JP2002228307A - Mixed refrigerant filling method and apparatus filled with mixed refrigerant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a refrigerant filling method for filling a mixed refrigerant capable of being used as a substitute for R22, R502 or R12, or an apparatus filled with the same. SOLUTION: A method for filling a refrigerant container with a mixture consisting of a flammable fluorohydrocarbon refrigerant (a), a mixed refrigerant of a nonflammable hydrocarbon refrigerant (b) forming an azeotropic or azeotropic-like mixture with the refrigerant (a), and another nonflammable fluorohydrocarbon refrigerant (c) other than the refrigerant (a) without premixing the three refrigerants (a), (b) and (c), is provided. Change in the composition of the mixed refrigerant can be suppressed at the time when a nonazeotropic mixed refrigerant containing the flammable fluorohydrocarbon refrigerant is prepared, and simple safe substitution can be realized in a variety of applications.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to R22 and R502.
Or, the present invention relates to a refrigerant charging method or a charged device for a mixed refrigerant as an alternative to R12.

[0002]

2. Description of the Related Art Conventionally, various refrigeration cycle devices such as an air conditioner, a refrigerator, a refrigerator, a car air conditioner, etc., include a compressor, a four-way valve, if necessary, a condenser, a throttle device such as a capillary tube and an expansion valve, and an evaporator. The cooling operation is performed by connecting a pipe to these components to form a refrigeration cycle, filling the inside with a refrigerant, and circulating the inside of the refrigeration cycle. In these refrigeration cycle apparatuses, a halogenated hydrocarbon refrigerant derived from methane or ethane, which is called a chlorofluorocarbon refrigerant (hereinafter referred to as ROO or ROO), is usually used as a refrigerant.

[0003] Among them, chlorodifluoromethane (CHClF2,
R22 (boiling point -40.8 ° C, non-flammable) is for air conditioners, refrigerators, etc. R502 (azeotropic refrigerant mixture of chlorodifluoromethane R22 and chloropentafluoroethane R115, boiling point -45.3 ° C, nonflammable) is Dichlorodifluoromethane (CCl2F2, R12, boiling point -29.
8 ℃, non-flammable) refrigerators, car air conditioners, etc., trichlorofluoromethane (CCl3F, R11, boiling point 23.7 ℃,
Incombustibility) has been widely used as a refrigerant for refrigerators and the like.

However, in recent years, stratospheric ozone depletion due to chlorofluorocarbon refrigerants has become a global environmental problem, and because of its stratospheric ozone depletion potential, regulations on its use and production have already been determined by the Montreal International Protocol. There is a movement to abolish its use and production. In order to eliminate the influence on the stratospheric ozone layer, it is a necessary condition that the molecular structure does not contain chlorine, and a fluorinated hydrocarbon refrigerant containing no chlorine has been proposed as a suitable material.

[0005] Examples of chlorine-free fluorinated hydrocarbon refrigerants include difluoromethane (CH2F2, R32, boiling point -5).
1.7 ° C, weakly flammable, pentafluoroethane (CF3-C
HF2, R125, boiling point-48.1 ° C, nonflammable), 1,
1,1-trifluoroethane (CF3-CH3, R143a,
Boiling point-47.2 ° C, weakly flammable), 1,1,1,2-tetrafluoroethane (CF3-CH2F, R134a, boiling point-2)
6.1 ° C, non-flammable), 1,1-difluoroethane (CHF
2-CH3, R152a, boiling point -24.0 ° C, weakly flammable),
Etc.

Here, R134a is mostly used as a substitute refrigerant for R12 in refrigerators and car air conditioners, and R125 / R125 is used as a substitute refrigerant for R502 in refrigerators and refrigerators.
Mixed refrigerants such as R32 / R125 / R134a and R32 / R125 have been proposed as alternative refrigerants to R22 such as R143a / R134a and R125 / R143a and air conditioners and refrigerators.

[0007]

However, the above-mentioned fluorinated hydrocarbon refrigerant or a mixed refrigerant comprising the fluorinated hydrocarbon refrigerant has compatibility with mineral oil and alkylbenzene oil which have been used as conventional lubricating oils for compressors. Poorly, the lubricating oil discharged together with the refrigerant from the compressor may not return to the compressor from the low-temperature evaporator. Therefore, when using a fluorinated hydrocarbon refrigerant or a mixed refrigerant composed of a fluorinated hydrocarbon refrigerant as the refrigerant, it is essential that the lubricating oil for the compressor be replaced with a synthetic oil such as an ester oil or an ether oil having good compatibility. Is considered as.

Accordingly, various existing refrigeration cycle devices such as air conditioners, refrigerators, refrigerators, car air conditioners and the like using a refrigerant having a stratospheric ozone depleting ability, such as R22, R502, R12, etc., are used for a fluorinated hydrocarbon refrigerant or a fluorinated refrigerant. It becomes difficult to use a mixed refrigerant composed of a hydrocarbon refrigerant.

Also, various existing refrigeration cycle devices such as air conditioners, refrigerators, refrigerators, car air conditioners and the like using a refrigerant having a stratospheric ozone depleting ability such as R22, R502 and R12 have different use temperatures and refrigeration capacities. In addition, the setting of the throttle device such as the capillary tube and expansion valve, which are the components of the refrigeration cycle device, and the setting of the steam pressure of the additionally installed high pressure switch and various safety devices, etc., are set according to the usage conditions. The replacement with the alternative refrigerant requires adjustment and change every time.

[0010] The present invention provides a simple and safe method for exchanging the refrigerant with an alternative refrigerant having no effect on the stratospheric ozone layer in various existing refrigeration cycle apparatuses and refrigerant containers using the refrigerant having the stratospheric ozone depleting ability. To realize an apparatus filled with an alternative refrigerant having no influence on the stratospheric ozone layer.

According to the present invention, in order to ensure the oil return of the conventional compressor lubricating oil to the compressor, the effect of the present invention on a small amount of stratospheric ozone layer which is close in chemical structure to mineral oil and alkylbenzene oil and has good compatibility. On the other hand, utilizing the property that only a hydrocarbon refrigerant having no flammability is used, the disadvantage of a highly flammable hydrocarbon refrigerant is compensated for by mixing a large amount of a weakly flammable or nonflammable fluorinated hydrocarbon refrigerant. Things.

Further, the present invention provides a method of mixing a weakly flammable or non-flammable fluorocarbon refrigerant with a highly flammable hydrocarbon refrigerant, wherein the highly azeotropic fluorocarbon refrigerant (a) is mixed with the flammable hydrocarbon refrigerant. A mixed refrigerant with the hydrocarbon refrigerant (b) is used. When the mixed refrigerant of the fluorinated hydrocarbon refrigerant (a) and the combustible hydrocarbon refrigerant (b) is a non-azeotropic mixed refrigerant, not only the boiling point temperature and the dew point temperature are different, but also the low boiling point in the gas phase. This is because components having a high boiling point tend to be concentrated in the liquid phase, and the mixture composition ratio of a small amount of the hydrocarbon refrigerant greatly fluctuates.

Further, the present invention selects an appropriate alternative refrigerant in view of the respective operating temperature and refrigeration capacity, setting of a throttle device such as a capillary tube and an expansion valve, and setting of vapor pressure of a high pressure switch and various safety devices. In order to achieve this, a highly azeotropic fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b)
And the refrigerant mixture is further mixed and adjusted.

The mixed refrigerant according to the present invention is usually a non-azeotropic mixed refrigerant, but the non-combustible fluorinated hydrocarbon refrigerant (c) is first used.
By subsequently charging a mixed refrigerant of a highly azeotropic fluorinated hydrocarbon refrigerant (a) and a combustible hydrocarbon refrigerant (b),
The change in the composition of the mixed refrigerant can be suppressed, and the mixture composition ratio of a small amount of the hydrocarbon refrigerant can be safely charged without largely changing.

As a result, even in various refrigeration cycle apparatuses using R22 and R502 for both medium temperature and low temperature, the fluorinated hydrocarbon refrigerant (a) which usually has a lower boiling point than R22 or R502 and the flammable Two types of refrigerant containers, a refrigerant container of a mixed refrigerant with a non-reactive hydrocarbon refrigerant (b) and a refrigerant container of a non-combustible fluorinated hydrocarbon refrigerant (c) which usually has a higher boiling point than R22 or R502 are prepared. Just fill while weighing appropriately to any ratio, various air conditioners, refrigerators,
An alternative refrigerant that does not affect the stratospheric ozone layer for applications such as refrigerators can be easily replaced.

Also, in various refrigeration cycle devices using both medium-temperature and low-temperature R12, a fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) which usually have a lower boiling point than R12. And a refrigerant container of a refrigerant mixture of
Various types of refrigerators and car air conditioners can be prepared simply by preparing two types of refrigerant containers of a nonflammable fluorinated hydrocarbon refrigerant (c) having a boiling point higher than 2 and filling them while appropriately measuring them at an arbitrary ratio. It is possible to easily replace an alternative refrigerant that does not affect the stratospheric ozone layer for such uses.

