retardant range so that a compressor lubricating oil other than ester oil can be used together. It can be used as it is in a normal refrigeration cycle device. As the lubricating oil required for the compressor, not only conventional mineral oil and alkylbenzene oil, but also non-hydrolyzing lubricating oil such as ether oil and fluorine oil can be used.

Furthermore, in the present invention, when only R1270, which has a lower boiling point than R22, and trifluoroiodomethane, which has a higher boiling point than R22, are mixed, the operating temperature of the refrigeration cycle apparatus such as an air conditioner is approximately 0 to approximately. At 50 ° C., it has a vapor pressure equivalent to that of R22 and has the same coefficient of performance, so that it is possible to provide a refrigerant that can be used even in the existing equipment using R22.

The present invention also provides R having a lower boiling point than R22.
When 1270 and R290, which has a higher boiling point than R22 at 0 ° C. or higher, are mixed with trifluoroiodomethane, the composition range is specified so that the operating temperature of the refrigeration cycle apparatus such as an air conditioner is approximately 0 to approximately. At 50 ° C., it has a vapor pressure equivalent to that of R22 and is expected to have a coefficient of performance equivalent to that of R22. Therefore, it is possible to provide a refrigerant that can be used even in a current device using R22.

The present invention also provides R, which has a lower boiling point than R22.
When 1270 and RC270, which has a higher boiling point than R22, and trifluoroiodomethane are mixed, by specifying the composition range thereof, at a use temperature of a refrigeration cycle device such as an air conditioner of approximately 0 to approximately 50 ° C., R22
Since it has a vapor pressure equivalent to that of R22 and can be expected to have a coefficient of performance equivalent to that of R22, it is possible to provide a refrigerant that can be used in existing equipment using R22.

The present invention also provides R having a lower boiling point than R22.
When 1270 and R600a are mixed with trifluoroiodomethane having a boiling point higher than that of R22, by specifying the composition range thereof, at a use temperature of a refrigeration cycle device such as an air conditioner of approximately 0 to approximately 50 ° C., R22
Since it has a vapor pressure equivalent to that of R22 and can be expected to have a coefficient of performance equivalent to that of R22, it is possible to provide a refrigerant that can be used in existing equipment using R22.

Further, the mixed refrigerant has a boiling point difference of about 40.
Propylene (R1270), Propane (R
290), cyclopropane (RC270), trifluoroiodomethane, and isobutane (R600a), resulting in a nearly azeotropic non-azeotropic mixture with a small temperature gradient in the condensation and evaporation processes. Therefore, a refrigeration cycle apparatus having a higher coefficient of performance (COP) than that of R22, which is a substitute, can be configured by configuring a Lorentz cycle in which the temperature difference between the heat source fluid such as air is close.

Further, the present invention is stabilized by adding a radical chain inhibitor. In other words, trifluoroiodomethane may decompose due to the release of iodine due to the incorporation of active molecules such as oxygen, but the trifluoromethane radical generated at that time and the chain decomposition reaction by the iodine radical or ion may occur. By stopping, it can be stably used for a long period of time.

Further, according to the present invention, since the accumulator of the refrigeration cycle such as the air conditioner is arranged on the outdoor side, the composition separation of the gas phase and the liquid phase occurs in the accumulator,
The concentration of flammable propylene increases and even if it leaks from the device it is released into the atmosphere, avoiding the danger of explosion.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention comprises a lubricating oil other than ester oil and a mixture, wherein the mixture comprises 20 to 80% by weight of trifluoroiodomethane and 20 to 80% by weight. % Propylene and a mixed working fluid.

The above mixture further comprises 60% by weight or less of propane, 40% by weight or less of cyclopropane or 2% by weight.
It may contain 5 wt% or less of either isobutane.

The invention described in claim 3 includes a lubricating oil other than ester oil and a mixture, and the mixture is 20 to 60.
Wt% trifluoroiodomethane and 20-70 wt%
Of propylene and 60% by weight or less of propane.

The invention according to claim 4 comprises a lubricating oil other than ester oil and a mixture, the mixture being 20-60.
Wt% trifluoroiodomethane and 40-80 wt%
Of propylene and 40% by weight or less of cyclopropane.

The invention according to claim 5 comprises a lubricating oil other than ester oil and a mixture, the mixture being 20 to 60.
Wt% trifluoroiodomethane and 40-80 wt%
Of propylene and 25% by weight or less of isobutane.

The mixed working fluid may further contain a radical chain inhibitor.

According to a seventh aspect of the present invention, a compressor, a condenser, an expansion mechanism and an evaporator are provided, a lubricating oil other than ester oil and a mixture are used as a mixed working fluid, and the refrigerant is 2
0-80 wt% trifluoroiodomethane and 20-8
The refrigeration cycle apparatus is characterized by containing 0% by weight of propylene.

The mixed working fluid may further contain a radical chain inhibitor.

Further, the refrigeration cycle apparatus may include an accumulator arranged outside the room.

Embodiments of the present invention will be described below with reference to the drawings.

An embodiment of the mixed working fluid of the present invention will be described. The mixed working fluid in the present embodiment contains a lubricating oil other than ester oil and a refrigerant, and the refrigerant is propane (R290) or cyclopropane (RC27).
0) or isobutane (R600a), and trifluoroiodomethane and propylene (R1270).

Here, propylene (R1270), propane (R290), cyclopropane (RC270), and isobutane (R600a) are combustible substances, and are referred to as "Refrigerant Freon emission reduction and alternative technology" edited by the Japan Refrigeration Association.
(Published March 1, 1994) According to page 81, the combustion range of propane in the air is 2.1 to 9.6 vol%, the combustion range of isobutane is 1.8 to 9.7 vol%, and propylene Although the combustion range of cyclopropane and cyclopropane is not described, it is known to be almost equivalent to propane and isobutane. The combustion range of the mixed refrigerant in the case of mixing an ordinary inert gas with these flammable substances is calculated by the method described on page 79 of the same document, and conversely of the inert gas for decompressing the mixed refrigerant. The composition ratio is also calculated. That is, when mixing a normal inert gas with hydrocarbons,
It can be seen that the mixed refrigerant can be almost made incombustible when the composition ratio of the inert gas is approximately 99% by weight or more. But,
Approximately 99% by weight when considered as a normal inert gas as described above
Where necessary above, when trifluoroiodomethane is used, since it has a strong negative catalytic action on combustion by iodine and fluorine, especially iodine, it is about 10
A nonflammable effect can be obtained from 20% by weight to 20% by weight or more.

