JPH11124569A - Method for subdividing and filling non-axeotropic refrigerant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for subdividing and filling a non-azeotropic refrigerant, which prevents the composition of the dispensed refrigerant m from varying from one acceptor to another, when a refrigerant M for subdividing, which comprises a non-azeotropic refrigerant filled in a refrigerant storage tank, is successively dispensed and filled in multiple acceptors. SOLUTION: A vapor or liquid phase of a refrigerant M for subdividing in a refrigerant storage tank 1 is dispensed and filled while conducting with an adjustment refrigerant H having a composition substantially identical to that of this refrigerant M for subdividing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a non-azeotropic mixed refrigerant filled in a refrigerant storage tank which is sequentially divided and charged into a plurality of receivers, wherein the composition of the divided refrigerant changes for each receiver. The present invention relates to a subdivision filling method of a non-azeotropic mixed refrigerant for preventing the occurrence of azeotropic refrigerant.

[0002]

2. Description of the Related Art Conventionally, refrigerants having a single composition such as dichlorodifluoromethane (commonly referred to as CFC12, the same applies hereinafter) and chlorodifluoromethane (HCFC22) have been widely used as refrigerants for air conditioning / refrigeration equipment. However, in recent years, stratospheric ozone depletion by chlorofluorocarbons (CFCs) has been raised as a serious environmental problem.
Its production was discontinued at the end of 1995. Therefore, the existing CFC
Air-conditioning and refrigeration equipment using a plurality of hydrochlorofluorocarbons (HCFC), hydrofluorocarbons (HFC), and fluorocarbons (F
C), mixed refrigerants comprising hydrocarbons (HC) and the like have been developed.

[0003] Further, the above-mentioned HCFC is also
Although the impact on ozone depletion is smaller than
Since there is a high possibility that the amount of CFC used will increase due to alternative uses, it was decided to abolish the principle in 2020, and international total regulation was started in 1996. Therefore, in particular, refrigerants using HFC components having an ozone depletion potential of zero, which are not subject to regulations, are being studied as alternatives to HCFC22 widely used in air conditioners and the like.

[0004] As a refrigerant composition that can be substituted for HCFC22, there is no refrigerant having a single composition that can be used as it is in conventional HCFC22 equipment. Therefore, a two-component refrigerant whose physical properties are adjusted by mixing a plurality of components is used. An HFC-based mixed refrigerant of a system or a ternary system or more has been developed.
Further, from a similar viewpoint, a mixed refrigerant of HC, HC and HFC
And a mixed refrigerant with hydrofluoroether (HF)
Various mixed refrigerants containing E) or fluoroether (FE) have been proposed.

[0005]

However, these mixed refrigerants are refrigerants having a single composition such as CFC12 or HCFC22, or R5 which has been conventionally used as a low-temperature refrigerant.
Unlike azeotropic mixed refrigerants such as 02, most of them are non-azeotropic mixtures. Therefore, when the refrigerant is gradually filled into a plurality of receivers from the storage tank, the composition of each receiver is changed to the original composition (original composition). ). This problem,
In these non-azeotropic mixtures, the concentration of low-boiling components contained in the gas phase is higher than that in the liquid phase due to the vapor-liquid equilibrium relationship. As the capacity of the liquid phase decreases, the capacity of the gas phase relatively increases with this, and more low-boiling components are transferred to the gas phase. As a result, the concentration of the low-boiling components in the refrigerant (liquid phase) gradually decreases. It is due to If the composition of the refrigerant in the partially filled receiver changes beyond the allowable limit, the cooling performance and other performances of the air conditioning / refrigeration equipment change, making it difficult to use. Actually, as described above, the composition change becomes large as the amount of the residual refrigerant in the refrigerant storage tank decreases. Therefore, from the allowable limit of the composition, for example, the residual refrigerant after being extracted from the refrigerant storage tank by about 80% is subdivided. It is often returned to the filling factory without being used for filling. However, even if returned to a filling factory, the recovery and regeneration of the refrigerant whose composition has changed requires a great deal of cost and time, and this has contributed to an increase in the price of the refrigerant product.

As means for solving the problem of fluctuation of the liquid phase composition at the time of subdivision filling in a non-azeotropic mixed refrigerant, for example, Japanese Patent Application Laid-Open No. 8-157810 and WO 96/33377
International Patent Publication No. WO 2006/073139 proposes a method in which the composition of the subdivision refrigerant to be charged into the refrigerant storage tank is adjusted in advance so that the low-boiling component is excessive. However, even with these methods, it was not possible to prevent the composition fluctuation of each receiver due to the capacity of the refrigerant storage tank, the amount of extraction, the number of times of subdivision filling, and the like. The present invention has been made in order to solve the above-described problems, and therefore, an object of the present invention is to sequentially fill a plurality of receivers with a non-azeotropic mixed refrigerant filled in a refrigerant storage tank.
It is an object of the present invention to provide a subdivision filling method of a non-azeotropic refrigerant mixture that prevents the composition of the subdivided refrigerant from changing for each receiver.