Further, the filling method according to the present invention relates to a method of filling a non-azeotropic mixed refrigerant containing a highly flammable hydrocarbon refrigerant, such as replacement with a refrigeration cycle device, repair, or filling from a service can at the time of leakage. Not only can it be used in the field of refrigeration, but also in fields such as filling refrigerant containers by refrigerant manufacturers.

In the case of charging a non-azeotropic mixed refrigerant of a three-component mixed refrigerant, a method of individually charging each component is conceivable. However, the individual charging requires a large number of components, requires a large amount of equipment cost, and requires a charging operation. Not only is there a very complicated problem, but non-azeotropic refrigerant mixtures containing highly flammable hydrocarbon refrigerants can exhibit flammability due to the high concentration of flammable refrigerants. According to the filling method of the present invention, it is possible to always fill with a constant composition while ensuring safety.

[0019]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a fluorinated hydrocarbon refrigerant (a) and an azeotropic or azeotropic mixture of the fluorinated hydrocarbon refrigerant (a). The mixed refrigerant preliminarily mixed with the flammable hydrocarbon refrigerant (b) to be formed and the non-flammable fluorocarbon refrigerant (c) other than the fluorinated hydrocarbon refrigerant (a) are mixed without premixing. A mixed refrigerant charging method characterized by filling a refrigerant container with a mixed refrigerant composed of a fluorinated hydrocarbon refrigerant (a), a combustible hydrocarbon refrigerant (b) and an incombustible fluorinated hydrocarbon refrigerant (c).

Further, in the present invention, the refrigerant container is a refrigeration cycle apparatus, and a mixed refrigerant comprising a fluorinated hydrocarbon refrigerant (a), a combustible hydrocarbon refrigerant (b), and an incombustible fluorinated hydrocarbon refrigerant (c). Is filled.

In the present invention, the mixed refrigerant of the fluorinated hydrocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b) is a low-boiling refrigerant, and the incombustible fluorinated hydrocarbon refrigerant (c) is a high-boiling refrigerant. It is characterized by being.

In the present invention, the mixed refrigerant of the fluorocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b) is a high-boiling refrigerant, and the nonflammable fluorocarbon refrigerant (c) is a low-boiling refrigerant. It is characterized by being.

Further, the present invention is characterized in that it is a mixed refrigerant composed of a fluorinated hydrocarbon refrigerant (a), an incombustible fluorinated hydrocarbon refrigerant (c), and a combustible hydrocarbon refrigerant (b) in ascending order of boiling point. Is what you do.

In the present invention, difluoromethane (R32), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1 are used as the fluorinated hydrocarbon refrigerant (a). , 2-tetrafluoroethane (R134a), 1,1-difluoroethane (R15
2a), 1,1,2,2-tetrafluoroethane (R1
34), 1,1,1,2,2-pentafluoropropane (R245cb), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,1
3,3,3-hexafluoropropane (R236f
a), perfluoropropane (R218), and flammable hydrocarbon refrigerant (b) include propane (R290), cyclopropane (RC270), and isobutane (R600).
a), butane (R600), nonflammable fluorinated hydrocarbon refrigerants (c) other than the fluorinated hydrocarbon refrigerants (a) include:
Pentafluoroethane (R125), 1,1,1,2-
Tetrafluoroethane (R134a), 1,1,2,2
-Tetrafluoroethane (R134), 1,1,1,
2,3,3,3-heptafluoropropane (R227e
a), 1,1,1,3,3,3-hexafluoropropane (R236fa), perfluoropropane (R21
8) is selected from the following.

In the present invention, the fluorinated fluorinated refrigerant (a) is preferably difluoromethane (R32), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a) or 1,1,1,1,2. 2-tetrafluoroethane (R134a) or 1,1-difluoroethane (R152a), flammable hydrocarbon refrigerant (b) is isobutane (R600a) or butane (R600), nonflammable fluorinated hydrocarbon refrigerant other than (a) above (C) is pentafluoroethane (R125) or 1,1,1,2-tetrafluoroethane (R134a).

The present invention also relates to a fluorinated fluorinated refrigerant (a) of not less than 80% by weight of R32 and a flammable hydrocarbon refrigerant (b) of not more than 20% by weight of R600a or R60.
0, and a mixed refrigerant comprising R125 or R134a as the non-combustible fluorinated hydrocarbon refrigerant (c).

Also, the present invention relates to a non-combustible fluorinated fluorinated refrigerant (a) containing 90% by weight or more of R143a and a flammable hydrocarbon refrigerant (b) containing 10% by weight or less of R600a. The hydrocarbon refrigerant (c) is a mixed refrigerant comprising R125 or R134a.

Further, the present invention relates to a fluorinated hydrocarbon refrigerant (a) having R134a of 75% by weight or more and a flammable hydrocarbon refrigerant (b) having R600a or R6 of 25% by weight or less.
00, and a non-flammable fluorinated hydrocarbon refrigerant (c) is a mixed refrigerant comprising R125.

The present invention also relates to a fluorinated fluorinated refrigerant (a) of 70% by weight or more of R152a and a flammable hydrocarbon refrigerant (b) of 30% by weight or less of R600a or R6a.
No. 00, and a non-combustible fluorinated hydrocarbon refrigerant (c) is a mixed refrigerant comprising R125 or R134a.

The present invention also relates to a fluorinated hydrocarbon refrigerant (a)
And a mixed refrigerant comprising a combustible hydrocarbon refrigerant (b) forming an azeotropic or azeotrope-like mixture with (a), and a nonflammable fluorinated hydrocarbon refrigerant (c) other than the above (a). A refrigeration cycle device characterized by the following.

[0031]

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

(Embodiment 1) There are various combinations of mixed refrigerants comprising a highly azeotropic fluorocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) used in the mixed refrigerant charging method of the present invention. It is necessary to select from among the candidates.

The flammable hydrocarbon refrigerant (b) having no effect on the stratospheric ozone layer includes propane (CH3-CH2-CH
3, R290, boiling point -42.1 ° C, strong flammability), cyclopropane (C3H6, RC270, boiling point -32.9 ° C, strong flammability), isobutane (i-C4H8, R600a, boiling point -1)
1.7 ° C, strong flammability, butane (n-C4H8, R600,
Boiling point -0.5 ° C, highly flammable).

A combination of a fluorinated hydrocarbon refrigerant (a) having no effect on the stratospheric ozone layer and a mixed refrigerant with a combustible hydrocarbon refrigerant (b) forms an azeotropic or azeotropic mixture. Examples of the hydrogen refrigerant (a) include difluoromethane (CH2F2, R32, boiling point -51.7 ° C, weakly flammable), pentafluoroethane (CF3-CHF2, R125, boiling point -48.1 ° C, nonflammable), 1,1,1-trifluoroethane (CF3-CH3, R143a, boiling point -47.2 ° C,
Weakly flammable), 1,1,1,2-tetrafluoroethane (CF3-CH2F, R134a, boiling point -26.1 ° C, nonflammable), 1,1-difluoroethane (CHF2-CH3, R152
a, boiling point -24.0 ° C, weakly flammable).

Other than the above, an azeotropic or azeotrope-like mixture is used in a combination of a fluorinated hydrocarbon refrigerant (a) having no effect on the stratospheric ozone layer and a flammable hydrocarbon refrigerant (b). As the fluorinated hydrocarbon refrigerant (a) to be formed, 1,1,2,2-tetrafluoroethane (CHF2-C
HF2, R134, boiling point -19.8 ° C, nonflammable), 1,
1,1,2,2-pentafluoropropane (CF3-CF2-CH
3, R245cb, boiling point -17.6 ° C, weak flammability),
1,1,1,2,3,3,3-heptafluoropropane (CF3-CHF-CF3, R227ea, boiling point -15.6 ° C, nonflammable), 1,1,1,3,3,3- Hexafluoropropane (CF3-CH2-CF3, R236fa, boiling point -1.4 ° C,
Nonflammable).

In the combination of the fluorinated hydrocarbon refrigerant (a) containing no hydrogen and the refrigerant mixture containing the flammable hydrocarbon refrigerant (b), the fluorinated hydrocarbon containing no hydrogen that forms an azeotropic or azeotropic mixture is used. As the fluorinated hydrocarbon refrigerant (a), perfluoropropane (CF3-CF2-CF3, R218, boiling point -3)
6.8 ° C, non-flammable).

In these mixed refrigerants of the fluorinated hydrocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b), the main azeotropic or azeotrope-like mixture (approximate azeotropic composition) is as follows: However, the present invention is not limited to these.