The flammability test was carried out as follows as a simple burning test method.

First, as a first method, the volume is 75.6 m.
1 test tube or graduated cylinder of 325 ml in volume is used, the opening is installed at the bottom, the container is filled with a mixed gas of a predetermined concentration and sufficiently diffused, and then the opening is matched immediately after opening. Ignited by The combustion was determined by determining the combustion concentration when the flame reached the entire container from the lower opening, that is, the upper part of the container. By this method, a mixed gas composition having no combustion concentration was made nonflammable. As a verification of this method, when the combustion range of a single combustible gas was measured, the lower limit was ± 0.1 vol% and the upper limit was ± 0.4 vo
The experiment was performed after confirming that the agreement was within the range of 1%.

As a second method, the same container is installed with the opening on the top, the mixed gas of a predetermined concentration is filled in the container and sufficiently diffused, and then the opening is matched by a match immediately after opening. I ignited. The combustion was determined by determining the combustion concentration when the flame reached the entire container from the upper opening, that is, the lower part of the container. By this method, a mixed gas composition having no combustion concentration was made flame-retardant.

Non-flammable trifluoroiodomethane and flammable propylene (R1270), propane (R29
0), cyclopropane (RC270), isobutane (R
When mixed with 600a), the concentration of trifluoroiodomethane increased to about 2.5 vol in any combustible gas when the amount of trifluoriodomethane was increased.
%, Ie, about 10% by weight, becomes flame retardant, and about 5 vo
It was found that it became nonflammable from 1%, that is, about 20% by weight. The reason why trifluoroiodomethane can obtain the incombustibility effect from such a low mixture concentration is that the negative catalytic effect on the combustion of iodine or fluorine in the molecule works as described above.

Next, trifluoroiodomethane, propylene (R1270), propane (R290) or cyclopropane (RC270) or isobutane (R60).
The vapor pressure of the mixed refrigerant containing any one of
An embodiment of a composition range specified to be equivalent to will be described with reference to a vapor pressure diagram.

1A and 1B show propylene (C
₃ H ₆ , R1270, boiling point-47.7 ° C.) and trifluoroiodomethane (CF ₃ I, boiling point-22.7 ° C.) mixed refrigerant composed of a mixture of two kinds, a constant temperature of 0 ° C. and 5 ° C.
The equilibrium state at 0 ° C. is shown using Cartesian coordinates. In this rectangular coordinate, trifluoroiodomethane is arranged at the left end and R1270 is arranged at the right end, and the composition ratio (weight ratio) of each component at a certain point on the coordinate plane is R1.
It is represented as a composition of 270.

In FIG. 1B, 1L and 1V are temperatures 0.
Is the vapor-liquid equilibrium line of the mixture at 0 ° C, and the broken line is the pressure of 0.
This is a line of 498 MPa, and this temperature / pressure corresponds to the saturated state of R22 at a temperature of 0 ° C. The upper gas-liquid equilibrium line (corresponding to 0 ° C) 1L is the saturated liquidus line, and the lower gas-liquid equilibrium line (0 ° C)
1 V (corresponding to ° C) represents a saturated vapor phase line, and a vapor-liquid equilibrium state is reached in the range sandwiched by these lines. Moreover, FIG.
2 is a vapor-liquid equilibrium line composed of a saturated liquidus line 2L and a saturated vaporous line 2V of the mixture at a temperature of 50 ° C., and a broken line is a line of pressure 1.943 MPa, and this temperature / pressure is also the temperature of R22. This corresponds to a saturated state at 50 ° C.

Each point in FIG. 1 corresponds to the vapor phase composition (subscript V) and the liquid phase composition (subscript L) in the composition pairs A to E of the mixed refrigerant shown in (Table 1).

[0055]

[Table 1]

The points A _L to C _L are gas-liquid equilibrium lines (corresponding to 0 ° C.) 1
On the saturated liquid phase line 1L, points A _V to C _V are gas-liquid equilibrium lines (0 ° C).
(Corresponding to) 1 on the saturated vapor phase line 1V, the temperature at points B _L and B _V is 0 ° C., and the pressure is the same as R22. Therefore, point B
_The composition represented by the liquid phase composition of _L or the gas phase composition of point B _V achieves a saturated state under the conditions of the saturated vapor pressure of R22 at 0 ° C. Points D _L to E _L are on the saturated liquid phase line 1 _L of the gas-liquid equilibrium line (corresponding to 50 ° C.) 1 and points D _V to Point E _V are the saturated gas phase line 1 _V of the gas-liquid equilibrium line (corresponding to 50 ° C.) 1. Above, points D _L and D _V have a temperature of 50 ° C. and a pressure of R22.
Therefore, the composition represented by the liquid phase composition at the point D _L or the gas phase composition at the point D _V achieves the saturated state under the condition of the saturated vapor pressure of R22 at 50 ° C.

R1270 and trifluoroiodomethane are 38.9% and 61.1% by weight, respectively, and the composition at the point B _L on the saturated liquidus line 1L at the same pressure as R22 has the same temperature as R22. At 0 ° C., it vaporizes at the same pressure as R22 and liquefies at a pressure lower than R22. R1270 and trifluoroiodomethane are 58.1% by weight and 41.9% by weight, respectively, and the composition at the point B _V on the saturated vapor line 1V where the pressure is the same as that of R22 is 0 ° C. at the same temperature as R22. , R22 is vaporized at a pressure higher than R22 and liquefied at the same pressure as R22. The composition in the area between these two compositions vaporizes at a pressure higher than R22 and liquefies at a pressure lower than R22 at the same temperature of 0 ° C. as R22. That is, the composition in the area of the composition range while the gas-liquid equilibrium line 1 at 0 ° C. intersects with the pressure of 0.498 MPa changes the liquid phase to the gas phase at 0 ° C. at a pressure higher than R22,
At the same pressure as above, the liquid phase below 0 ° C evaporates and changes to the gas phase above 0 ° C.