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is directed to a method of sequentially filling a plurality of receivers with a subdivision refrigerant composed of a non-azeotropic mixed refrigerant filled in a refrigerant storage tank. There is provided a subdivision filling method of a non-azeotropic mixed refrigerant, in which a gaseous phase or a liquid phase of the subdivision refrigerant is conducted to a gaseous phase of an adjustment refrigerant having substantially the same composition as the refrigerant. In the above, each of the subdivision refrigerant and the adjustment refrigerant may be filled in a plurality of containers in which respective gas phases are conducted to each other. In the above, it is preferable that the total amount of the refrigerant for adjustment is at least 1 weight times the total amount of the refrigerant for subdivision. Further, it is preferable that the composition of the adjustment refrigerant is equal to the composition of the subdivision refrigerant within an error range of ± 2% by weight. Further, in the above, it is preferable that the temperature of the adjusting refrigerant is in the range of the same as the temperature of the subdivision refrigerant to + 5 ° C. Furthermore, the temperature of the subdivision refrigerant from the start to the end of subdivision filling is ± 10% of the temperature at the start of subdivision filling.
It is preferable to be within the fluctuation range of ° C. The subdivision refrigerant is HCFC, HFC, HC, FC, HFE, F
It is preferably a non-azeotropic refrigerant mixture of two or more selected from the group consisting of E and fluoroiodocarbon (FIC). In particular, the subdivision refrigerants are difluoromethane (HFC32) and pentafluoroethane (HFC12).
5) and 1,1,1,2-tetrafluoroethane (HFC134
It is preferably a non-azeotropic mixed refrigerant composed of two or more types selected from the group a). In this specification, the term “refrigerant” means its liquid phase unless otherwise specified. "Composition" indicates the weight ratio of each component constituting the refrigerant (liquid phase).

[0008]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment of a method for subdividing and charging a non-azeotropic mixed refrigerant of the present invention. Reference numeral 1 in FIG. 1 is a refrigerant tank, to the coolant tank 1, a predetermined amount of dispensing refrigerant M having a predetermined composition S ₀ of a non-azeotropic refrigerant is filled. The refrigerant storage tank 1 has a liquid phase discharge pipe 2 reaching the bottom of the vessel.
And the liquid refrigerant M provided in the extension outside the tank, the subdivision refrigerant M receives the subdivision filling receivers R ₁ , R ₂ ,.
It can be extracted to _n . A gas phase valve 4 is attached to a conduit extending from the top of the refrigerant storage tank 1.

[0009] Each receiver _{R 1, R 2, ...,} R n is the capacitance is optional, inlet valve V _1, V ₂ for receiving refrigerant m which is subdivided and packed respectively, ..., have a V _n By connecting these introduction valves and the liquid phase valve 3 of the refrigerant storage tank 1 with a flexible hose 5 or the like, a corresponding amount of the subdivided refrigerant m is filled in the receiver. . FIG. 1 shows a state where the receiver R ₁ is connected to the refrigerant storage tank 1.

In the present invention, another container (adjustment container) 6 is filled with an adjustment refrigerant (adjustment refrigerant) H having a composition substantially equivalent to the composition S ₀ of the subdivision refrigerant M. Then, a gas-phase valve 8 provided in a top conduit of the adjustment container 6 and a gas-phase valve 4 of the refrigerant storage tank 1 are connected by a conduction pipe 7. In this state, when the gas phase valve 4 and the gas phase valve 8 are opened, the gas phase of the subdivision refrigerant M and the gas phase of the adjustment refrigerant H are conducted to each other. It is preferable that the total amount of the adjusting refrigerant H be at least 1 weight times the total amount of the subdivision refrigerant M. .

The composition S of the adjusting refrigerant H used at this time is
_H needs to be substantially equal to the composition S ₀ of the subdivision refrigerant M, but does not have to completely match the composition S ₀ , and is preferably ± with respect to the composition S ₀ of the subdivision refrigerant M. 2
What is necessary is just to make it equivalent within the error range of weight%. Further, the temperature of the adjusting refrigerant H at the time of subdivision is determined by the subdivision refrigerant M.
It is preferable that the temperature is adjusted within the range of the same temperature to + 5 ° C.

The coupling system is at a constant temperature (preferably at room temperature)
When stable, when opening the Ekishoben 3 and inlet valve V _1, aliquoted refrigerant M (liquid phase) is pushed out by the pressure of the vapor phase in the refrigerant tank 1, liquid phase extraction pipe 2, Ekishoben 3, through the flexible hose 5 and the introduction valve V ₁ sequentially, a predetermined amount is filled as a refrigerant m to receiver R _1.

At this time, if the refrigerant storage tank 1 and the adjusting container 6
Is disconnected, the liquid phase amount in the refrigerant storage tank 1 becomes
As the gas volume decreases and the gas phase capacity increases,
The composition changes in the direction in which the concentration of low boiling components in the liquid phase decreases.
Get up. Therefore, the receiver R ₁From receiver R_Two,
…, R_nWhen the subdivision filling is continued by sequentially switching to
Composition S of refrigerant filled in these receivers_Two, ..., S_nIs
Initial composition (hereinafter referred to as "original composition") S of the subdivision refrigerant M
₀Will change from. However, the refrigerant storage tank 1 and the adjustment container
In the case of the present invention, in which
Vapor-Liquid Equilibrium Relationship in Regulating Container 6
As a result, the gas volume capacity of the refrigerant storage tank 1 increases.
Regardless, the composition of the remaining subdivision refrigerant M is the original composition S₀of
Will be kept as it is. Therefore, receiver R₁, R_Two, ..., R_n
Are switched in order, and subdivision filling is repeated.
Receiver R₁, R_Two, ..., R_nComposition of refrigerant to be filled
± 1 fold, regardless of the capacity of these receivers or the filling order
%, Preferably within ± 0.5% by weight.
S₀Becomes equal to In another embodiment of the present invention
As will be described later with reference to FIG.
Substantially even if the gas phase is in communication with the liquid phase of the subdivision refrigerant M
Yields similar results.

If the temperature of the subdivision refrigerant M in the refrigerant storage tank 1 fluctuates greatly during the subdivision period, the gas-liquid equilibrium relationship in the refrigerant storage tank 1 changes, causing a change in the composition of the refrigerant to be subdivided and charged. It is desirable that the temperature does not fluctuate, but at least ± 1 with respect to the temperature at the start of subdivision filling.
It is preferable to control the temperature within a fluctuation range of 0 ° C.