1) R32 / R290 (75/25% by weight), R32 / RC270 (80/20% by weight), R3
2 / R600a (85/15% by weight), R32 / R60
0 (90/10% by weight) 2) R125 / R290 (90/10% by weight), R12
5 / RC270 (95/5% by weight) 3) R143a / R290 (75/25% by weight), R1
43a / RC270 (85/15% by weight), R143a
/ R600a (95/5% by weight) 4) R134a / R290 (55/45% by weight), R1
34a / RC270 (65/35% by weight), R134a
/ R600a (80/20% by weight), R134a / R6
00 (95/5% by weight) 5) R152a / R290 (40/60% by weight), R1
52a / RC270 (45/55% by weight), R152a
/ R600a (75/25% by weight), R152a / R6
00 (85/15% by weight) In the above-mentioned combination forming an azeotropic or azeotropic mixture, the combination in which the azeotropic composition of the fluorohydrocarbon refrigerant (a) is 70% by weight or more is From the fluorinated hydrocarbon refrigerant (a) (azeotropic composition-5% by weight) to 100
%, The boiling point temperature and the dew point temperature are almost the same, the gas phase composition and the liquid phase composition are almost the same in a wide composition range including an azeotropic composition of less than 10%, so that it can be handled as if it were a single refrigerant. It has been shown to form a near azeotropic mixture.

For example, the following combinations can be exemplified.

1) A mixed refrigerant of 70% by weight or more of R32 as the fluorinated hydrocarbon refrigerant (a) and 30% by weight or less of R290 as the combustible hydrocarbon refrigerant (b).

2) A mixed refrigerant of 75% by weight or more of R32 as the fluorinated hydrocarbon refrigerant (a) and 25% by weight or less of RC270 as the combustible hydrocarbon refrigerant (b).

3) A mixed refrigerant of 80% by weight or more of R32 as the fluorinated hydrocarbon refrigerant (a) and 20% by weight or less of R600a as the combustible hydrocarbon refrigerant (b).

4) A mixed refrigerant of 85% by weight or more of R32 as the fluorinated hydrocarbon refrigerant (a) and 15% by weight or less of R600 as the combustible hydrocarbon refrigerant (b).

5) A mixed refrigerant of 85% by weight or more of R125 as the fluorinated hydrocarbon refrigerant (a) and 15% by weight or less of R290 as the combustible hydrocarbon refrigerant (b).

6) A mixed refrigerant of 90% by weight or more of R125 as the fluorinated hydrocarbon refrigerant (a) and 10% by weight or less of RC270 as the combustible hydrocarbon refrigerant (b).

7) A mixed refrigerant comprising 70% by weight or more of R143a as the fluorinated hydrocarbon refrigerant (a) and 30% by weight or less of R290 as the combustible hydrocarbon refrigerant (b).

8) A mixed refrigerant of R143a of 80% by weight or more as the fluorinated hydrocarbon refrigerant (a) and RC270 of 20% by weight or less as the combustible hydrocarbon refrigerant (b).

9) A mixed refrigerant of 90% by weight or more of R143a as the fluorinated hydrocarbon refrigerant (a) and 10% by weight or less of R600a as the combustible hydrocarbon refrigerant (b).

10) As the fluorinated hydrocarbon refrigerant (a), 75
At least R134a by weight and a combustible hydrocarbon refrigerant (b)
Mixed refrigerant with 25% by weight or less of R600a.

11) As the fluorinated hydrocarbon refrigerant (a), 90
At least R134a by weight and a combustible hydrocarbon refrigerant (b)
As a mixed refrigerant with 10% by weight or less of R600.

12) 70% as the fluorinated hydrocarbon refrigerant (a)
By weight or more of R152a and a combustible hydrocarbon refrigerant (b)
30% by weight or less of a mixed refrigerant with R600a.

13) Fluorohydrocarbon refrigerant (a) as 80
By weight or more of R152a and a combustible hydrocarbon refrigerant (b)
Refrigerant mixed with 20% by weight or less of R600.

In the mixed refrigerant of the fluorinated hydrocarbon refrigerant (a) and a small amount of the flammable hydrocarbon refrigerant (b), any combination that forms an azeotropic or azeotropic mixture is a fluorinated hydrocarbon refrigerant. The mixture has a lowest boiling point azeotropic mixture in which the boiling points are lower than those of the components (a) and the combustible hydrocarbon refrigerant (b).

Here, the mixed refrigerant of the fluorinated hydrocarbon refrigerant (a) and a small amount of the flammable hydrocarbon refrigerant (b) is a weakly flammable or non-flammable mixture. In order to reduce the number of times of filling as much as possible, an azeotropic-like refrigerant mixture of a fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) and a non-combustible refrigerant other than the above (a) are used. It would be desirable to mix a fluorinated hydrocarbon refrigerant.

For example, conventional refrigerants R22 and R50
2. There are the following two methods for configuring an alternative refrigerant having a vapor pressure substantially equal to that of R12.

A) An azeotropic mixture of a fluorocarbon refrigerant (a) having a low boiling point and a flammable hydrocarbon refrigerant (b), and a non-combustible fluorocarbon other than the above (a) having a high boiling point Combination of hydrogen refrigerant (c).

B) An azeotropic mixture of a fluorocarbon refrigerant (a) having a high boiling point and a flammable hydrocarbon refrigerant (b), and a nonflammable fluorocarbon other than the above (a) having a low boiling point Combination of hydrogen refrigerant (c). Furthermore, it is very advantageous that the flammable hydrocarbon refrigerant (b), which forms a near azeotropic mixture over a wide composition range, including the azeotropic composition, is R600a or R600. That is, R60
Since 0a or R600 has a boiling point closer to that of a conventional compressor lubricating oil such as mineral oil or alkylbenzene oil as compared with other hydrocarbon refrigerants, the compatibility is most improved and an azeotropic mixture is formed in a wide composition range. This facilitates the adjustment when mixing with a large amount of fluorohydrocarbon refrigerant.

The flammable hydrocarbon refrigerant (b) is R60
0a or R600 means that the boiling point is almost the highest in most cases as compared with the fluorinated hydrocarbon refrigerant (a) and the non-combustible fluorinated hydrocarbon refrigerant (c). Is the least likely to leak and can be safely filled.

Accordingly, R22 used in the method of the present invention
The following combinations are suitable as alternative refrigerants for R502 and R502.

A) Azeotropic refrigerant mixture of a fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) having a low boiling point, and an incombustible fluorinated hydrocarbon refrigerant (c) having a high boiling point 1) 80% by weight or more of R as a fluorohydrocarbon refrigerant (a)
32 and 20% by weight or less of R600a or R600 as a combustible hydrocarbon refrigerant (b), and R125 or R134a as a noncombustible fluorinated hydrocarbon refrigerant (c)
A mixed refrigerant consisting of

2) A mixed refrigerant of 90% by weight or more of R143a as the fluorinated hydrocarbon refrigerant (a) and 10% by weight or less of R600a as the flammable hydrocarbon refrigerant (b); c) R125 or R134 as
a mixed refrigerant consisting of a.

A mixture of an azeotropic mixture of a fluorinated hydrocarbon refrigerant (a) and a combustible hydrocarbon refrigerant (b) having a higher boiling point, and an incombustible fluorinated hydrocarbon refrigerant (c) having a lower boiling point 3) 75% by weight or more of R as the fluorinated hydrocarbon refrigerant (a)
A mixed refrigerant of 134a and 25% by weight or less of R600a or R600 as a combustible hydrocarbon refrigerant (b) and R125 as an incombustible fluorinated hydrocarbon refrigerant (c).

4) A mixed refrigerant of 70% by weight or more of R152a as the fluorinated hydrocarbon refrigerant (a) and 30% by weight or less of R600a or R600 as the flammable hydrocarbon refrigerant (b), incombustible fluorinated hydrocarbon R125 as refrigerant (c)
A mixed refrigerant consisting of

As the alternative refrigerant for R12 used in the method of the present invention, the following combinations are suitable as candidates.

A) An azeotropic-like mixed refrigerant of a fluorinated hydrocarbon refrigerant (a) and a combustible hydrocarbon refrigerant (b) having a low boiling point, and an incombustible fluorinated hydrocarbon refrigerant (c) having a high boiling point 5) 70% by weight or more of R as the fluorohydrocarbon refrigerant (a)
A mixed refrigerant of 152a and 30% by weight or less of R600a or R600 as a combustible hydrocarbon refrigerant (b), and a mixed refrigerant of R134a as a nonflammable fluorinated hydrocarbon refrigerant (c).

The above description is based on the conventional refrigerants R22 and R50.
2. Although a main representative example of forming a substitute refrigerant having a vapor pressure substantially equal to that of R12 is shown, the present invention is not limited to this, and a substitute refrigerant of R11 which is a conventional refrigerant may be used.

Accordingly, the fluorohydrocarbon refrigerant (a) includes difluoromethane (R32), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1,2- Tetrafluoroethane (R134a), 1,1-difluoroethane (R15
2a), 1,1,2,2-tetrafluoroethane (R1
34), 1,1,1,2,2-pentafluoropropane (R245cb), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,1
3,3,3-hexafluoropropane (R236f
a), perfluoropropane (R218), and flammable hydrocarbon refrigerant (b) include propane (R290), cyclopropane (RC270), and isobutane (R600).
a), butane (R600).