Similarly, R1270 and trifluoroiodomethane are 60.8% by weight and 39.2% by weight, respectively, and the point D on the saturated liquidus line 2L at which the pressure is the same as that of R22.
The composition of _L vaporizes at the same temperature as R22 at 50 ° C. at the same pressure as R22 and liquefies at a pressure lower than R22. R
1270 and trifluoroiodomethane each 7
The composition at the point D _V on the saturated vapor phase line 2V at which the pressures of 0.8% by weight and 29.2% by weight are the same as those of R22 is R22.
At the same temperature of 50 ° C, vaporizes at a pressure higher than R22,
It liquefies at the same pressure as R22. The composition in the area between these two compositions shows that at the same temperature as R22, 50 ° C,
It vaporizes at a pressure higher than R22 and liquefies at a pressure lower than R22. That is, the vapor-liquid equilibrium line 2 at 50 ° C. has a pressure of 1.94.
The composition in the area of the composition range while intersecting with 3 MPa changes from a gas phase to a liquid phase at a pressure lower than R22 at 50 ° C., and a gas phase higher than 50 ° C. condenses at the same pressure as R22. Change to liquid phase below 50 ° C.

Here, the gas-liquid equilibrium line 1 at 0 ° C. has a pressure of 0.4.
The area where the vapor-liquid equilibrium line 2 at 50 ° C. intersects with the pressure of 1.943 MPa does not overlap, but conversely, the saturated vapor phase line 1V of the vapor-liquid parallel line 1 has a pressure of 0. The composition lying between the composition intersecting with .498 MPa and the composition having the saturated liquidus line 2L of the gas-liquid equilibrium line 2 intersecting with the pressure of 1.943 MPa has R22 at a temperature of 0 ° C to 50 ° C.
It can be seen that the compression ratio can be reduced due to the higher evaporation pressure and lower condensing pressure. Therefore, the composition between the composition in which the saturated liquidus line 1L of the gas-liquid parallel line 1 crosses the pressure of 0.498 MPa and the composition in which the saturated liquidus line 2V of the gas-liquid equilibrium line 2 crosses the pressure of 1.943 MPa are Since it has an evaporation pressure equal to or higher than that of R22 and a condensation pressure equal to or lower than that of R22 at a temperature of 0 ° C. to 50 ° C., it is suitable for a refrigeration cycle device such as an air conditioner or a refrigerator.

As can be seen from the figure, R1270 and trifluoroiodomethane are each approximately 40 to 70% by weight,
The composition range of about 30 to about 60% by weight is about 0.
It is desirable because it has a vapor pressure almost equal to that of R22 at a use temperature of about 50 ° C. Further, if a slight range of vapor pressure is allowed as compared with R22, a composition range in which R1270 and trifluoroiodomethane are approximately 20 to approximately 80% by weight and approximately 20 to approximately 80% by weight, respectively, is desirable.

Further, in the mixed refrigerant composed of two components of R1270 and trifluoroiodomethane of about 80% by weight and about 20% by weight, respectively, even if R1270 having a low boiling point leaks from the apparatus, the composition of R1270 at that time is leaked. Is less than approximately 90% by weight and is flame retardant,
It can be seen from (Table 1). Therefore, the composition range in which R1270 and trifluoroiodomethane are approximately 20 to approximately 80% by weight and approximately 20 to approximately 80% by weight, respectively, is R127.
It is desirable because it eliminates the flammability of 0 by the incombustibility of trifluoromethane.

Table 2 shows the ideal refrigeration performance of a binary system composed of propylene (R1270) and trifluoroiodomethane. The conditions are the case where the condensation average temperature is 50 ° C., the evaporation average temperature is 0 ° C., the condenser outlet supercooling degree is 0 deg, and the evaporator outlet superheat degree is 0 deg.

[0063]

[Table 2]

As can be seen from (Table 2), the two-component system consisting only of trifluoroiodomethane and propylene (R1270) has an increased refrigerating capacity as the amount of propylene increases, and R1270 and trifluoroiodomethane each contain about 20 to about 20%. The composition range of about 80% by weight, about 20 to about 20% by weight, has a refrigerating capacity inferior to that of R22 but secures a refrigerating capacity of propane (R290) or more, and the coefficient of performance shows the same characteristics as R22. In particular, the composition range in which R1270 and trifluoroiodomethane are about 40 to about 70% by weight and about 30 to about 60% by weight, respectively,
It has almost the same vapor pressure as R22. Low boiling point R12
Even if 70 leaks from the device, R at that time
The composition of 1270 never enters the combustion range, and R127
The flammability of 0 can be eliminated by the incombustibility of trifluoromethane. Further, the temperature gradient in the condensation process and the evaporation process is about 5 deg or less, and a near azeotropic mixture is formed. By utilizing this temperature gradient in reverse to construct a Lorentz cycle in which the temperature difference with the heat source fluid is close, a higher coefficient of performance can be expected than in (Table 2).

Next, FIG. 2 shows propylene (C ₃ H ₆ , R12
70, boiling point -47.7 ℃), propane (C ₃ H _8, R29
0, boiling point-42.1 ° C), trifluoroiodomethane (CF ₃ I, boiling point-22.7 ° C), the equilibrium state of the mixed refrigerant at a constant temperature and a constant pressure is represented by triangular coordinates. It is shown by using. In this triangular coordinate, a single substance is arranged at each vertex of the triangle counterclockwise from the upper vertex in the descending order of boiling point,
Composition ratio (weight ratio) of each component at a point on the coordinate plane
Is represented by the ratio of the distance between the point and each side of the triangle. At this time, the distance between the point and the side of the triangle corresponds to the composition ratio of the substance described at the vertex of the triangular coordinates on the side opposite to the side.

In FIG. 2, 1L and 1V are temperatures of 0 ° C.
This is a vapor-liquid equilibrium line of the mixed refrigerant at a pressure of 0.498 MPa, and this temperature / pressure corresponds to the saturated state at a temperature of R22 of 0 ° C. The upper vapor-liquid equilibrium line (corresponding to R220 ° C) 1V is the saturated vapor phase line, and the lower vapor-liquid equilibrium line (R220 ° C).
1 L represents a saturated liquidus line, and a gas-liquid equilibrium state is reached in the range sandwiched by the two lines. Further, 2 is a vapor-liquid equilibrium line consisting of a saturated liquidus line 2L and a saturated vaporous line 2V of the mixture at a temperature of 50 ° C. and a pressure of 1.943 MPa,
This temperature and pressure also correspond to the saturated state of R22 at a temperature of 50 ° C.