In this embodiment, since the total amount of the adjusting refrigerant H is at least 1 weight times the total amount of the subdivision refrigerant M, the gaseous phase from the adjusting refrigerant H is obtained at any stage of subdivision filling. , The low-boiling component is quickly supplied to the subdivision refrigerant M, and the subdivision can be quickly filled while maintaining the original composition S ₀ within the allowable range in each receiver.

In the specific example shown in FIG. 1, the number of the adjusting containers 6 is one. However, the number of adjusting containers is not necessarily limited to one. .
In this case, the amount of the adjusting refrigerant filled in each adjusting container may be constant or different. In short, the total amount of these adjusting refrigerants is at least 1 weight times the amount of the subdivision refrigerant. It should just be.

Similarly, the number of the refrigerant storage tanks 1 does not necessarily have to be one, and the gas phases of a plurality of refrigerant storage tanks filled with the respective amounts of the subdivision refrigerant may be used in a state where they are connected by a conduit. That is, for example, in a state where the gas phases of the plurality of adjustment containers and the plurality of refrigerant storage tanks are conducted, it is also possible to perform the subdivision filling from the plurality of refrigerant storage tanks simultaneously and in parallel.
In this case as well, it is preferable that the total amount of the adjusting refrigerant be at least 1 weight times the total amount of the subdivision refrigerant. .

According to the method of the present invention, the original composition S ₀ is maintained until the remaining amount of the subdivision refrigerant M in the refrigerant storage tank 1 reaches the extraction limit (limit of the liquid phase disappearing due to the characteristics of the refrigerant). Since a plurality of receivers can be sequentially filled in small quantities as they are, there is no need to return the residual refrigerant of which composition has changed to the filling factory to perform refrigerant recovery or regeneration processing. The factors can be eliminated and it is simple and economical.

Refrigerant to which the subdivision filling method of the present invention is applied
Are HCFC, HFC, HC, FC, HFE, FE, and
And non-azeotropic mixture of two or more selected from the group of FIC
It is preferably an object. Of these, specifics of HCFC
As an example, for example, HCFC22 (CHClF_Two), H
CFC123 (CHCl_Two-CF_Three), HCFC124
(CHClF-CF_Three), HCFC141b (CH_Three-CC
l_TwoF), HCFC142b (CH_Three-CCIF_Two), HC
FC225ca (CHCl_Two-CF_Two-CF_Three), HCFC
225cb (CHClF-CF_Two-CCIF_Two) Etc.
be able to. As a specific example of HFC, for example, HFC
23 (CHF_Three), HFC32 (CH_TwoF_Two), HFC4
1 (CH_ThreeF), HFC134 (CHF_Two-CHF_Two), H
FC134a (CH_TwoF-CF_Three), HFC143a (C
H_Three-CF_Three), HFC125 (CHF_Two-CF_Three), HFC
161 (CH_Three-CH_TwoF), HFC227ea (CF_Three-
CHF-CF_Three), HFC227ca (CHF_Two-CF_Two-C
F_Three), HFC236ca (CHF_Two-CF_Two-CHF_Two),
HFC236cb (CH_TwoF-CF_Two-CF_Three), HFC2
36ea (CHF_Two-CHF-CF_Three), HFC236fa
(CF_Three-CH_Two-CF _Three), HFC245ca (CH_TwoF-
CF_Two-CHF_Two), HFC245cb (CH_Three-CF_Two-C
F_Three), HFC245fa (CHF_Two-CH_Two-CF_Three), H
FC254cb (CH_Three-CF_Two-CHF_Two) Etc.
Can be. As a specific example of HC, for example, HC290
(CH_Three-CH_Two-CH_Three), HC600 (CH_Three-CH_Two-C
H_Two-CH_Three), HC600a ((CH_Three)_TwoCH-C
H_Three), HC601 (CH_Three-CH_Two-CH_Two-CH_Two-C
H_Three), HC601a ((CH_Three)_TwoCH-CH_Two-C
H_Three), HC601b ((CH_Three)_FourC), HC170
(CH_Three-CH_Three), HC-C270 (cyclic-CH_Two-CH_Two-
CH_Two-), HC1270 (CH_Three-CH = CH _Two)
Can be As a specific example of FC, for example, FC2
18 (CF_Three-CF_Two-CF_Three), FC-C318 (cyclic-C
_FourF₈-) And the like. Specifics of HFE and FE
As an example, for example, HFE134 (CHF_Two-O-CH
F_Two), HFE143a (CH_Three-O-CF_Three), HFE1
25 (CHF_Two-O-CF_Three), HFE227ca2 (CH
F_Two-CF_Two-O-CF_Three), HFE245cb2 (CH_Three-C
F_Two-O-CF_Three), HFE-C318 (cyclic-CF_Two-CF_Two
-CF_Two-O-CF_Two-), FE116 (CF_Three-O-CF_Three)etc
Can be mentioned. As a specific example of FIC,
BA FIC13I1 (CF_ThreeI), FIC115I1 (C
F_Three-CF_TwoI) and the like.

In particular, the subdivision charging method of the present invention can be effectively applied to subdivision charging of a non-azeotropic mixed refrigerant which has been regarded as a promising alternative refrigerant. Examples of these non-azeotropic mixed refrigerants include a common name and a component / composition (% by weight). For example, R403B: HC290 / HCFC22 / FC218 =
5/56/39 R407C: HFC32 / HFC125 / HFC134
a = 23/25/52 R407E: HFC32 / HFC125 / HFC134
a = 25/15/60 R900JA: HFC32 / HFC134a = 30/7
0 and so on.