Examples of the nonflammable fluorinated hydrocarbon refrigerant (c) other than the fluorinated hydrocarbon refrigerant (a) include pentafluoroethane (R125), 1,1,1,2-tetrafluoroethane (R134a), , 1,2,2-tetrafluoroethane (R134), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,1
3,3,3-hexafluoropropane (R236f
a) and perfluoropropane (R218).

(Embodiment 2) Next, an example of a three-component mixed refrigerant produced by using the mixed refrigerant charging method of the present invention and a specific refrigerant charging method will be described with reference to a vapor pressure diagram. I do. Here, as the three-component mixed refrigerant used as a substitute refrigerant for R22, A) an azeotropic-like mixed refrigerant of a fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) having a low boiling point, and a high boiling point An embodiment including R32 as a combination of the non-combustible fluorohydrocarbon refrigerant (c) will be described. However, the same refrigerant charging method can be used for other three-component mixed refrigerants.

FIG. 1 shows that a fluorinated hydrocarbon refrigerant (a) is difluoromethane (CH2F2, R32, boiling point -51.7 ° C.,
Isobutane (i-C4H8, R600a, boiling point -11.7 ° C, strongly flammable) as a flammable hydrocarbon refrigerant (b), 1,1,1 as a nonflammable fluorinated hydrocarbon refrigerant (c)
1,2-tetrafluoroethane (CF3-CH2F, R134
a, boiling point −26.1 ° C., non-flammable), at a temperature of 50 ° C., 0 ° C., -5
The equilibrium state at the same pressure as the pressure of R22 at 0 ° C. is shown using triangular coordinates.

In the present triangular coordinates, R32, R134
a and R600a have lower boiling points in the order of R32a and R13a.
4a, R600a, a single substance is arranged in this order, and the composition ratio (weight ratio) of each component at a certain point on the coordinate plane is:
It is expressed as 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 the phase equilibrium diagram of FIG. 1, 1 is a temperature of 50 °.
The gas-liquid equilibrium line of the mixture showing the same pressure as the pressure of R22 at C, 2 is the vapor-liquid equilibrium line of the mixture showing the same pressure as the R22 pressure at 0 ° C, and 3 is the R22 at -50 ° C. 3 is a vapor-liquid equilibrium line of a mixture showing the same pressure as that of the mixture. The upper lines 1V, 2V, and 3V of the vapor-liquid equilibrium lines 1, 2, and 3 are the saturated vapor line, and the lower lines 1L, 2L, and 3B of the vapor-liquid equilibrium lines 1, 2, and 3.
L represents a saturated liquidus line, and a gas-liquid equilibrium state is established in a range sandwiched between these lines, and at each temperature, R
It shows almost the same pressure as 22.

The composition in the area between 1 V and 1 L of the vapor-liquid equilibrium line will condense the gaseous phase at a temperature higher than 50 ° C. at the same pressure as R22 and turn into a liquid phase at a temperature lower than 50 ° C. At the same pressure as R22, the liquid phase evaporates at a temperature lower than 50 ° C and changes to a gas phase at a temperature higher than 50 ° C. For compositions in the area between 2V and 2L of the vapor-liquid equilibrium line, at the same pressure as R22, the gas phase condenses at a temperature higher than 0 ° C and changes to a liquid phase at a temperature lower than 0 ° C, R22
At the same pressure, the liquid phase evaporates below 0 ° C,
Transforms into gas phase above 0 ° C. Vapor-liquid equilibrium line 3
The composition in the area between V and 3 L, at the same pressure as R22, the gas phase condenses at a temperature above -50 ° C. and
The liquid phase changes to a liquid phase at a temperature lower than 0 ° C., and at the same pressure as R22, the liquid phase evaporates at a temperature lower than −50 ° C. to −50 ° C.
Changes to gas phase at temperatures higher than ゜ C.

That is, a condensation temperature of 50 ° C. and an evaporation temperature of 0
In equipment using medium temperature R22 such as ゜ C,
The area between 1 V and 1 L of the vapor-liquid equilibrium line
1V of the gas-liquid equilibrium line where the area between V and 2L overlaps
Compositions in the area between 2 and 2L are suitable for the R22 replacement refrigerant. Similarly, the condensation temperature is 0 ° C and the evaporation temperature is
In a device using R22 for a low temperature such as 50 ° C., the gas-liquid equilibrium line where the area between the gas-liquid equilibrium line 2V and 2L overlaps the area between the gas-liquid equilibrium line 3V and 3L Compositions in the area between 2V and 3L of the above are suitable for R22 alternative refrigerants.

As can be seen from the phase equilibrium diagram of FIG.
In the case of a three-component mixed refrigerant consisting of / R134a / R600a, from the viewpoint of making the vapor pressure almost equal to R22, a composition suitable for medium temperature and a composition suitable for low temperature are partially However, the composition range that can be selected for the low temperature range is broader than the range suitable for the medium temperature range.

From the example of FIG. 1, R32 / R134a / R
The range in which the three-component mixed refrigerant consisting of 600a is substituted so that the vapor pressure is substantially the same as that of R22 for both medium temperature and low temperature is as follows: R32 is 4 to 75% by weight, and R134a is 0 to 77%.
%, R600a is a three-component system consisting of 0 to 93% by weight.

Here, difluoromethane (CH2F2, R32, boiling point -51.7 ° C.,
When isobutane (i-C4H8, R600a, boiling point -11.7 ° C, strong flammability) is used as the flammable hydrocarbon refrigerant (b), 80 is used as the fluorinated hydrocarbon refrigerant (a). At least R32 by weight and a combustible hydrocarbon refrigerant (b)
To form an azeotropic or azeotrope-like mixture at not more than 20% by weight of R600a. In particular, a composition comprising 85% by weight of R32 as the fluorinated hydrocarbon refrigerant (a) and 15% by weight of R600a as the flammable hydrocarbon refrigerant (b) forms an azeotropic mixture, and each component of R32 or R600a In addition, the non-flammable fluorohydrocarbon refrigerant (c) 1,
1,1,2-tetrafluoroethane (CF3-CH2F, R13
4a, boiling point -26.1 ° C, nonflammable).

Thus, for example, 85% by weight of R32a as the fluorinated hydrocarbon refrigerant (a) to be an azeotropic mixture and 15% by weight of R600a as the flammable hydrocarbon refrigerant (b)
A straight line connecting the composition consisting of and R134a as the nonflammable fluorohydrocarbon refrigerant (c) is drawn on the phase equilibrium diagram of FIG. That is, 85% by weight of R32 is used as the fluorinated hydrocarbon refrigerant (a), and 15% is used as the flammable hydrocarbon refrigerant (b).
A refrigerant container of a mixed refrigerant consisting of R600a in weight%;
(C) Two kinds of refrigerant containers of R134a are prepared, and R134a is used as a non-combustible fluorohydrocarbon refrigerant (c) by about 45-7.
5% by weight, 85% by weight of R32 as the fluorinated hydrocarbon refrigerant (a) and 15% by weight as the flammable hydrocarbon refrigerant (b)
R600a from the refrigerant container of the mixed refrigerant
It is considered that filling is performed while appropriately measuring an arbitrary ratio in the range of ~ 55% by weight.

This means that, on the phase equilibrium diagram of FIG. 1, a composition comprising 85% by weight of R32 as the fluorinated hydrocarbon refrigerant (a) and 15% by weight of R600a as the flammable hydrocarbon refrigerant (b). And a nonflammable fluorinated hydrocarbon refrigerant (c) R134
This corresponds to filling a line connecting a in an arbitrary ratio appropriately. Therefore, on the phase equilibrium diagram of FIG. 1, a composition consisting of 85% by weight of R32 as the fluorinated hydrocarbon refrigerant (a), 15% by weight of R600a as the flammable hydrocarbon refrigerant (b), and Hydrocarbon refrigerant (c) R13
If the straight line connecting 4a is internally divided between 1 V and 2 L of the gas-liquid equilibrium line and filled, it can be replaced with an alternative refrigerant having a vapor pressure almost equivalent to that of R22 in equipment using R22 for medium temperature,
If the gas is internally divided between 2 V and 3 L of the gas-liquid equilibrium line, the refrigerant can be replaced with an alternative refrigerant having a vapor pressure almost equal to that of R22 in a device using R22 for low temperature.

At this time, from the example of FIG. 1, R32 / R1
34a / R600a is a ternary mixed refrigerant filled with R32 having a vapor pressure substantially equal to that of R22 for both medium temperature and low temperature, in the range of about 20 to 45% by weight of R32 and R1.
34a is about 45 to 75% by weight, and R600a is about 3.5 to 75% by weight.
It is a three-component system consisting of 8.5% by weight.