Each point in FIG. 2 corresponds to the vapor phase composition (subscript V) and the liquid phase composition (subscript L) in the composition pairs A to E of the mixed refrigerant shown in (Table 3).

[0068]

[Table 3]

Points A _L to C _L are gas-liquid equilibrium lines (R220 ° C.
Equivalent) 1 saturated liquid phase line 1L, points A _V to point C _V are gas-liquid equilibrium lines (R220 equivalent to 0 ° C) 1 saturated gas phase line 1 V, point D _L
~ Point E _L is on the saturated liquidus line 2L of the vapor-liquid equilibrium line (R22 50 ° C equivalent) 2, and points D _V to E _V are the gas-liquid equilibrium line (R225.
It is on the saturated vapor phase line 2V of 2). Therefore, the composition shown in the liquid phase composition or the gas phase composition of (Table 3) is 0
Saturation is achieved under conditions of saturated vapor pressure of R22 at ℃ or 50 ℃.

The composition on the saturated vapor phase line V is vaporized at a pressure higher than that of R22 at the same temperature as R22 and liquefied at the same pressure as R22. The composition on the saturated liquidus line L is vaporized at the same temperature as R22 at the same pressure as R22 and liquefied at a pressure lower than R22. The composition in the area between these two lines vaporizes at a pressure higher than R22 and liquefies at a pressure lower than R22 at the same temperature as R22. That is, the composition in the area between the vapor-liquid equilibrium lines 2 at 50 ° C. is 5
At 0 ° C, the gas phase changes to a liquid phase at a pressure lower than R22, and at the same pressure as R22, a gas phase higher than 50 ° C condenses and changes to a liquid phase lower than 50 ° C. The composition in the area between the vapor-liquid equilibrium line 1 at 0 ° C changes from the liquid phase to the vapor phase at a pressure higher than R22 at 0 ° C, and the liquid phase lower than 0 ° C evaporates at the same pressure as R22. Then, the gas phase changes to a temperature higher than 0 ° C.

Here, the area between the gas-liquid equilibrium line 1 at 0 ° C. and the area between the gas-liquid equilibrium line 2 at 50 ° C. does not overlap, but conversely, the saturated vapor phase of the gas-liquid parallel line 1 The composition between the line 1V and the saturated liquidus line 2L of the vapor-liquid equilibrium line 2 has a temperature of 0 ° C to 5 ° C.
It can be seen that at 0 ° C., the compression ratio can be reduced because it has a higher evaporation pressure and a lower condensation pressure than R22. Therefore, the composition between the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated liquidus line 2V of the gas-liquid equilibrium line 2 has a vaporization pressure equal to or higher than that of R22 at a temperature of 0 ° C to 50 ° C. Since it has the following condensation pressure, it is suitable for refrigeration cycle devices such as air conditioners and refrigerators.

As can be seen from the figure, R1270 and R29
0 and trifluoroiodomethane are approximately 20 to approximately 70% by weight, 0 to approximately 80% by weight, and 0 to approximately 60% by weight, respectively, and the composition range is approximately R22 at a use temperature of approximately 0 to approximately 50 ° C. It is desirable because it has the same vapor pressure.

Further, the mixed refrigerant composed of the three components of R1270, R290 and trifluoroiodomethane is combustible with R1270 in a mixture having a small composition ratio of trifluoroiodomethane when the gas phase refrigerant leaks from the device, for example. It can be seen from Table 3 that the total composition of R290 only increases in concentration by about 10% by weight. 1
A mixture containing 0% by weight or more of trifluoroiodomethane has a composition of combustible components of 90% by weight or less and is inflammable. Therefore, as a composition of a mixed refrigerant, 20% by weight or more of trifluoroiodomethane is used. It is desirable that the mixture contains In a mixture containing a large proportion of trifluoroiodomethane, flammable R1270 and R29
The total composition of 0 has a higher concentration, but there is no fear of flammability because the composition ratio of trifluoroiodomethane is also large. Therefore, R1270, R290 and trifluoroiodomethane are approximately 20 to approximately 70% by weight, and 0 to approximately 6 respectively.
A composition range of 0% by weight, approximately 20 to approximately 60% by weight is desirable because the flammability of R1270 and R290 is eliminated by the incombustibility of trifluoromethane.

Table 4 shows the ideal refrigerating performance of a ternary composition between the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated liquidus line 2V of the gas-liquid equilibrium line 2. Is. The conditions are as follows: condensing average temperature is 50 ° C., evaporation average temperature is 0 ° C., condenser outlet supercooling degree is 0 deg, evaporator outlet superheat degree is 0 de
This is the case of g.

[0075]

[Table 4]

As can be seen from (Table 4), the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated gasline 2V of the gas-liquid equilibrium line 2 which are composition ranges for making the vapor pressure equivalent to R22. The three-component system in between has a refrigerating capacity lower than that of R22, but it has a refrigerating capacity of propane (R290) or higher, a coefficient of performance equivalent to that of R22, and a discharge temperature of trifluoroiodomethane. It can be kept low compared to. Even if low-boiling point R1270 or R290 leaks from the device, for example, the total composition of combustible components at that time is only about 10% by weight higher than the filling composition.
The above-mentioned mixture containing trifluoroiodomethane is flame-retardant even if the composition of combustible components exceeds 80% by weight. The temperature gradient in the condensation process and the evaporation process is about 2d.
It is not more than eg and becomes a near azeotropic mixture. By utilizing this temperature gradient in reverse to construct a Lorentz cycle in which the temperature difference with the heat source fluid is close, a higher coefficient of performance can be expected than in (Table 4).

Next, FIG. 3 shows propylene (C ₃ H ₆ , R127
0, boiling point −47.7 ° C.), cyclopropane (C ₃ H ₆ , RC
270, boiling point −33 ° C.), trifluoroiodomethane (CF ₃ I, boiling point −22.7 ° C.), the equilibrium state of the mixed refrigerant at a constant temperature and a constant pressure using triangular coordinates. It is shown. In this triangular coordinate, a single substance is arranged at each vertex of the triangle counterclockwise from the upper vertex in the descending order of boiling point,
Composition ratio (weight ratio) of each component at a point on the coordinate plane
Is represented by the ratio of the distance between the point and each side of the triangle. At this time, the distance between the point and the side of the triangle corresponds to the composition ratio of the substance described at the vertex of the triangular coordinates on the side opposite to the side.