Of these, especially R407C is HCF
Promising as an alternative refrigerant to C22. Therefore, one application example of the present invention when the R407C is filled in small portions will be described in detail below. In FIG. 1, a refrigerant R407C as a subdivision refrigerant M
kg, while the adjustment container 6 is filled with, for example, 20 kg of a refrigerant R407C having substantially the same composition as the adjustment refrigerant H, the gas phase valves 4 and 8 are opened, and the refrigerant storage tank 1 and the adjustment container 6 are connected. Conducts in the gas phase. In this state, withdrawing refrigerant through liquid discharge pipe 2 from the refrigerant tank 1, a plurality of receiver R _1, R _2, ..., filled by each 0.5kg to R _n. This operation is continued until the refrigerant storage tank 1 is removed.
Next, a sample of the refrigerant m filled in each receiver was collected and analyzed for composition by gas chromatography, and HFC32 in the receiver liquid phase (standard boiling point −51.7) with respect to the liquid phase withdrawal rate from the refrigerant storage tank 1 was measured. ° C) and HFC125 (standard boiling point -4)
(8.5 ° C.), the result of FIG. 3 is obtained.

From the results shown in FIG. 3, according to the method of the present invention, by allowing the gas phase of the subdivision refrigerant M to communicate with the gas phase of the adjustment refrigerant H, the composition hardly changes to the extraction limit of the refrigerant storage tank 1. It can be seen that subdivision filling can be performed.

On the other hand, without using the method of the present invention, the gas phase valve 4 in FIG.
While blocking conduction between the a receiver R ₁ from the refrigerant tank 1 a plurality of similar, R _2, ..., aliquoted filled refrigerant m of each 0.5kg to R _n, the refrigerant of each receiver FIG. 4 shows the results of the analysis to determine the composition change of HFC32 and HFC125 in the receiver liquid phase with respect to the liquid phase withdrawal rate from the refrigerant storage tank 1 when the adjusting refrigerant H is not used.

FIG. 4 shows that when the adjusting refrigerant H is not used, the receivers R ₁ , R
_2, ..., concentrations of HFC32 and HFC125 in the liquid phase of R _n is gradually decreased, although not shown, relatively HFC13
It can be seen that the concentration of 4a (normal boiling point -26.5 ° C) increases, and the composition change becomes remarkable especially when the withdrawal rate is 70% to 80% or more.

Actually, a predetermined amount of the subdivision refrigerant is stored in the refrigerant storage tank by a plurality of refrigeration / cooling methods by the conventional method without using the adjustment refrigerant H.
If the refrigerant tank of an air conditioner is filled in small batches, the composition of each machine will inevitably change.As a result, in order to maintain the performance of the machine within the control limits, when the extraction rate reaches a certain level, the Must be stopped. Normally, at room temperature, if the withdrawal is stopped at a liquid phase withdrawal rate of, for example, about 70% to 80%, the HFC 32 and H
Each change in the composition of FC125 was approximately -0.5 of the original composition.
% By weight. HFC32 and HF
The composition change of -0.5% by weight of C125 is relatively HF.
Since + 1% by weight of composition change is caused to C134a, the composition change of each component can be made within ± 1% by weight of the original composition as a result. To this extent, the performance of refrigeration and air conditioning equipment is acceptable. Within the range. Therefore HFC32,
In the case of a non-azeotropic refrigerant mixture consisting of HFC125 and HFC134a, the method of the present invention will be particularly effectively applied to the late residual refrigerant of 20% to 30% remaining after the initial withdrawal.

In the method of the present invention, when the gas phase or the liquid phase of the subdivision refrigerant M in the refrigerant storage tank 1 and the gas phase of the adjustment refrigerant H are conducted, the composition of the subdivision refrigerant M is larger. Therefore, the total amount of the adjusting refrigerant H as the composition adjusting source is preferably at least 1 weight times the total amount of the subdivision refrigerant M. Further, in order to keep the composition of the subdivision refrigerant M constant up to the extraction limit, it is more preferable that the composition be 2 times or more. However, in practice, as described above, the method of the present invention is particularly effective for the late residual refrigerant of 20% to 30% remaining after the initial withdrawal. It is only necessary to have a certain degree of adjustment refrigerant H. Therefore, it is effective even if the total amount of the adjusting refrigerant H is, for example, about 重量 weight times the initial total amount of the subdivision refrigerant M in the refrigerant storage tank 1.

As described above, the gas phase of the subdivision refrigerant M
Or, when conducting the liquid phase and the gas phase of the adjusting refrigerant H,
The composition of the cooling medium M is in the direction of approaching the composition with the larger amount.
But the composition of the subdivided refrigerant m
To keep within the limit of ± 1% by weight,
Composition S of refrigerant M₀The composition S of the adjusting refrigerant H _H
Is within ± 2% by weight even if not completely equivalent
It is preferable that it is adjusted to. Composition of adjustment refrigerant H
S_HIs the original composition S of the subdivision refrigerant M₀± 2% by weight
If it has changed beyond the
Possibility that the composition of subdivided refrigerant m changes beyond the allowable limit
Is not preferred.

In the method of the present invention, the low-boiling component contained in the gas phase of the adjusting refrigerant H compensates for the decrease in the concentration of the low-boiling component of the subdivision refrigerant M in the refrigerant storage tank due to the subdivision filling. Therefore, as shown in FIG. 2, the refrigerant storage tank 21 side terminal of the conduction pipe 27 that connects the adjustment container 26 and the refrigerant storage tank 21 is formed as an extension pipe 29 through the gas phase valve 24 to near the bottom of the refrigerant storage tank 21. By extending, the adjusting refrigerant H
May directly contact the liquid phase of the subdivision refrigerant M.