In the above-mentioned example of the filling method, an example is shown in which the gas is exchanged so that the vapor pressure is substantially equal to R22.
Since the vapor pressure is almost proportional to the refrigerating capacity, the refrigerating capacity can be made substantially equal. In the case of adjusting to the setting of a throttle device such as a capillary tube or an expansion valve which is a component of the refrigeration cycle device, for example, the density of the saturated liquid is R
The liquid may be filled in such a manner that the density is substantially equal to the density of the saturated liquid at the condensation temperature of 22.

The filling method here is such that R134a, which is a non-combustible, high-boiling non-combustible fluorinated hydrocarbon refrigerant (c), is charged first, and a weakly flammable, low-boiling fluorocarbon refrigerant ( It is practical to fill a composition comprising 85% by weight of R32 as a) and 15% by weight of R600a as a combustible hydrocarbon refrigerant (b) while monitoring the status of the equipment.

According to the filling method of the present invention, R
The ternary mixed refrigerant consisting of 32 / R134a / R600a is a non-azeotropic mixed refrigerant, but R32, R134a, R6
Compared to the method of individually filling each component of the liquid refrigerant No. 00a, the concentration of the highly flammable R600a, which should be a small amount, does not increase, the composition change of the mixed refrigerant can be suppressed, and safety is always ensured, while always being constant. It can be filled with the composition.

FIG. 2 shows that difluoromethane (CH2F2, R32, boiling point -51.7 ° C.,
Butane (n-C4H8, R600, boiling point -0.5 ° C, strong flammability) as flammable hydrocarbon refrigerant (b),
1,1,1,2-, as a non-combustible fluorinated hydrocarbon refrigerant (c)
Tetrafluoroethane (CF3-CH2F, R134a, boiling point-
26.1 ° C., non-flammable), R at temperatures of 50 ° C., 0 ° C. and -50 ° C.
The equilibrium state at the same pressure as the pressure 22 is shown using triangular coordinates.

From the example of FIG. 2, R32 / R134a / R
The range in which the three-component mixed refrigerant of 600 has a vapor pressure substantially equal to that of R22 for both medium temperature and low temperature is as follows: R32 is 7 to 74% by weight, R134a is 0 to 77% by weight, and R600a is It is a three-component system consisting of 0 to 92% by weight.

Accordingly, for example, a composition comprising 90% by weight of R32 as the fluorinated hydrocarbon refrigerant (a) to be an azeotropic mixture, 10% by weight of R600 as the flammable hydrocarbon refrigerant (b), A straight line connecting R134a as the fluorinated hydrocarbon refrigerant (c) is drawn on the phase equilibrium diagram of FIG. That is, a refrigerant container of a mixed refrigerant composed of 90% by weight of R32 as the fluorinated hydrocarbon refrigerant (a), 10% by weight of R600 as the flammable hydrocarbon refrigerant (b), and a non-combustible fluorinated hydrocarbon refrigerant (c )), Two kinds of refrigerant containers of R134a are prepared. About 45 to 75% by weight of R134a is used as the non-combustible fluorinated hydrocarbon refrigerant (c), 90% by weight of R32 is used as the fluorinated hydrocarbon refrigerant (a), and flammable. It is conceivable to charge the mixed hydrocarbon refrigerant (b) from the refrigerant container of 10% by weight of R600 in a range of about 25 to 55% by weight while appropriately measuring it at an arbitrary ratio.

At this time, from the example of FIG. 2, R32 / R1
The range of the three-component mixed refrigerant of 34a / R600 filled so as to have a vapor pressure almost equal to that of R22 for both medium temperature and low temperature is about 25 to 50% by weight of R32, R13
4a is about 45 to 75% by weight, R600a is about 2.5 to
It is a three-component system consisting of 5.5% by weight.

Therefore, if the range in which the vapor pressure is substituted so as to be substantially equal to that of R22 is replaced by R32 / R600 instead of R32 / R600a, R3
2 is about 20-50% by weight, R134a is about 45-75% by weight, and R600a or R600 is about 2.5-8.5% by weight.
2 can be used as an alternative refrigerant.

Table 1 shows that 85% by weight / 15% by weight of R
It shows ideal refrigeration performance in a specific mixed composition of a three-component system composed of a 32 / R600a mixed refrigerant and R134a in comparison with R22 for medium temperature. The conditions for medium temperature are as follows: the average condensing temperature is 50 ° C, the average evaporating temperature is 0 ° C, the degree of supercooling at the condenser outlet is 0 deg, and the degree of superheat at the evaporator is 0d
eg.

As can be seen from Table 1, for example, R3
2 / R600a (85% by weight / 15% by weight) is 30% by weight and R134a is 70% by weight, a three-component system, that is, R32 is 25.5% by weight, R134a is 70% by weight, and R600a is 4.5% by weight. % Of the three-component system is R
Although it has a refrigerating capacity slightly lower than that of 22, it can be filled as a substitute for a device that wants to make the pressure almost equal or a device that wants to lower the discharge temperature.

Further, for example, R32 / R600a (85
Wt% / 15 wt%) and R134a is 6 wt%.
A three-component system consisting of 0% by weight, that is, a three-component system consisting of 34% by weight of R32, 60% by weight of R134a, and 6% by weight of R600a has a slightly higher pressure than R22, but wants to increase the refrigerating capacity. It has the feature that it can be filled as an alternative to equipment.

In the example of Table 1, 85% by weight / 15% by weight of an azeotropic refrigerant mixture of R32 / R600a was mixed with R134a.
A high-boiling-point refrigerant is mixed at an arbitrary ratio and charged as an alternative to equipment using R22.
It is also possible to adjust the vapor pressure and the refrigerating capacity arbitrarily even when filling as an alternative to the equipment using.

Further, instead of R32 / R600a, R3
2 / R600 is also the same when R32 is about 20 to 50% by weight, R134a is about 45 to 75% by weight,
The three-component system in which R600a or R600 is about 2.5 to 8.5% by weight can adjust the vapor pressure and refrigeration capacity arbitrarily when filled as a substitute for equipment using R22. And various R22 and R502
When R32 is filled as a substitute for various purposes in an apparatus using R32, about 15 to 60% by weight of R32 and about 40% by weight of R134a are used.
~ 85% by weight, R600a or R600 is about 0-10
A three component system consisting of weight percent is preferred.

[0094]

[Table 1]

(Embodiment 3) A three-component mixed refrigerant produced by using the refrigerant charging method of the present invention and a specific example of the refrigerant charging method will be described with reference to a vapor pressure diagram. Here, 3 used as a substitute refrigerant for R22
As the component-mixed refrigerant, A) an azeotropic-like mixed refrigerant of a fluorinated hydrocarbon refrigerant (a) having a high boiling point and a flammable hydrocarbon refrigerant (b), and an incombustible fluorinated hydrocarbon refrigerant (c) having a low boiling point )
An example including R125 will be described as a combination of the above, but the same refrigerant charging method can be used for other three-component mixed refrigerants.

FIG. 3 shows that 1,1,1,2-tetrafluoroethane (CF3-CH2F, R
134a, boiling point -26.1 ° C, non-flammable), butane (n-C4H8, R600, boiling point -0.5 ° C, strongly flammable) as nonflammable hydrocarbon refrigerant (b), nonflammable fluorocarbon As a refrigerant (c), pentafluoroethane (CF3-CHF2, R12
5, 50 ° C, 0 ° C, -5 of a mixed refrigerant composed of three kinds of mixtures having a boiling point of -48.1 ° C and nonflammability.
The equilibrium state at the same pressure as the pressure of R22 at 0 ° C. is shown using triangular coordinates.

In the present triangular coordinates, R125, R13
Although the boiling points are lower in the order of 4a and R600, R125 and R1 are counterclockwise at each vertex of the triangle with the upper vertex as the base point.
34a, a single substance is arranged in the order of R600, and the composition ratio (weight ratio) of each component at a certain point on the coordinate plane is:
It is expressed as 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 the phase equilibrium diagram of FIG. 3, 1 is a temperature of 50 °.
The gas-liquid equilibrium line of the mixture showing the same pressure as the pressure of R22 at C, 2 is the vapor-liquid equilibrium line of the mixture showing the same pressure as the R22 pressure at 0 ° C, and 3 is the R22 at -50 ° C. 3 is a vapor-liquid equilibrium line of a mixture showing the same pressure as that of the mixture. The upper lines 1V, 2V, and 3V of the vapor-liquid equilibrium lines 1, 2, and 3 are the saturated vapor line, and the lower lines 1L, 2L, and 3B of the vapor-liquid equilibrium lines 1, 2, and 3.
L represents a saturated liquidus line, and a gas-liquid equilibrium state is established in a range sandwiched between these lines, and at each temperature, R
It shows almost the same pressure as 22.