In FIG. 3, 1L and 1V are temperatures 0 ° C.
This is a vapor-liquid equilibrium line of the mixed refrigerant at a pressure of 0.498 MPa, and this temperature / pressure corresponds to the saturated state at a temperature of R22 of 0 ° C. The upper vapor-liquid equilibrium line (corresponding to R220 ° C) 1V is the saturated vapor phase line, and the lower vapor-liquid equilibrium line (R220 ° C).
1 L represents a saturated liquidus line, and a gas-liquid equilibrium state is reached in the range sandwiched by the two lines. Further, 2 is a vapor-liquid equilibrium line consisting of a saturated liquidus line 2L and a saturated vaporous line 2V of the mixture at a temperature of 50 ° C. and a pressure of 1.943 MPa,
This temperature and pressure also correspond to the saturated state of R22 at a temperature of 50 ° C.

Each point in FIG. 3 corresponds to the gas phase composition (subscript V) and the liquid phase composition (subscript L) in the composition pairs A to E of the mixed refrigerant shown in (Table 5).

[0080]

[Table 5]

Points A _L to C _L are gas-liquid equilibrium lines (R220 ° C.).
Equivalent) 1 saturated liquid phase line 1L, points A _V to point C _V are gas-liquid equilibrium lines (R220 equivalent to 0 ° C) 1 saturated gas phase line 1 V, point D _L
~ Point E _L is on the saturated liquidus line 2L of the vapor-liquid equilibrium line (R22 50 ° C equivalent) 2, and points D _V to E _V are the gas-liquid equilibrium line (R225.
It is on the saturated vapor phase line 2V of 2). Therefore, the composition shown in the liquid phase composition or the gas phase composition of (Table 5) is 0
Saturation is achieved under conditions of saturated vapor pressure of R22 at ℃ or 50 ℃.

The composition on the saturated vapor phase V is vaporized at a pressure higher than that of R22 at the same temperature as R22 and liquefied at the same pressure as R22. The composition on the saturated liquidus line L is vaporized at the same temperature as R22 at the same pressure as R22 and liquefied at a pressure lower than R22. The composition in the area between these two lines vaporizes at a pressure higher than R22 and liquefies at a pressure lower than R22 at the same temperature as R22. That is, the composition in the area between the vapor-liquid equilibrium lines 2 at 50 ° C. is 5
At 0 ° C, the gas phase changes to a liquid phase at a pressure lower than R22, and at the same pressure as R22, a gas phase higher than 50 ° C condenses and changes to a liquid phase lower than 50 ° C. The composition in the area between the vapor-liquid equilibrium line 1 at 0 ° C changes from the liquid phase to the vapor phase at a pressure higher than R22 at 0 ° C, and the liquid phase lower than 0 ° C evaporates at the same pressure as R22. Then, the gas phase changes to a temperature higher than 0 ° C.

Here, the area between the gas-liquid equilibrium line 1 at 0 ° C. and the area between the gas-liquid equilibrium line 2 at 50 ° C. do not overlap, but conversely, the saturated gas phase of the gas-liquid parallel line 1 The composition between the line 1V and the saturated liquidus line 2L of the vapor-liquid equilibrium line 2 has a temperature of 0 ° C to 5 ° C.
It can be seen that at 0 ° C., the compression ratio can be reduced because it has a higher evaporation pressure and a lower condensation pressure than R22. Therefore, the composition between the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated liquidus line 2V of the gas-liquid equilibrium line 2 has a vaporization pressure equal to or higher than that of R22 at a temperature of 0 ° C to 50 ° C. Since it has the following condensation pressure, it is suitable for refrigeration cycle devices such as air conditioners and refrigerators.

As can be seen from the figure, R1270, RC2
70 and trifluoroiodomethane are approximately 40-
A composition range of about 85% by weight, 0 to about 40% by weight, and 0 to about 60% by weight is desirable because it has a vapor pressure equivalent to that of R22 at a use temperature of about 0 to about 50 ° C. Furthermore, the mixed refrigerant consisting of the three components of R1270, RC270, and trifluoroiodomethane is a total of flammable R1270 and RC270 in a mixture with a small composition ratio of trifluoroiodomethane when the gas-phase refrigerant leaks from the device, for example. It can be seen from Table 5 that the composition only increases in concentration by about 10% by weight. A mixture containing 10% by weight or more of trifluoroiodomethane has a composition of combustible components of 90% by weight or less and is flame retardant.
The composition of the mixed refrigerant is preferably a mixture containing 20% by weight or more of trifluoroiodomethane.
In the mixture containing a large proportion of trifluoroiodomethane, the total composition of flammable R1270 and RC270 becomes more concentrated, but there is no fear of flammability due to a large proportion of trifluoroiodomethane. Therefore,
R1270, RC270 and trifluoroiodomethane are each approximately 40 to approximately 80% by weight, 0 to approximately 40% by weight,
The composition range of about 20 to about 60% by weight is R12.
70 and RC270 are desirable because they eliminate the flammability of trifluoromethane.

Table 6 shows the ideal refrigerating performance of a ternary composition between the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated liquidus line 2V of the gas-liquid equilibrium line 2. Is. The conditions are as follows: condensing average temperature is 50 ° C., evaporation average temperature is 0 ° C., condenser outlet supercooling degree is 0 deg, evaporator outlet superheat degree is 0 de
This is the case of g.

[0086]

[Table 6]

As can be seen from (Table 6), the saturated liquidus line 1L of the gas-liquid parallel line 1 and the saturated gasus line 2V of the gas-liquid equilibrium line 2 which are composition ranges for making the vapor pressure equivalent to R22. The three-component system in between has a refrigerating capacity lower than that of R22, but secures a refrigerating capacity of propane (R290) or higher, and the coefficient of performance exhibits the same characteristics as R22. Low boiling point R1270 and RC
Even if 270 leaks from the device, for example, the total composition of combustible components at that time is only about 10% by weight higher than the filling composition. Therefore, a mixture containing 20% by weight or more of trifluoroiodomethane is combustible. Composition of ingredients is 8
It is flame-retardant even if it exceeds 0% by weight. The temperature gradient in the condensation process and the evaporation process is about 2 deg or less,
It becomes a near azeotropic mixture. By utilizing this temperature gradient in reverse to construct a Lorentz cycle in which the temperature difference with the heat source fluid is close, a higher coefficient of performance can be expected than in (Table 6).