In any of the systems shown in FIGS. 1 and 2, the refrigerant storage tank and the adjusting container must be kept at the same temperature because the internal gas-liquid equilibrium relationship must be matched. Is preferred. That is, the temperature of the adjusting refrigerant H is
It is preferable that the temperature is equal to or lower than the temperature of the subdivision refrigerant M up to + 5 ° C. even if there is a temperature difference. When the temperature of the refrigerant for adjustment H is lower than the temperature of the refrigerant for subdivision M or higher than + 5 ° C., the function of the refrigerant for adjustment H keeps the composition of the refrigerant for subdivision M within a certain range from a gas-liquid equilibrium relationship. May not be able to be exhibited.

The temperature of the subdivision refrigerant M at the time of subdivision filling can be set arbitrarily. However, in general, if the temperature is higher than 40 ° C., it is not preferable because the internal pressure becomes high and there is a possibility of being restricted as a high pressure gas. Usually, it is preferable to perform the subdivision filling operation while maintaining the room temperature of less than 40 ° C. Further, the temperature of the subdivision refrigerant M during the subdivision filling operation is preferably constant from the start to the end of the subdivision filling, and even if there is a temperature change, it is preferable to keep it within ± 10 ° C. When changing the temperature exceeds this range, receiver R _1, R ₂ for subdivided and packed for vapor-liquid equilibrium in the refrigerant tank changes, ..., the composition of the refrigerant m withdrawn in R _n is acceptable It is not preferable because it may change beyond the limit.

When applying the method of the present invention, the volume, shape and number of the refrigerant storage tank, the adjusting container and the receivers (R ₁ , R ₂ ,..., R _n ) are particularly limited. Not something. For example, it may be a metal thin plate can called a service can, a transfer container such as a cylinder, a tank lorry, or an iso-container, or a fixed refrigerant container such as a refrigerant tank attached to refrigeration / air-conditioning equipment or a product tank.
Further, the refrigerant storage tank, the adjustment container, and the receiver may be the same or different. Therefore, both the refrigerant storage tank and the adjustment container may be constituted by several cylinders.

According to the method of the present invention, the composition of the refrigerant remaining after extracting a part of the liquid phase of the subdivision refrigerant from the refrigerant storage tank can be maintained without changing from the original composition.
Until the refrigerant storage tank is emptied, sub-filling is possible without a change in composition. In addition, since the composition of the adjusting refrigerant does not substantially change during the subdivision filling, for example, after the substituting refrigerant in the refrigerant storage tank is used up, the container containing the adjusting refrigerant is filled with a new refrigerant having the same composition. After using the container as an adjusting container, it can be used as a refrigerant storage tank for the next subdivision filling.

[0033]

Examples of the present invention will be described below. In each of the examples, the composition ratios are all by weight. (Example 1) In FIG. 1, a refrigerant storage tank 1 was filled with 20 kg of a non-azeotropic mixed refrigerant R407C as a subdivision refrigerant M.
The refrigerant M for subdivision in the container was sampled from the liquid phase extraction pipe 2 and the composition was measured by gas chromatography. HFC32 / HFC125 / HFC134a = 22.9
/24.9/52.2.

Separately, the same R40 as described above is placed in the adjusting container 6.
20 kg of 7C was charged and used as refrigerant H for adjustment. The composition of the adjusting refrigerant H is as follows: HFC32 / HFC125 / HFC134a = 23.3
/25.2/51.5, and it was confirmed that the composition was substantially the same as the composition of the subdivision refrigerant M within an error range of ± 1% by weight.

Next, as shown in FIG. 1, the top of the refrigerant storage tank 1 and the top of the adjusting vessel 6 are connected by a conducting pipe 7, and while the gas phase valves 4, 8 at the top of each vessel are closed, The exhaust pipe 10 of the side pipe is opened to evacuate the inside of the conduction pipe 7, and after the exhaust, the exhaust valve 1 is exhausted.
0 was closed, and the gas phase valves 4 and 8 were opened, and the gas phase portions of both containers were conducted. In this state, the liquid phase extraction pipe 2 of the refrigerant storage tank 1
Ekishoben 3 and receiver R _1, R ₂ for dispensing filled with refrigerant through a flexible hose 5, ..., to R _n, are sequentially extracted filled by 0.5 kg.

The receivers R ₁ , R ₂ ,.
_{When the} liquid phase was sampled from _n and the composition was analyzed for each, the results shown in FIG. 3 were obtained. That is, the concentration drop of the low boiling components of HFC32 and HFC125 is about 0.1% by weight up to the liquid phase extraction rate of about 95%, which is the extraction limit of the refrigerant storage tank 1, and is divided into a plurality of subdivision filling receivers. R407C whose composition variation was within ± 1% by weight with respect to the original composition of the refrigerant M was able to be charged.

After the above-mentioned subdivision filling operation was completed, the refrigerant in the adjusting container 6 was sampled and analyzed. HFC32 / HFC125 / HFC134a = 23.1
/25.0/51.9, which was substantially the same as the original composition of the subdivision refrigerant M. Therefore, when this adjusting container 6 is used as the refrigerant storage tank 1 and a new adjusting container is connected and reused as it is for the next subdivision filling, the new subdivision refrigerant M is used until the extraction limit is reached. R407C having a composition variation of ± 1% by weight with respect to the original composition could be filled.

(Comparative Example 1) The same method as in Example 1 was repeated except that the top gas phase valve 4 of the refrigerant storage tank 1 was closed and the gas phase of the refrigerant storage tank 1 and the gas phase of the adjustment container 6 were shut off. . The original composition of the subdivision refrigerant M in the refrigerant storage tank 1 is HFC32 / HFC125 / HFC134a = 23.1
/25.0/51.9. Receiver R _1, R ₂ for each subdivided and packed, ..., R _n
When the liquid phase was collected from and analyzed for each composition,
The result shown in FIG. 4 was obtained. As a result of the subdivision filling, the composition of the refrigerant in the subdivided and filled receiver near the liquid phase extraction rate of about 95%, which is the extraction limit of the refrigerant storage tank 1, is HFC32 /
HFC125 / HFC134a = 21.6 / 23.9 / 5
4.5, which is ± 1 with respect to the original composition of the subdivision refrigerant M.
Weight percent was out of tolerance.

