JPH1161110A - Regeneration of residual refrigerant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply regenerating a residual non-azeotropic, mixed refrigerant whose composition is changed in a container by keeping it in communication with the vapor phase of an adjusting refrigerant to restore its composition in the container. SOLUTION: This method regenerates the vapor of liquid phase of a residual non-azeotropic, mixed refrigerant R (preferably composed of two or more compounds selected from hydrochlorofluorocarbon, hydrofluorocarbon, hydrocarbon, fluorocarbon, hydrofluoroether, fluoroether and fluoroiodocarbon compounds) whose composition is changed in a container by keeping it in communication with the vapor phase of an adjusting refrigerant H, having virtually the same composition as the refrigerant R of the original composition and also having at least the same weight of, preferably at least twice as much as, the residual refrigerant R for a period until the composition of the refrigerant R is restored to within an acceptable range of ±1 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simple method for regenerating a non-azeotropic mixed refrigerant remaining in a container and having a changed composition, in which the composition is restored and reused in the container.

[0002]

2. Description of the Related Art Conventionally, refrigerants having a single composition such as dichlorodifluoromethane (commonly called CFC12, the same applies hereinafter) and chlorodifluoromethane (HCFC22) have been widely used as refrigerants for cooling / refrigeration equipment. However, in recent years, stratospheric ozone depletion due to chlorofluorocarbons (CFCs) has been raised as a serious environmental problem.
Its production ceased at the end of 995. Therefore,
For cooling and refrigeration equipment using existing CFCs, a plurality of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), fluorocarbons (FCs), hydrocarbons (FCCs) whose physical properties and cooling performance have been adjusted as replacements or supplements Mixed refrigerants composed of carbons (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 in alternative applications, the principle of abolition in 2020 was decided, and international total regulation was started in 1996. Therefore, in particular, as an alternative to HCFC22 widely used in air conditioners and the like, an HFC with an ozone depletion potential of zero, which is not subject to regulation,
Refrigerants using components have been studied.

[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, since most of these mixed refrigerants are non-azeotropic mixtures, CFCs
Unlike azeotropic mixed refrigerants such as R12 and HCFC22 having a single composition, and so-called R502, which has been conventionally used as a low-temperature refrigerant, when extracted from a container and used or subdivided, the initial and late stages of extraction are different. There is a problem that the composition of the residual liquid phase changes. In other words, in these non-azeotropic mixtures, the concentration of low-boiling components contained in the gas phase becomes higher in the gas phase than in the liquid phase due to the gas-liquid equilibrium relationship. Decreases, the capacity of the gas phase relatively increases, and the low-boiling components move to the gas phase, and as a result, the concentration of the low-boiling components in the liquid phase decreases. If the composition of the liquid phase changes beyond the permissible limit, the cooling performance and other performances change, making it difficult to use. In practice, the residual refrigerant after being extracted from the container by about 80% is often returned to the filling factory without being reused. However, even when returned to the filling factory, the collection and the reprocessing process require a great deal of cost and time, and this has caused an increase in the price of the product. Further, even if a new refrigerant is replenished to the residual refrigerant, there is a problem in product management such that component analysis and composition adjustment of the replenished refrigerant product must be performed again.

As means for solving the problem of fluctuation of the liquid phase composition in a non-azeotropic mixed refrigerant, for example, Japanese Patent Application Laid-Open No. 8-15878
No. 10 proposes a method in which the composition of the refrigerant to be charged into the container is adjusted in advance so that the low boiling point component becomes excessive. However, this method also cannot avoid fluctuations in the liquid composition due to the capacity of the container, the amount of withdrawal, the number of withdrawals, and the like. The present invention has been made in order to solve the above-described problems, and an object of the present invention is to reuse a non-azeotropic mixed refrigerant having a changed composition remaining in a container by restoring the composition in the container. It is an object of the present invention to provide a simple and easy method for regenerating a residual refrigerant.