The composition in the area between 1 V and 1 L of the gas-liquid equilibrium line will condense the gaseous phase at a temperature higher than 50 ° C. at the same pressure as R22 and turn into a liquid phase at a temperature lower than 50 ° C. At the same pressure as R22, the liquid phase evaporates at a temperature lower than 50 ° C and changes to a gas phase at a temperature higher than 50 ° C. For compositions in the area between 2V and 2L of the vapor-liquid equilibrium line, at the same pressure as R22, the gas phase condenses at a temperature higher than 0 ° C and changes to a liquid phase at a temperature lower than 0 ° C, R22
At the same pressure, the liquid phase evaporates below 0 ° C,
Transforms into gas phase above 0 ° C. Vapor-liquid equilibrium line 3
The composition in the area between V and 3 L, at the same pressure as R22, the gas phase condenses at a temperature above -50 ° C. and
The liquid phase changes to a liquid phase at a temperature lower than 0 ° C., and at the same pressure as R22, the liquid phase evaporates at a temperature lower than −50 ° C. to −50 ° C.
Changes to gas phase at temperatures higher than ゜ C.

That is, a condensation temperature of 50 ° C. and an evaporation temperature of 0
In equipment using medium temperature R22 such as ゜ C,
The area between 1 V and 1 L of the vapor-liquid equilibrium line
1V of the gas-liquid equilibrium line where the area between V and 2L overlaps
Compositions in the area between 2 and 2L are suitable for the R22 replacement refrigerant. Similarly, the condensation temperature is 0 ° C and the evaporation temperature is
In a device using R22 for low temperature such as 50 ° C., the gas-liquid equilibrium line where the area between the gas-liquid equilibrium line 2V and 2L overlaps the area between the gas-liquid equilibrium line 3V and 3L Compositions in the area between 2V and 3L of the above are suitable for R22 alternative refrigerants.

As can be seen from the phase equilibrium diagram of FIG.
In the case of a three-component mixed refrigerant composed of 5 / R134a / R600, from the viewpoint of making the vapor pressure almost equal to R22, a composition suitable for medium temperature and a composition suitable for low temperature are partially However, the composition range that can be selected for the low temperature range is broader than the range suitable for the medium temperature range.

From the example of FIG. 3, R125 / R134a /
The range in which the three-component mixed refrigerant composed of R600 is substituted so that the vapor pressure is substantially the same as that of R22 for both medium temperature and low temperature is as follows: R125 is 57 to 97% by weight, and R134a is 0 to 0.
A three-component system comprising 43% by weight and R600a of 0 to 39% by weight.

Here, 1,1,1,2-tetrafluoroethane (CF3-CH2F, R
134a, boiling point -26.1 ° C, non-flammable), butane (n-C4H8, R600, boiling point -0.5 ° C, strong flammability) is used as the flammable hydrocarbon refrigerant (b). 90% by weight or more of R134a as the hydrogenated hydrocarbon refrigerant (a);
10% by weight or less of R6 as a combustible hydrocarbon refrigerant (b)
At 00 an azeotropic or azeotrope-like mixture is formed. In particular, 95% by weight of R13 as the fluorohydrocarbon refrigerant (a)
4a and 5% by weight of R as a combustible hydrocarbon refrigerant (b).
The composition consisting of 600 forms an azeotropic mixture and has a lower boiling point than R134a and R600 of each component, but pentafluoroethane (CF3-CHF2, R125, boiling point- 48.1 ゜ C, nonflammable)
Has a higher boiling point.

Therefore, for example, an azeotropic mixture is obtained (95% by weight of R134 as the fluorohydrocarbon refrigerant (a)).
a and 5% by weight of R6 as a combustible hydrocarbon refrigerant (b).
And a non-flammable fluorohydrocarbon refrigerant (c).
Let us draw a straight line connecting R125 on the phase equilibrium diagram of FIG. That is, 95% is used as the fluorinated hydrocarbon refrigerant (a).
A refrigerant container of a mixed refrigerant comprising R134a of 5% by weight and R600 of 5% by weight as a combustible hydrocarbon refrigerant (b);
Two kinds of refrigerant containers of R125, which is a non-combustible fluorinated hydrocarbon refrigerant (c), are prepared. (95% by weight of R134a as the fluorinated hydrocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b)
About 20 to 40% by weight of a refrigerant container of a mixed refrigerant composed of 5% by weight of R600, and about 125 to 60% by weight of R125 which is a non-combustible fluorinated hydrocarbon refrigerant (c) at an arbitrary ratio. Consider filling while measuring.

This means that the composition comprising 95% by weight of R134a as the fluorohydrocarbon refrigerant (a) and 5% by weight of R600 as the flammable hydrocarbon refrigerant (b) in the phase equilibrium diagram of FIG. And R, which is a non-combustible fluorinated hydrocarbon refrigerant (c)
This corresponds to filling a line connecting the lines 125 at an arbitrary ratio. Therefore, on the phase equilibrium diagram of FIG.
(95% by weight of R134 as the fluorocarbon refrigerant (a)
a and 5% by weight of R6 as a combustible hydrocarbon refrigerant (b).
And a non-flammable fluorohydrocarbon refrigerant (c).
Is a straight line connecting R125 with 1V and 2L of the gas-liquid equilibrium line.
If it is filled internally, it can be replaced with an alternative refrigerant having a vapor pressure almost equivalent to R22 in equipment using R22 for medium temperature, and internally divided between 2V and 3L of the gas-liquid equilibrium line. When the refrigerant is charged, it can be replaced with an alternative refrigerant having a vapor pressure almost equal to that of R22 in equipment using R22 for low temperature.

At this time, from the example of FIG. 3, R125 / R
The range filled with a three-component mixed refrigerant consisting of 134a / R600 so as to have a vapor pressure substantially equal to that of R22 for both medium temperature and low temperature is about 125 to 80% by weight of R125,
134a is a ternary system comprising about 20 to 40% by weight and R600 about 1 to 2% by weight.

In the above-described example of the filling method, an example is shown in which the gas is exchanged so that the vapor pressure is substantially equal to R22.
Since the vapor pressure is almost proportional to the refrigerating capacity, the refrigerating capacity can be made substantially equal. In the case of adjusting to the setting of a throttle device such as a capillary tube or an expansion valve which is a component of the refrigeration cycle device, for example, the density of the saturated liquid is R
The liquid may be filled in such a manner that the density is substantially equal to the density of the saturated liquid at the condensation temperature of 22.

The filling method used here is a non-flammable, high-boiling fluorohydrocarbon refrigerant (a) containing 95% by weight of R13.
4a and 5% by weight of R as a combustible hydrocarbon refrigerant (b)
R125 as a non-combustible, low-boiling, non-combustible fluorinated hydrocarbon refrigerant (c).
It is practical if filling is performed while monitoring the condition of the equipment.

According to the filling method of the present invention, R
The three-component mixed refrigerant consisting of 125 / R134a / R600 is a non-azeotropic mixed refrigerant.
Compared with the method of individually filling each component of 600, the concentration of the highly flammable R600, which should be a small amount, does not increase, the composition change of the mixed refrigerant can be suppressed, and safety is always ensured while always being constant. It can be filled with the composition.

FIG. 4 shows that 1,1,1,2-tetrafluoroethane (CF3-CH2F, R
134a, boiling point -26.1 ° C, nonflammable), isobutane (i-C4H8, R600) as a flammable hydrocarbon refrigerant (b)
a, boiling point -11.7 ° C, strong flammability), pentafluoroethane (CF3-CHF)
2, R125, boiling point -48.1 ° C, non-flammable).
The equilibrium state at the same pressure as the pressure of R22 at ゜ C and −50 ° C. is shown using triangular coordinates.

From the example shown in FIG. 4, it can be seen that R125 / R134a /
The range in which the three-component mixed refrigerant composed of R600a is substituted so that the vapor pressure becomes almost the same as that of R22 for both the medium temperature and low temperature is 52 to 91% by weight for R125 and 0 for R134a.
3 to 43% by weight and R600a of 0 to 45% by weight.
It is a component system.

Therefore, for example, 80% by weight of R134a is used as the fluorinated hydrocarbon refrigerant (a) to be an azeotropic mixture.
And 20% by weight of R6 as a combustible hydrocarbon refrigerant (b).
A straight line connecting the composition of No. 00a and the non-combustible fluorinated hydrocarbon refrigerant (c) R125 is drawn on the phase equilibrium diagram of FIG. That is, a refrigerant container of a mixed refrigerant composed of 80% by weight of R134a as the fluorinated hydrocarbon refrigerant (a), 20% by weight of R600a as the combustible hydrocarbon refrigerant (b), and a non-combustible fluorinated hydrocarbon refrigerant (c) R)
125 kinds of refrigerant containers are prepared. From the refrigerant container of the mixed refrigerant consisting of 80% by weight of R134a as the fluorinated hydrocarbon refrigerant (a) and 20% by weight of R600a as the combustible hydrocarbon refrigerant (b), It is considered that about 25 to 45% by weight of R125, which is a non-combustible fluorinated hydrocarbon refrigerant (c), is charged in an arbitrary ratio in the range of about 55 to 75% by weight while being appropriately measured.