(Embodiment 2) In FIG. 1, a non-azeotropic mixed refrigerant R407E as a subdivision refrigerant M is stored in a refrigerant storage tank 1 for 20 minutes.
kg filled. The subdivision refrigerant in the container was sampled from the liquid phase extraction pipe 2 and the original composition was measured by gas chromatography. HFC32 / HFC125 / HFC134a = 25.1
/14.9/60.0.

Separately, the same R40 as described above is placed in the adjusting container 6.
10 kg of 7E was charged and used as refrigerant H for adjustment. The amount of the refrigerant for adjustment H is 1 / the amount of the refrigerant for subdivision M in the refrigerant storage tank 1.
It was 2 weight times. The composition of the adjusting refrigerant H is HFC32 / HFC125 / HFC134a = 25.2.
/15.4/59.4, and it was confirmed that the composition was substantially the same as the original composition of the subdivision refrigerant M within an error range of ± 1% by weight.

Next, as shown in FIG. 1, the top of the refrigerant storage tank 1 and the top of the adjustment vessel 6 are connected by a conducting pipe 7, and while the gas phase valves 4, 8 at the top of each vessel are closed, The exhaust pipe 10 of the side pipe is opened to evacuate the inside of the conduction pipe 7, and after the exhaust, the exhaust valve 1 is exhausted.
0 was closed, and the gas phase valves 4 and 8 were opened, and the gas phase portions of both containers were conducted. In this state, the liquid phase extraction pipe 2 of the refrigerant storage tank 1
Ekishoben 3 and receiver R _1, R ₂ for dispensing filled with refrigerant through a flexible hose 5, ..., to R _n, are sequentially extracted filled by 0.5 kg.

Receiving units R ₁ , R ₂ ,.
_The liquid phase was sampled from _n and the composition was analyzed for each. The results show that almost the same composition is obtained for each of the receivers. The composition of the refrigerant in the receiver which is subdivided and filled near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is the same as that for the subdivision. The composition variation was within ± 1% by weight with respect to the original composition of the refrigerant M.

Comparative Example 2 The same method as in Example 2 was repeated, except that the top gas phase valve 4 of the refrigerant storage tank 1 was closed to shut off the gas phase of the refrigerant storage tank 1 and the gas phase of the adjustment container 6. . The original composition of the subdivision refrigerant M in the refrigerant storage tank 1 is HFC32 / HFC125 / HFC134a = 24.9
/15.1/60.0. As a result of the subdivision filling, the composition of the refrigerant in the subdivided and filled receiver near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is HFC32 / HFC125 / HFC134a = 22.4.
/14.0/63.6, ± 1% by weight based on the original composition of the subdivision refrigerant M
Was out of the allowable range.

(Embodiment 3) In FIG. 1, a non-azeotropic mixed refrigerant R900JA as a subdivision refrigerant M
0 kg was filled. Liquid phase discharge pipe 2 for subdivision refrigerant M in container
And the original composition was measured by gas chromatography. The result was HFC32 / HFC134a = 29.9 / 70.1.

Separately, the adjusting container 6 was filled with 40 kg of the refrigerant R900JA to obtain the adjusting refrigerant H. The amount of the adjusting refrigerant H was twice as large as the amount of the subdivision refrigerant M filled in the refrigerant storage tank 1. The composition of the conditioning refrigerant H is HFC32 / HFC134a = 31.4 / 68.6, which is substantially the same as the original composition of the subdivision refrigerant M within an error range of ± 2% by weight. It was confirmed that.

Next, as shown in FIG. 1, the top of the refrigerant storage tank 1 and the top of the adjusting vessel 6 are connected by a conducting pipe 7, and the gas phase valves 4 and 8 at the top of each vessel are kept closed. The exhaust pipe 10 of the side pipe is opened to evacuate the inside of the conduction pipe 7, and after the exhaust, the exhaust valve 1 is exhausted.
0 was closed, and the gas phase valves 4 and 8 were opened, and the gas phase portions of both containers were conducted. In this state, the liquid phase extraction pipe 2 of the refrigerant storage tank 1
Ekishoben 3 and receiver R _1, R ₂ for dispensing filled with refrigerant through a flexible hose 5, ..., to R _n, are sequentially extracted filled by 0.5 kg.

The receivers R ₁ , R ₂ ,.
_The liquid phase was sampled from _n and the composition was analyzed for each. The results show that almost the same composition is obtained for each of the receivers. The composition of the refrigerant in the receiver which is subdivided and filled near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is the same as that for the subdivision. The composition variation was within ± 1% by weight with respect to the original composition of the refrigerant M.

Comparative Example 3 The same method as in Example 3 was repeated, except that the top gas phase valve 4 of the refrigerant storage tank 1 was closed and the gas phase of the refrigerant storage tank 1 and the gas phase of the adjustment container 6 were shut off. The original composition of the subdivision refrigerant M in the refrigerant storage tank 1 in the initial stage was HFC32 / HFC134a = 30.2 / 69.8. As a result of subdivision filling, the composition of the refrigerant in the receiver subdivided and filled near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is HFC32 / HFC134a = 28.6 / 71.4. ± 1% by weight based on the original composition of refrigerant M
Was out of the allowable range.

(Embodiment 4) In FIG. 1, a non-azeotropic mixed refrigerant R403B was stored in a refrigerant storage tank 1 as a subdivision refrigerant M for 20 minutes.
kg filled. The refrigerant M for subdivision in the container was sampled from the liquid phase extraction pipe 2 and the original composition was measured by gas chromatography. HC290 / HCFC22 / FC218 = 4.9 / 56.
1 / 39.0.