Next, FIG. 4 shows propylene (C ₃ H ₆ , R127
0, boiling point -47.7 ℃), trifluoroiodomethane (CF ₃ I, boiling point -22.7 ℃), isobutane (iC ₄ H _8, R
3 shows the equilibrium state at a constant temperature and a constant pressure of a mixed refrigerant constituted by a mixture of three kinds (600a, boiling point-11.7 ° C.) using triangular coordinates. In the triangular coordinates, a single substance is arranged at each vertex of the triangle in the order of lower boiling point in a counterclockwise direction from the upper vertex as a base point, and the composition ratio (weight ratio) of each component at a certain point on the coordinate plane Is represented by the ratio of the distance between the point and each side of the triangle. At this time, the distance between the point and the side of the triangle corresponds to the composition ratio of the substance described at the vertex of the triangular coordinates on the side opposite to the side.

In FIG. 4, 1L and 1V are temperatures 0 ° C.
This is a vapor-liquid equilibrium line of the mixed refrigerant at a pressure of 0.498 MPa, and this temperature / pressure corresponds to the saturated state at a temperature of R22 of 0 ° C. The upper vapor-liquid equilibrium line (corresponding to R220 ° C) 1V is the saturated vapor phase line, and the lower vapor-liquid equilibrium line (R220 ° C).
1 L represents a saturated liquidus line, and a gas-liquid equilibrium state is reached in the range sandwiched by the two lines. Further, 2 is a vapor-liquid equilibrium line consisting of a saturated liquidus line 2L and a saturated vaporous line 2V of the mixture at a temperature of 50 ° C. and a pressure of 1.943 MPa,
This temperature and pressure also correspond to the saturated state of R22 at a temperature of 50 ° C.

Each point in FIG. 4 corresponds to the vapor phase composition (subscript V) and the liquid phase composition (subscript L) in the composition pairs A to E of the mixed refrigerant shown in (Table 7).

[0091]

[Table 7]

The points A _L to C _L are the gas-liquid equilibrium line (R220 0 ° C.
Equivalent) 1 saturated liquid phase line 1L, points A _V to point C _V are gas-liquid equilibrium lines (R220 equivalent to 0 ° C) 1 saturated gas phase line 1 V, point D _L
~ Point E _L is on the saturated liquidus line 2L of the vapor-liquid equilibrium line (R22 50 ° C equivalent) 2, and points D _V to E _V are the gas-liquid equilibrium line (R225.
It is on the saturated vapor phase line 2V of 2). Therefore, the composition shown in the liquid phase composition or the gas phase composition of (Table 7) is 0
Saturation is achieved under conditions of saturated vapor pressure of R22 at ℃ or 50 ℃.

The composition on the saturated vapor phase line V is vaporized at a pressure higher than that of R22 at the same temperature as R22 and liquefied at the same pressure as R22. The composition on the saturated liquidus line L is vaporized at the same temperature as R22 at the same pressure as R22 and liquefied at a pressure lower than R22. The composition in the area between these two lines vaporizes at a pressure higher than R22 and liquefies at a pressure lower than R22 at the same temperature as R22. That is, the composition in the area between the vapor-liquid equilibrium lines 2 at 50 ° C. is 5
At 0 ° C, the gas phase changes to a liquid phase at a pressure lower than R22, and at the same pressure as R22, a gas phase higher than 50 ° C condenses and changes to a liquid phase lower than 50 ° C. The composition in the area between the vapor-liquid equilibrium line 1 at 0 ° C changes from the liquid phase to the vapor phase at a pressure higher than R22 at 0 ° C, and the liquid phase lower than 0 ° C evaporates at the same pressure as R22. Then, the gas phase changes to a temperature higher than 0 ° C.

Here, the area between the gas-liquid equilibrium line 1 at 0 ° C. and the area between the gas-liquid equilibrium line 2 at 50 ° C. overlap, and the saturated liquidus line 1L of the gas-liquid parallel line 1 and the gas-liquid line. The composition between the saturated vapor phase line 2V of the equilibrium line 2 has a temperature of 0 ° C to 50 ° C.
Since it has a vapor pressure equivalent to that of R22, it is suitable for refrigeration cycle devices such as air conditioners and refrigerators.

As can be seen from the figure, R1270, trifluoroiodomethane and R600a are each about 40 to 40%.
A composition range of about 95% by weight, 0 to about 60% by weight, and 0 to about 25% by weight is desirable because it has a vapor pressure equivalent to that of R22 at a use temperature of about 0 to about 50 ° C.

Furthermore, the mixed refrigerant consisting of R1270, trifluoroiodomethane, and R600a is a flammable mixture of R1270 in a mixture having a small composition ratio of trifluoroiodomethane when the gas-phase refrigerant leaks from the device, for example. It can be seen from Table 7 that the total composition of R600a only increases in concentration by about 5% by weight.
A mixture containing 10% by weight or more of trifluoroiodomethane has a composition of combustible components of 90% by weight or less and is inflammable.
Any mixture containing the above trifluoroiodomethane can be made nonflammable. In a mixture containing a large proportion of trifluoroiodomethane, flammable R1
The total composition of 270 and R600a is more concentrated, but since the composition ratio of trifluoroiodomethane is high,
There is no fear of flammability. Therefore, R1270, trifluoroiodomethane, and R600a are approximately 40 to approximately 8 respectively.
A composition range of 0% by weight, about 20 to about 60% by weight, and 0 to about 25% by weight is desirable because the flammability of R1270 and R600a is eliminated by the incombustibility of trifluoromethane.

Table 8 shows the saturated liquidus line 1 of the gas-liquid parallel line 1.
It is an ideal refrigeration performance of a composition consisting of a ternary system that is substantially between L and the saturated vapor phase line 2V of the vapor-liquid equilibrium line 2. The conditions are as follows: condensing average temperature is 50 ° C., evaporation average temperature is 0 ° C., condenser outlet supercooling degree is 0 deg, evaporator outlet superheat degree is 0 de
This is the case of g.