At this time, from the example of FIG.
The range filled with a three-component mixed refrigerant consisting of 134a / R600a so as to have a vapor pressure almost equal to that of R22 for both medium temperature and low temperature is about 55 to 75% by weight of R125.
R134a is about 20-40% by weight, R600a is about 5
It is a three-component system consisting of 9% by weight.

Therefore, if the range of substitution so as to have a vapor pressure almost equal to that of R22 is replaced with R125 / R600a instead of R125 / R600,
R125 is about 55 to 80% by weight, R134a is about 20 to
A ternary system consisting of 40% by weight, R600a or about 1 to 9% by weight of R600 provides R22 for both medium and low temperatures.
It can be used as an alternative refrigerant.

Table 2 shows 95% by weight / 5% by weight of R1.
It shows ideal refrigeration performance in a specific mixed composition of a three-component system composed of a refrigerant mixture of 34a / R600 and R125 in comparison with R502 for medium temperature. The conditions for medium temperature are as follows: the average condensing temperature is 50 ° C., the average evaporating temperature is 0 ° C., the degree of supercooling at the condenser outlet is 0 deg, and the degree of superheating at the evaporator is 0 d.
eg.

As can be seen from Table 2, R134a /
40% by weight of R600 (95% by weight / 5% by weight)
A three-component system comprising 125% by weight of 60%
The three-component system consisting of 60% by weight, 5% by weight of R5a, 38% by weight of R134a and 2% by weight of R600 has a refrigerating capacity slightly lower than that of R502, but can be filled as an alternative to equipment for which pressure and discharge temperature are to be lowered. There is.

Further, for example, R134a / R600 (9
5% by weight / 5% by weight) and 30% by weight of R125.
A three-component system consisting of 70% by weight of R125, 28.5% by weight of R134a, and 1.5% by weight of R600 slightly improves the refrigerating capacity lower than that of R502 and increases the pressure. It has the feature that it can be filled as an alternative to equipment that approaches R502 to reduce the discharge temperature.

In the example of Table 2, 95% by weight / 5% by weight
R134a / R600 azeotropic mixture refrigerant of R134a
A high-boiling-point refrigerant was mixed at an arbitrary ratio and charged as an alternative to the equipment using R502.
It is also possible to adjust the vapor pressure and the refrigerating capacity arbitrarily even when filling as an alternative to the equipment using.

Instead of R134a / R600, R134
The same applies to the case where a / R600a is substituted.
Is about 55-80% by weight, R134a is about 20-40% by weight, R600a or R600 is about 1-9% by weight, when filled as an alternative to equipment using R502. It is possible to adjust the vapor pressure and the refrigerating capacity. When filling various devices using R22 and R502 as alternatives for various purposes, R125 is about 50 to 85% by weight and R134a is used. Is about 1
5 to 50% by weight, R600a or R600 is about 0 to 1
A three component system comprising 0% by weight is desirable.

[0120]

[Table 2]

(Embodiment 4) A three-component mixed refrigerant charging method according to the present invention will be described with reference to the embodiment of FIG. In FIG. 5, reference numeral 11 denotes a high-boiling-point refrigerant container in which R134a, which is a noncombustible fluorinated hydrocarbon refrigerant (c), is enclosed.
2 is a metering device for high boiling point refrigerant, 13 is a fluorocarbon refrigerant (a), a flammable hydrocarbon refrigerant (b) that forms an azeotropic or azeotropic mixture with the fluorohydrocarbon refrigerant (a), R3.
An azeotropic mixture refrigerant container of 2 / R600a mixed refrigerant, 14 is an azeotropic mixture refrigerant measurement device, and an azeotropic mixture refrigerant container 13 contains an azeotropic mixture refrigerant having a lower boiling point than the high boiling refrigerant container 11. It is enclosed. These, the evacuation device 15 and valves for opening and closing operations are connected to one piping system 17 having a refrigerant charging port 16.

Here, the refrigeration cycle device 20 is
1, a four-way valve 22, a condenser 23, a throttle device 24 such as a capillary tube and an expansion valve, an evaporator 25, and the like are connected by pipes. Inside the compressor 21, a conventional refrigerant R22 and mineral oil or alkylbenzene oil or These mixed oils are enclosed. Note that the four-way valve 22 is not required in the case of a device such as a refrigerator or a refrigerator that performs only a simple cooling operation. At this time, the evacuation device 15 also uses the refrigerant injection port 26, the connection pipe 27, and the refrigerant charging port 16 provided in a low-pressure line such as between the evaporator 25 and the compressor 21 suction port of the refrigeration cycle device 20 for exhaust. Then, the conventional refrigerant R22 is evacuated by evacuation. Next, the three-component mixed refrigerant is measured from the refrigerant inlet 26 while measuring the high-boiling refrigerant from the high-boiling refrigerant container 11 and the lower-boiling azeotropic mixed refrigerant from the azeotropic mixed refrigerant container 13 in this order. Refrigeration cycle device 20
Is to be filled. Thus, the conventional refrigerant R
22 is replaced with R32 / R134a / R600a, which is an alternative refrigerant having no effect on the stratospheric ozone layer.

Therefore, after the high-boiling-point refrigerant measured from the high-boiling-point refrigerant container 11 is filled, the azeotropic-like mixed refrigerant charged from the azeotropic-like mixed refrigerant container 13 has almost the same boiling point temperature and dew point temperature. Yes, since the gas phase composition and liquid phase composition are almost the same, it can be handled as a single refrigerant, and the strongly flammable hydrocarbon refrigerant contained in the azeotropic mixture refrigerant is related to liquid filling and gas filling. No, it is not filled more than the desired composition in the refrigeration cycle device 20,
It becomes possible to fill a desired three-component composition in an appropriate amount.

At this time, since the non-combustible fluorinated hydrocarbon refrigerant (c), which is a high boiling point refrigerant, is charged first, the pressure in the refrigeration cycle apparatus 20 does not greatly increase, and the fluorinated carbonized refrigerant, which is a low boiling point refrigerant, does not rise. An azeotropic mixture refrigerant of a hydrogen refrigerant (a) and a flammable hydrocarbon refrigerant (b) can be charged. When the azeotropic mixture refrigerant is charged while operating the refrigeration cycle device 20, the refrigeration cycle Since the pressure in the low pressure line of the device 20 is reduced, the filling can be performed more easily. Here, the azeotropic-like mixed refrigerant of the fluorinated hydrocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b) is a high-boiling refrigerant, and the incombustible fluorinated hydrocarbon refrigerant (c) is a low-boiling refrigerant. What can be done is, of course.

In the embodiment shown in FIG. 5, the evacuation operation by the evacuation device 15, the operation of charging the high-boiling-point refrigerant from the high-boiling-point refrigerant container 11, the operation of charging the azeotropic-like mixed refrigerant from the azeotropic-type mixed refrigerant container 13 are performed. In the order of the weighing operation, the operation has been described in which the connection pipe 27 to the refrigerant inlet 26 is connected and changed at the installation site of the refrigeration cycle device 20, but the high-boiling-point refrigerant container 11, the high-boiling-point refrigerant measuring device 12, the azeotropic It is a matter of course that the three-component mixed refrigerant filling device in which the mixed refrigerant container 13, the azeotropic mixed refrigerant measuring device 14, the evacuation device 15, and the refrigerant charging port 16 are connected to one piping system 17 is also possible. It is.

Thus, the fluorinated hydrocarbon refrigerant (a), the flammable hydrocarbon refrigerant (b) which forms an azeotropic or azeotropic mixture with the fluorinated hydrocarbon refrigerant (a), and the fluorinated hydrocarbon refrigerant A refrigeration cycle apparatus filled with a non-azeotropic mixed refrigerant composed of a nonflammable fluorinated hydrocarbon refrigerant (c) other than the hydrogen refrigerant (a) is a conventional refrigerant having a stratospheric ozone depleting ability such as R22, R502, and R12 of conventional refrigerants. Is replaced in a simple and safe way by alternative refrigerants that have no effect on the stratospheric ozone layer,
This eliminates the need for changing mineral oil or alkylbenzene oil, setting throttle devices such as capillary tubes and expansion valves, and changing steam pressure settings of additionally installed high pressure switches and various safety devices.

In the above embodiment, the description was made using R134a as the high boiling point refrigerant and R32 / R600a mixed refrigerant as the azeotropic mixture refrigerant as the low boiling point refrigerant.
It is not always necessary to stick to a combination of these three components. For example, as an alternative to R22 and R502, R32
/ R600 and R134a, R143a / R600a and R
134a, R134a / R600a and R125, R13
As alternatives to 4a / R600 and R125, R152a / R600a and R125, R152a / R600 and R125, and R12, R152a / R600a and R134a;
A three-component mixed refrigerant including R152a / R600 and R134a may be used.