Separately, the same R40 as described above is placed in the adjusting container 6.
100 kg of 3B was charged, and used as refrigerant H for adjustment. The amount of the refrigerant for adjustment H is 5 times the amount of the refrigerant for subdivision M in the refrigerant storage tank 1.
It was weight-fold. The composition of the adjusting refrigerant H is as follows: HC290 / HCFC22 / FC218 = 5.2 / 55.
3 / 39.5, and it was confirmed that the composition was substantially the same as the original composition of the subdivision refrigerant M within an error range of ± 1% by weight.

Next, as shown in FIG. 1, the top of the refrigerant storage tank 1 and the top of the adjusting vessel 6 are connected by a conducting pipe 7, and the gas phase valves 4, 8 at the top of each vessel are kept closed. The exhaust pipe 10 of the side pipe is opened to evacuate the inside of the conduction pipe 7, and after the exhaust, the exhaust valve 1 is exhausted.
0 was closed, and the gas phase valves 4 and 8 were opened, and the gas phase portions of both containers were conducted. In this state, the liquid phase extraction pipe 2 of the refrigerant storage tank 1
Ekishoben 3 and receiver R _1, R ₂ for dispensing filled with refrigerant through a flexible hose 5, ..., to R _n, are sequentially extracted filled by 0.5 kg.

Each of the receivers R ₁ , R ₂ ,.
_The liquid phase was sampled from _n and the composition was analyzed for each. The results show that almost the same composition is obtained for each of the receivers. The composition of the refrigerant in the receiver which is subdivided and filled near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is the same as that for the subdivision. The composition variation was within ± 1% by weight with respect to the original composition of the refrigerant M.

(Comparative Example 4) The same method as in Example 4 was repeated, except that the top gas phase valve 4 of the refrigerant storage tank 1 was closed to shut off the gas phase of the refrigerant storage tank 1 and the gas phase of the adjustment container 6. . The original composition of the subdivision refrigerant M in the refrigerant storage tank 1 is HC290 / HCFC22 / FC218 = 5.1 / 56.
2 / 38.7. As a result of the subdivision filling, the composition of the refrigerant in the subdivision-filled receiver near the liquid phase extraction rate of 95%, which is the extraction limit of the refrigerant storage tank 1, is HC290 / HCFC22 / FC218 = 4.7 / 58.
3 / 37.0, ± 1% by weight based on the original composition of subdivision refrigerant M
Was out of the allowable range.

(Embodiment 5) Referring to FIG.
20 kg of the non-azeotropic mixed refrigerant R407C as the subdivision refrigerant M was charged into the refrigerant storage tank 21 in which the extension pipe 29 was inserted so that the gas phase of the above directly contacted the liquid phase of the subdivision refrigerant M.
The subdivision refrigerant M in the refrigerant storage tank 21 is supplied to the liquid phase extraction pipe 2 at the bottom.
HFC32 / HFC125 / HFC134a = 23.2
/24.9/51.9.

Separately, 20 kg of the refrigerant R407C was charged into the adjusting container 26 to obtain the adjusting refrigerant H. This adjusting refrigerant H
Was 1 weight times the amount of the subdivision refrigerant M in the refrigerant storage tank 21. The composition of the adjusting refrigerant H is as follows: HFC32 / HFC125 / HFC134a = 24.1
/25.8/50.1, and it was confirmed that the composition was substantially the same as the original composition of the subdivision refrigerant M within an error range of ± 2% by weight.

Next, as shown in FIG. 2, the gas phase valves 24 and 28 provided at the top of the refrigerant storage tank 21 and the top of the adjustment vessel 26 are connected by a conduction pipe 27. With the valves 24 and 28 closed, the exhaust valve 30 provided on the side pipe of the conduit 27 is opened to evacuate the interior of the conduit 27. After the exhaust, the exhaust valve 30 is closed and the gas phase valves 24 and 28 are opened. Were made conductive. In this state, the refrigerant was sequentially extracted and filled into a receiver (not shown) for subdivision filling at a rate of 0.5 kg through the liquid phase extraction pipe 22 and the liquid phase valve 23 of the refrigerant storage tank 21.

The liquid phase was sampled from each of the subdivision filling receivers, and the composition was analyzed for each. As a result, the original composition of the subdivision refrigerant M was transferred to a plurality of subdivision filling receivers until the extraction limit of the refrigerant storage tank 21 was reached. ± composition variation
It was within 1% by weight.

[0058]

According to the method for subdividing and charging a non-azeotropic mixed refrigerant of the present invention, the gas phase or the liquid phase of the subdivision refrigerant is brought into communication with the gas phase of a conditioning refrigerant having substantially the same composition as this refrigerant. Since the refrigerant is filled in the divided state in the divided state, the composition of the divided refrigerant can be maintained at a constant level up to the limit of extracting the refrigerant from the refrigerant storage tank.

[Brief description of the drawings]

FIG. 1 is a process chart showing one embodiment of the present invention.

FIG. 2 is a process chart showing another embodiment of the present invention.

FIG. 3 is a graph showing a relationship between a liquid phase extraction rate and a liquid phase composition in one example of the present invention.

FIG. 4 is a graph showing a relationship between a liquid phase extraction rate and a liquid phase composition in a comparative example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Refrigerant storage tank, 2 ... Liquid phase extraction pipe, 3 ... Liquid phase valve, 4, 8 ... Gas phase valve, 5 ... Flexible hose, 6 ... Adjustment container, 7 ... Conducting pipe, 10 ... Exhaust valve, 21 ... Refrigerant storage tank, 22: liquid phase extraction pipe, 23: liquid phase valve, 24, 28: gas phase valve, 26: adjustment container, 27: conduction pipe, 29: extension pipe, 30: exhaust valve, M: subdivision refrigerant, m ... refrigerant, H ... adjusting _{refrigerant, R 1, R 2, R} n ... _{receiver, V 1, V 2, V} n ... introduction valve.