[0098]

[Table 8]

As can be seen from Table 8, the gas-liquid parallel line 1 which is the composition range for making the vapor pressure almost equal to R22.
The three-component system between the saturated liquid phase line 1L of 1 and the saturated liquid phase line 2V of the gas-liquid equilibrium line 2 has a refrigerating capacity lower than that of R22, but has a refrigerating capacity equivalent to that of propane (R290). Shows the same characteristics as R22. Low boiling point R1270
Even if R600a having a high boiling point leaks from the apparatus, for example, the total composition of combustible components at that time is only about 5% by weight higher than the filling composition, so that 20% by weight or more of trifluoroiodomethane is contained. The mixture is flame-retardant even when the composition of combustible components is increased above 80% by weight.
The temperature gradient in the condensation process and the evaporation process is about 7 deg.
And is a near azeotrope. By utilizing this temperature gradient in reverse to construct a Lorentz cycle in which the temperature difference from the heat source fluid is close, a higher coefficient of performance can be expected than in (Table 8).

Further, the mixed refrigerant described above is stabilized by adding a radical chain inhibitor. In other words, trifluoroiodomethane may decompose due to the release of iodine due to the incorporation of active molecules such as oxygen, but the trifluoromethane radical generated at that time and the chain decomposition reaction by the iodine radical or ion may occur. By stopping, it can be stably used for a long period of time. Specifically, compounds having a hindered phenol structure, an arylamine structure, a hindered piperidine structure, a thioether structure, and a phosphite structure can be used alone or in combination. For example, as the hindered phenol structure, 2,6-ditertiary butyl-4-methylphenol, 2,4,6-tritertiary butylphenol, alkylphenol such as styrenated phenol or a derivative having the structure, 2, 2'-methylenebis (4-methyl-6-tert-butylphenol),
4,4'-isopropylidene-bisphenol, 4,
Monoalkylenedialkylphenols such as 4′-butylidene-bis (6-tert-butyl-3-methyl) phenol, 1,1-bis- (4-oxyphenyl) cyclohexane and derivatives having the structure, 2,6-bis ( 2'-hydroxy-3'-tert-butyl-5'-
Dialkylenetrialkylphenols such as methylbenzyl) -4-methylphenol and its derivatives, 2,2 ′
Typical examples include bisphenol monosulfide such as -thiobis- (4-methyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tertialbutylphenol) and derivatives having the structure. Can be given as. As the arylamine structure,
Phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p -Phenylenediamine, p-hydroxy-diphenylamine, p-hydroxyphenyl-β-naphthylamine,
Examples include 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives. Further, as thioethers, thiobis (β-naphthol), mercaptobenzothiazole, mercaptobenzimidazole, dodecylmercaptan, and derivatives thereof, and as phosphites, triphenylphosphite, tri-2-ethylhexylphosphite, trinonylphenylphosphite, etc. The organic phosphite compound and the like are used.

Besides these compounds, compounds used for the purpose of radical chain inhibitors can be used. They are,
They may be used singly or in a mixture of two or more, and the amount may be about several wt% with respect to the lubricating oil to be used, and depending on the selection of the compound, 1 wt% or less may provide a sufficient effect. The criteria for selection are those having good compatibility or good solubility with lubricating oils other than ester oil,
Compounds of hindered phenolic structure such as di-tert-butyl-4-methylphenol or combinations of these compounds with organic phosphite compounds such as triphenylphosphite were suitable.

FIG. 5 is a block diagram of an embodiment relating to the refrigeration cycle apparatus of the present invention. The refrigeration cycle device in the present embodiment is used in an air conditioner. Inside the integrated housing of this air conditioner, a compressor 3, a four-way valve 4, an outdoor heat exchanger 5 acting as a condenser or an evaporator, a throttle device 6 such as a capillary tube or an expansion valve, an evaporator or a condenser. The indoor heat exchanger 7, the accumulator 8 and the like that function as a container are connected by piping. The outdoor heat exchanger 5 exchanges heat with the atmosphere by using an outdoor fan 9 connected to a motor that is commonly used indoors and outdoors.
Heat-exchanges with indoor air using the indoor heat exchanger 7.

In this refrigeration cycle device, a mixed working fluid containing a lubricating oil other than ester oil, a radical chain inhibitor, trifluoroiodomethane, and propylene is enclosed.

Next, the mixed working fluid used in this air conditioner and its operation will be described.

When the indoor heat exchanger 7 acts as an evaporator when trifluoroiodomethane and propylene circulate as refrigerants in the refrigeration cycle, the indoor heat exchanger 7 acts as a condenser and the indoor heat exchanger 7 acts as a condenser. If it does, a heating action is performed.

2 which is a component of the refrigerant in the present embodiment
0-80 wt% trifluoroiodomethane and 20-8
To 0% by weight of propylene either 60% by weight or less of propane or 40% by weight or less of cyclopropane or 25% by weight or less of isobutane can be added. In this case, the incombustibility of trifluoroiodomethane suppresses the inflammability of propylene and propane or cyclopropane or isobutane.

In particular, during the heating operation, the refrigerant is liable to liquid-back to the compressor 3, and the composition separation of the gas phase and the liquid phase occurs in the accumulator 8. R1270 and trifluoroiodomethane are each approximately 20 to approximately 80% by weight, approximately 20 to approximately
In the case of a mixed refrigerant composed of two components such as approximately 80% by weight, R12 having a low boiling point in the accumulator 8
The composition ratio of 70 increased, and the maximum composition of R1270 was about 9
It becomes about 0% by weight, and the flammability of R1270 is suppressed by the incombustibility of trifluoroiodomethane.

Even if flammable R1270 leaks from the device, since the accumulator 8 is arranged outside the room, it can be released into the atmosphere, and the safety can be further enhanced.

Further, the lubricating oil other than the ester oil, which mainly stays in the compressor 3, is hydrolyzed like the ester oil even if the refrigerant contains a small amount of water because the temperature of the compressor 3 becomes high. Never.

Further, the radical chain inhibitor can be stably used for a long period of time by stopping the decomposition reaction of trifluoromethane among trifluoroiodomethane and propylene circulating as refrigerants.