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method for converting a gaseous or liquid phase of a non-azeotropic mixed refrigerant having a composition changed and remaining in a container into an equal weight or more of the same. The residual refrigerant is communicated with the gas phase of the conditioning refrigerant having a composition substantially equivalent to the original composition of the residual refrigerant, and this conduction state is maintained until the composition of the residual refrigerant is restored within the allowable range of ± 1% by weight. A method for regenerating a refrigerant is provided. It is preferable that the amount of the adjusting refrigerant is at least 2 times the weight of the residual refrigerant. Further, it is preferable that the above-mentioned conduction state is maintained until the composition of the residual refrigerant is restored within an allowable range of ± 0.5% by weight. The non-azeotropic mixed refrigerant is HCFC, HFC, HC, FC, H
It is preferably a non-azeotropic mixture of two or more selected from the group consisting of FE, FE, and fluoroiodocarbon (FIC). Particularly, the non-azeotropic refrigerant mixture is difluoromethane (HFC32), pentafluoroethane (HF).
C125) and a non-azeotropic mixture of two or more selected from the group of 1,1,1,2-tetrafluoroethane (HFC134a). In this specification, the term “refrigerant” means its liquid phase unless otherwise specified. The term “composition” means 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 the method for regenerating the residual refrigerant of the present invention. In FIG. 1, reference numeral 1 denotes an actually used container. The actual use container 1 is originally filled with a specified amount of a non-azeotropic mixed refrigerant having a predetermined composition (original composition S ₀ ).
As a result, a part of the liquid phase is extracted, and the remaining liquid phase remains as the residual refrigerant R. Composition S of this residual refrigerant R
₁ changes from the original composition S ₀ with a relative quantitative change between the liquid phase and the gas phase in a certain vessel.

In the present invention, another container (adjusting container)
Unit) 3, the above-mentioned original set having a weight equal to or greater than the residual refrigerant R
S₀Conditioning refrigerant having a composition substantially equivalent to
(Conditioning refrigerant) H, and the top of the conditioner 3
Is connected to the top of the actual use container 1 by the conduit 4. to this
Therefore, the adjusting refrigerant H and the residual refrigerant R are in a gas phase with each other.
And it became conductive. Keep this connection at a constant temperature (preferably
Or room temperature), the container in the adjustment container 3
The gas-liquid equilibrium relationship matches the gas-liquid equilibrium relationship in the actual container 1
And as a result, the composition S of the residual refrigerant R₁
Gradually becomes the original composition S ₀To ± 1% by weight, preferably
Original composition S within the allowable range of ± 0.5% by weight₀Return to this
When the amount of the adjusting refrigerant H is 2 weight times or more of the residual refrigerant R,
In this case, restoration within the above-mentioned allowable range proceeds smoothly and promptly.
Run.

As a result, the residual refrigerant R in the actually used container 1 can be used up to the end while maintaining the original composition (S ₀ ), which is not only economical, but also has the composition S in the actually used container 1. _Refilling with a new mixed refrigerant having _zero does not substantially change the refrigerant composition in the container, so that the refilling operation in the filling factory is greatly simplified.

FIG. 2 shows another embodiment of the present invention. The embodiment of FIG. 2 is substantially similar to that of FIG. 1, except that the conduit 4 is connected to the actual container 1 via a valve 7.
Connected to an extension tube 11 extending to near the bottom of the inside,
When the valves 7 and 8 are opened, the residual refrigerant R in the actual use container 1
Is conducted to the gas phase of the adjusting refrigerant H.

In this embodiment, the shortage of the low boiling point component in the liquid phase of the residual refrigerant R is adjusted until the gas-liquid equilibrium relationship in the adjusting container 3 matches the gas-liquid equilibrium relationship in the actual use container 1. As a result, the composition S ₁ of the residual refrigerant R gradually approaches the original composition S _0, and the allowable range of ± 1% by weight, preferably ± 0.5% by weight. Back to the original composition S ₀ at the inner.

FIG. 3 shows still another embodiment of the present invention. This embodiment shows a method of collectively restoring the composition of residual refrigerant contained in various residual amounts in a plurality of actually used containers having various capacities, for example, in a filling factory. In FIG. 3, a plurality of practically used containers V ₁ ,
V ₂ , V ₃ ,..., V _n are each filled with a non-azeotropic mixed refrigerant originally having the same original composition S _0, and a liquid-phase discharge pipe reaching the bottom attached to each container. As a result, different amounts of the liquid phase are extracted, and as a result, the residual refrigerants R ₁ ,
R ₂ , R ₃ ,..., R _n are included.