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[Procedure amendment]

[Submission date] November 17, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Wherein the total amount of the adjustment refrigerant claim 1 or, characterized in that a 1 weight times the total amount of dispensing refrigerant
A method for subdividing and charging a non-azeotropic mixed refrigerant according to claim 2 .

The composition of claim 4 for adjusting the refrigerant, according to any one of claims 1 to 3, characterized in that the equivalent within an error range of ± 2% by weight relative to the composition of the subdivision refrigerant Subdivision filling method of non-azeotropic mixed refrigerant.

5. The temperature adjustment refrigerant, a non-azeotropic refrigerant mixture according to any one of claims 1 to 4, characterized in that the temperature within the range of equivalents ~ + 5 ° C. in small portions refrigerant Subdivision filling method.

6. The temperature of the subdivision refrigerant from the start to the end of subdivision filling is ± 10% of the temperature at the start of subdivision filling.
The method according to any one of claims 1 to 5 , wherein the temperature is within a fluctuation range of ° C.

7. The subdivision refrigerant is hydrochlorofluorocarbon, hydrofluorocarbon, hydrocarbon, fluorocarbon, hydrofluoroether,
The non-azeotropic refrigerant mixture according to any one of claims 1 to 6 , wherein the refrigerant is a non-azeotropic refrigerant mixture comprising two or more kinds selected from the group consisting of fluoroether and fluoroiodocarbon. Filling method.

8. A non-azeotropic mixed refrigerant comprising at least two refrigerants selected from the group consisting of difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane. 7. The method for subdividing and charging a non-azeotropic mixed refrigerant according to any one of claims 1 to 6 .

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is directed to a method of sequentially filling a plurality of receivers with a subdivision refrigerant composed of a non-azeotropic mixed refrigerant filled in a refrigerant storage tank. There is provided a subdivision filling method of a non-azeotropic mixed refrigerant, in which a gaseous phase or a liquid phase of the subdivision refrigerant is conducted to a gaseous phase of an adjustment refrigerant having substantially the same composition as the refrigerant. In the above, each of the subdivision refrigerant and the adjustment refrigerant may be filled in a plurality of containers in which respective gas phases are conducted to each other. In the above, subdivision with adjustment refrigerant
And the refrigerant used to maintain the same gas-liquid equilibrium relationship.
It is preferably passed through. In the above, it is preferable that the total amount of the refrigerant for adjustment is at least 1 weight times the total amount of the refrigerant for subdivision. Further, it is preferable that the composition of the adjustment refrigerant is equal to the composition of the subdivision refrigerant within an error range of ± 2% by weight. Further, in the above, the temperature of the adjusting refrigerant is
It is preferable that the temperature is equal to or higher than the temperature of the subdivision refrigerant and + 5 ° C. Further, it is preferable that the temperature of the subdivision refrigerant from the start to the end of the subdivision filling be within a fluctuation range of ± 10 ° C. with respect to the temperature at the start of the subdivision filling. The subdivision refrigerant is HCFC, HFC, HC, FC, HF
It is preferably a non-azeotropic mixed refrigerant composed of two or more selected from the group consisting of E, FE, and fluoroiodocarbon (FIC). In particular, the subdivision refrigerants are difluoromethane (HFC32) and pentafluoroethane (HFC32).
125) and 1,1,1,2-tetrafluoroethane (HFC1
It is preferably a non-azeotropic refrigerant mixture composed of two or more kinds selected from the group 34a). In this specification, the term “refrigerant” means its liquid phase unless otherwise specified. "Composition" indicates the weight ratio of each component constituting the refrigerant (liquid phase).

Claims (7)

[Claims] When a subdivision refrigerant composed of a non-azeotropic mixed refrigerant filled in a refrigerant storage tank is sequentially subdivided into a plurality of receivers, a gaseous phase or a liquid phase of the subdivision refrigerant is combined with the refrigerant. A subdivision filling method of a non-azeotropic refrigerant mixture, which is conducted to a gaseous phase of a conditioning refrigerant having substantially the same composition. 2. The method according to claim 1, wherein the total amount of the adjusting refrigerant is at least 1 weight times the total amount of the subdivision refrigerant. 3. The non-azeotropic composition according to claim 1, wherein the composition of the conditioning refrigerant is equal to the composition of the subdivision refrigerant within an error range of ± 2% by weight. Subdivision filling method of mixed refrigerant. 4. The non-azeotropic mixed refrigerant according to any one of claims 1 to 3, wherein the temperature of the adjusting refrigerant is in a range from the temperature of the subdivision refrigerant to + 5 ° C. Subdivision filling method. 5. The temperature of the subdivision refrigerant from the start to the end of the subdivision filling is ± 10% of the temperature at the start of the subdivision filling.
The method for subdividing and charging a non-azeotropic mixed refrigerant according to any one of claims 1 to 4, wherein the temperature is within a fluctuation range of ° C. 6. The subdivision refrigerant is hydrochlorofluorocarbon, hydrofluorocarbon, hydrocarbon, fluorocarbon, hydrofluoroether,
The non-azeotropic mixed refrigerant according to any one of claims 1 to 5, wherein the refrigerant is a non-azeotropic mixed refrigerant composed of two or more kinds selected from the group consisting of fluoroether and fluoroiodocarbon. Filling method. 7. A non-azeotropic mixed refrigerant comprising at least two refrigerants selected from the group consisting of difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane. The method for subdividing and charging a non-azeotropic mixed refrigerant according to any one of claims 1 to 5.