Furthermore, 20 to 80% by weight of trifluoroiodomethane and 20 to 80% by weight of propylene,
Regarding the mixed refrigerant to which 60% by weight or less of propane or 40% by weight or less of cyclopropane or 25% by weight or less of isobutane is added, although the refrigerating capacity is slightly inferior, the cylinder volume of the compressor 3 is slightly increased. Since the refrigerating capacity is the same and the coefficient of performance is also the same, it is possible to use this mixed refrigerant without changing the outdoor heat exchanger 5 and the indoor heat exchanger 7 even with the current equipment using R22. You can

[0112]

As is apparent from the above, according to the mixed working fluid of the present invention, a mixture having almost no influence on the stratospheric ozone layer can be selected from a wide range of selection.

The mixed working fluid of the present invention has almost no effect on global warming. This is trifluoroiodomethane, which can almost ignore the global warming potential,
Propylene with almost no global warming potential (R127
0), propane (R290), cyclopropane (RC270), or isobutane (R600a).

Further, according to the mixed working fluid of the present invention, propylene (R1270), propane (R290), cyclopropane (RC270), or isobutane () is produced by trifluoroiodomethane, which is a nonflammable substance having a negative catalytic effect. The composition range of the mixture with R600a) can be further restricted to the flame-retardant range. As a result, this mixed working fluid can be used as it is in a normal refrigeration cycle apparatus together with a conventional compressor lubricating oil other than ester oil.

According to the present invention, by specifying the composition range of the mixture containing trifluoroiodomethane and propylene (R1270), R22 is used at a temperature of about 0 to about 50 ° C., which is the use temperature of a refrigeration cycle apparatus such as an air conditioner. A coefficient of performance equivalent to that can be expected, and it can be used with the current equipment using R22.

Further, according to the present invention, trifluoroiodomethane, propylene (R1270) and propane (R29
By specifying the composition range of the mixture containing 0), a coefficient of performance equivalent to that of R22 can be expected at about 0 to about 50 ° C., which is the use temperature of a refrigeration cycle device such as an air conditioner
It can also be used with existing equipment using R22.

Further, according to the present invention, by specifying the composition range of the mixture containing trifluoroiodomethane, propylene (R1270) and cyclopropane (RC270), the operating temperature of the refrigerating cycle apparatus such as an air conditioner is about 0. At about 50 ° C, a coefficient of performance equivalent to that of R22 can be expected, and it can be used with existing equipment using R22.

According to the present invention, trifluoroiodomethane, propylene (R1270) and isobutane (R6
By specifying the composition range of the mixture containing 00a), a coefficient of performance equivalent to that of R22 can be expected at a use temperature of a refrigeration cycle device such as an air conditioner of about 0 to about 50 ° C., and even with current equipment using R22. Can be used.

The mixture of the present invention is expected to be an almost azeotropic non-azeotropic mixture, and by constructing the Lorenz cycle, a coefficient of performance higher than that of R22 can be expected.

Further, by adding a radical chain inhibitor to the mixed working fluid of the present invention, trifluoroiodomethane can be stabilized and stably used for a long period of time.

In the refrigeration cycle apparatus of the present invention, by disposing the accumulator in the refrigeration cycle such as the air conditioner outside the room, even if flammable propylene (R1270) leaks from the apparatus, it is released into the atmosphere. Therefore, it is possible to provide a device having a better safety aspect.

[Brief description of the drawings]

FIG. 1 is a Cartesian coordinate diagram of an equilibrium state of a refrigerant composed of a mixture of two kinds of R1270 and trifluoroiodomethane at a constant temperature.

FIG. 2 is a triangular coordinate diagram of an equilibrium state of a refrigerant composed of a mixture of R1270, R290 and trifluoroiodomethane at a constant temperature and a constant pressure.

FIG. 3 is a triangular coordinate diagram of an equilibrium state of a refrigerant composed of a mixture of R1270, RC270 and trifluoroiodomethane at a constant temperature and a constant pressure.

FIG. 4 R1270, trifluoroiodomethane, R6
Triangular coordinate diagram of the equilibrium state at constant temperature and constant pressure of the refrigerant composed of the three kinds of mixture 00a.

FIG. 5 is a configuration diagram of an embodiment relating to a refrigeration cycle device of the present invention.

[Explanation of symbols]

 1 Gas-liquid equilibrium line (0 ° C, R22 equivalent pressure) 2 Gas-liquid equilibrium line (50 ° C, R22 equivalent pressure) V Saturated gas phase line L Saturated gas phase line 3 Compressor 4 Four-way valve 5 Outdoor heat exchanger 6 Throttle Equipment 7 Indoor heat exchanger 8 Accumulator 9 Outdoor fan 10 Indoor fan

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Tagashira 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (9)

[Claims] 1. A mixed working fluid comprising a lubricating oil other than an ester oil and a mixture, the mixture comprising 20-80 wt% trifluoroiodomethane and 20-80 wt% propylene. . 2. The mixed working fluid according to claim 1, wherein the mixture further contains 60% by weight or less of propane, 40% by weight or less of cyclopropane, or 25% by weight or less of isobutane. 3. A lubricating oil other than an ester oil and a mixture, the mixture comprising 20-60 wt% trifluoroiodomethane, 20-70 wt% propylene and 60 wt% or less propane. A mixed working fluid characterized by: 4. A lubricating oil other than an ester oil and a mixture, the mixture comprising 20-60% by weight trifluoroiodomethane, 40-80% by weight propylene and 40% by weight or less cyclopropane. A mixed working fluid characterized by the following. 5. A lubricating oil other than an ester oil and a mixture, the mixture comprising 20 to 60% by weight trifluoroiodomethane, 40 to 80% by weight propylene and 25% by weight or less isobutane. A mixed working fluid characterized by: 6. The mixed working fluid according to claim 1, further comprising a radical chain inhibitor. 7. A compressor, a condenser, an expansion mechanism, and an evaporator, comprising a lubricating oil other than ester oil and a mixture as a working fluid, wherein the refrigerant is 20 to 80% by weight of trifluoroiodomethane. A refrigeration cycle apparatus comprising 20 to 80% by weight of propylene. 8. The refrigeration cycle apparatus according to claim 7, wherein the mixed working fluid further contains a radical chain inhibitor. 9. The refrigeration cycle apparatus according to claim 7, further comprising an accumulator arranged outdoors.