[0128]

As is apparent from the above description, the present invention forms the azeotropic or azeotropic mixture with the fluorinated hydrocarbon refrigerant (a) and the fluorinated hydrocarbon refrigerant (a). Without previously mixing the mixed refrigerant with the combustible hydrocarbon refrigerant (b) and the non-combustible fluorocarbon refrigerant of the non-combustible fluorocarbon refrigerant (c) other than the above-mentioned fluorocarbon refrigerant (a). Filling a refrigerant container with a mixed refrigerant consisting of fluorinated hydrocarbon refrigerant (a), combustible hydrocarbon refrigerant (b) and incombustible fluorinated hydrocarbon refrigerant (c); ), A flammable hydrocarbon refrigerant (b) that forms an azeotropic or azeotropic mixture with the fluorinated hydrocarbon refrigerant (a), and a nonflammable fluorinated hydrocarbon refrigerant other than the fluorinated hydrocarbon refrigerant (a) ( c) A refrigeration system filled with a mixed refrigerant comprising the non-combustible fluorinated hydrocarbon refrigerant Temperature and refrigeration capacity of air conditioners, refrigerators, refrigerators, car air conditioners, etc. using conventional refrigerants such as R22, R502, R12 and other refrigerants having stratospheric ozone depletion capacity and mineral oil or alkylbenzene oil. By setting the filling ratio of the azeotropic-like mixed refrigerant containing the non-combustible fluorinated hydrocarbon refrigerant and the highly flammable hydrocarbon refrigerant to an arbitrary ratio in various existing refrigeration cycle devices, A simple and safe method to replace the refrigerant without affecting the stratospheric ozone layer without changing the setting of expansion devices and other throttle devices, and the setting of the vapor pressure of additional high pressure switches and various safety devices. A method of filling a mixed refrigerant containing a highly flammable hydrocarbon refrigerant, which can be exchanged, for exchange to a refrigeration cycle device, or repair or leakage Not only can be used in areas such as filling from the service cans, it can be used in areas such as filling of the refrigerant container in the refrigerant manufacturer.

[Brief description of the drawings]

FIG. 1 is a triangular coordinate diagram of an equilibrium state of a mixed refrigerant constituted by three kinds of mixtures of R32 / R134a / R600a mixed refrigerants.

FIG. 2 is a triangular coordinate diagram of an equilibrium state of a mixed refrigerant composed of three types of mixtures of R32 / R134a / R600 mixed refrigerants.

FIG. 3 is a triangular coordinate diagram of an equilibrium state of a mixed refrigerant composed of three kinds of mixtures of R125 / R134a / R600 mixed refrigerants.

FIG. 4 is a triangular coordinate diagram of an equilibrium state of a mixed refrigerant composed of three kinds of mixtures of R125 / R134a / R600a mixed refrigerants.

FIG. 5 is an explanatory view of a method for charging a three-component mixed refrigerant according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 High-boiling-point refrigerant container 12 High-boiling-point refrigerant measuring device 13 Azeotropic-like mixed refrigerant container 14 Azeotropic-like mixed refrigerant measuring device 15 Vacuum evacuation device 16 Refrigerant filling port 17 Piping system 20 Refrigeration cycle device 1V R22 equivalent to 50 ° C Saturated vapor line of vapor-liquid equilibrium line 1 of 1L R22 saturated vapor line of vapor-liquid equilibrium line 1 equivalent to 50 ° C 2V Saturated vapor line of vapor-liquid equilibrium line 1 equivalent to 0 ° C of R22 2L R22 Saturated liquidus line of vapor-liquid equilibrium line 1 equivalent to 0 ° C 3V Saturated vapor phase line of vapor-liquid equilibrium line 1 equivalent to -50 ° C for R22 Liquidus

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) F25B 13/00 F25B 13/00 A (72) Inventor Shozo Funakura 1006 Kazuma, Kazuma, Kazuma, Osaka Matsushita Electric Industrial (72) Inventor Fumitoshi Nishiwaki 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. F term (reference) 3E072 AA01 DA01 3L092 AA14 BA21 EA01 FA34

Claims (12)

[Claims] 1. A premixed mixture of a fluorinated hydrocarbon refrigerant (a) and a flammable hydrocarbon refrigerant (b) which forms an azeotropic or azeotropic mixture with the fluorinated hydrocarbon refrigerant (a). The refrigerant and the non-flammable fluorinated hydrocarbon refrigerant (c) other than the fluorinated hydrocarbon refrigerant (a) are not mixed beforehand, and the fluorinated hydrocarbon refrigerant (a), the flammable hydrocarbon refrigerant (b) and A mixed refrigerant charging method, which comprises charging a mixed refrigerant comprising a non-combustible fluorinated hydrocarbon refrigerant (c) into a refrigerant container. 2. The refrigerant container is a refrigeration cycle device, and is filled with a mixed refrigerant composed of a fluorinated hydrocarbon refrigerant (a), a combustible hydrocarbon refrigerant (b), and an incombustible fluorinated hydrocarbon refrigerant (c). The mixed refrigerant charging method according to claim 1, wherein: 3. The refrigerant mixture of the fluorinated hydrocarbon refrigerant (a) and the flammable hydrocarbon refrigerant (b) is a low-boiling refrigerant, and the non-flammable fluorinated hydrocarbon refrigerant (c) is a high-boiling refrigerant. The mixed refrigerant charging method according to claim 1 or 2, wherein: 4. A refrigerant mixture of a fluorinated hydrocarbon refrigerant (a) and a combustible hydrocarbon refrigerant (b) is a high-boiling refrigerant, and the non-flammable fluorinated hydrocarbon refrigerant (c) is a low-boiling refrigerant. The mixed refrigerant charging method according to claim 1 or 2, wherein: 5. A refrigerant mixture comprising a fluorinated hydrocarbon refrigerant (a), an incombustible fluorinated hydrocarbon refrigerant (c), and a combustible hydrocarbon refrigerant (b) in ascending order of boiling point. 3. The mixed refrigerant charging method according to 1 or 2. 6. The fluorinated hydrocarbon refrigerant (a) includes difluoromethane (R32) and pentafluoroethane (R1
25), 1,1,1-trifluoroethane (R143
a), 1,1,1,2-tetrafluoroethane (R13
4a), 1,1-difluoroethane (R152a),
1,1,2,2-tetrafluoroethane (R134),
1,1,1,2,2-pentafluoropropane (R24
5cb), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,3,3,3
-Hexafluoropropane (R236fa), perfluoropropane (R218), flammable hydrocarbon refrigerant (b)
As propane (R290), cyclopropane (R
C270), isobutane (R600a), butane (R6
00), as the non-flammable fluorinated hydrocarbon refrigerant (c) other than the fluorinated hydrocarbon refrigerant (a), pentafluoroethane (R12
5), 1,1,1,2-tetrafluoroethane (R13
4a), 1,1,2,2-tetrafluoroethane (R1
34), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,3,3,3-
The method according to any one of claims 1 to 5, wherein the method is selected from hexafluoropropane (R236fa) and perfluoropropane (R218). 7. The fluorinated fluorinated refrigerant (a) is difluoromethane (R32) or pentafluoroethane (R12).
5) or 1,1,1-trifluoroethane (R143
a) or 1,1,1,1,2-tetrafluoroethane (R
134a) or 1,1-difluoroethane (R152
a), the flammable hydrocarbon refrigerant (b) is isobutane (R60
0a) or butane (R600), and the nonflammable fluorinated hydrocarbon refrigerant (c) other than (a) is pentafluoroethane (R125) or 1,1,1,2-tetrafluoroethane (R134a). The method for charging a mixed refrigerant according to claim 6, characterized in that: 8. R32 of 80% by weight or more as a fluorinated hydrocarbon refrigerant (a) and 2% as a combustible hydrocarbon refrigerant (b).
The mixed refrigerant charging method according to claim 7, wherein the refrigerant is a mixed refrigerant of 0 wt% or less of R600a or R600, and a mixed refrigerant of R125 or R134a as the incombustible fluorinated hydrocarbon refrigerant (c). 9. A refrigerant mixture comprising 90% by weight or more of R143a as a fluorinated fluorinated refrigerant (a) and 10% by weight or less of R600a as a combustible hydrocarbon refrigerant (b); (C) as R125 or R134a
The mixed refrigerant charging method according to claim 7, wherein the mixed refrigerant comprises: 10. A mixed refrigerant of 75% by weight or more of R134a as the fluorinated fluorinated refrigerant (a) and 25% by weight or less of R600a or R600 as the flammable hydrocarbon refrigerant (b). R125 as hydrogen refrigerant (c)
The mixed refrigerant charging method according to claim 7, wherein the mixed refrigerant comprises: 11. A mixed refrigerant of 70% by weight or more of R152a as a fluorinated fluorinated refrigerant (a) and 30% by weight or less of R600a or R600 as a flammable hydrocarbon refrigerant (b); R125 as hydrogen refrigerant (c)
8. The method according to claim 7, wherein the mixed refrigerant is R134a. 12. A refrigeration cycle apparatus, wherein a mixed refrigerant is charged using the mixed refrigerant charging method according to any one of claims 1 to 11.