First, each of the actually used containers V ₁ , V ₂ ,
The tops of V ₃ ,..., V _n are connected by a connecting pipe 5. On the other hand, an adjusting container 3 filled with the adjusting refrigerant H, preferably at least 2 times the total amount of the residual refrigerants R ₁ , R ₂ , R ₃ ,..., R _n is prepared. The composition of the adjusting refrigerant H is substantially equal to the original composition S ₀ . Then, the top of the adjusting container 3 and the connecting pipe 5 are connected by the connecting pipe 6.

As a result, the adjusting refrigerant H and each of the residual refrigerants R ₁ , R ₂ , R ₃ ,..., R _n are conducted in the gas phase. When this connection system is allowed to stand at a constant temperature (preferably room temperature) environment, the gas-liquid equilibrium relationship in the adjustment container 3 and the actual use containers V ₁ , V ₂ , V ₃ ,.
_n and the gas-liquid equilibrium relation within _n , and as a result, each of the residual refrigerants R ₁ , R ₂ , R ₃ ,.
_n composition of _{S 1, S 2, S 3} , ..., S n are both closer to the original composition S _0. In this way, the residual refrigerants contained in the actual use containers of various capacities and having different amounts and compositions are collectively collected within the allowable range of ± 1% by weight, preferably ± 0.5% by weight. It can be returned to S ₀ .

Hereinafter, the components of the present invention will be described in detail.
I will tell. Refrigerant treated by the method for regenerating residual refrigerant of the present invention
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)
Can be As a specific example of HFC, for example, HF
C23 (CHF_Three), HFC32 (CH_TwoF_Two), HFC
41 (CH_ThreeF), HFC134 (CHF_Two-CHF_Two),
HFC134a (CH_TwoF-CF_Three), HFC143a
(CH_Three-CF_Three), HFC125 (CHF_Two-CF_Three), H
FC161 (CH_Three-CH_TwoF), HFC227ea (C
F_Three-CHF-CF_Three), HFC227ca (CHF_Two-CF
_Two-CF_Three), HFC236ca (CHF_Two-CF_Two-CH
F_Two), HFC236cb (CH_TwoF-CF_Two-CF_Three), H
FC236ea (CHF_Two-CHF-CF_Three), HFC23
6fa (CF_Three-CH_Two-CF _Three), HFC245ca (C
H_TwoF-CF_Two-CHF_Two), HFC245cb (CH_Three-C
F_Two-CHF_Two), HFC245fa (CHF_Two-CH_Two-C
F_Three), HFC254cb (CH_Three-CF_Two-CHF_Two)Such
Can be mentioned. Specific examples of HC include, for example,
HC290 (CH_Three-CH_Two-CH_Three), HC600 (CH_Three
-CH_Two-CH_Two-CH_Three), HC600a ((CH_Three)_TwoCH
-CH_Three), HC601 (CH_Three-CH_Two-CH_Two-CH_Two-CH
_Three), HC601a ((CH_Three)_TwoCH-CH_Two-CH_Three),
HC601b ((CH_Three)_FourC), HC170 (CH_Three-C
H_Three), HC-C270 (cyclic-CH_Two-CH_Two-CH_Two-),
HC1270 (CH_Three-CH = CH _Two)
it can. As a specific example of FC, for example, FC218 (C
F_Three-CF_Two-CF_Three), FC-C318 (cyclic-C_FourF₈-)
And the like. Specific examples of HFE and FE
For example, HFE134 (CHF_Two-O-CHF_Two), H
FE143a (CH_Three-O-CF_Three), HFE125 (CH
F_Two-O-CF_Three), HFE227ca2 (CHF_Two-CF_Two-
O-CF_Three), HFE245cb2 (CH_Three-CF_Two-OC
F_Three), HFE-C318 (cyclic-CF_Two-CF_Two-CF_Two-O
-CF_Two-), FE116 (CF_Three-O-CF_Three)
Can be As a specific example of FIC, for example, FI
C13I1 (CF_ThreeI), FIC115I1 (CF_Three-C
F_TwoI) and the like.

In particular, the regeneration method of the present invention can be effectively applied to a conventionally known liquid phase remaining in a container of a non-azeotropic refrigerant mixture. 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.

[0018] Among the non-azeotropic mixed refrigerants known from the prior art, R407C in particular is considered to be promising as an alternative refrigerant to HCFC22. When R407C was filled in a certain container and the liquid phase was withdrawn from this container, HFC32 (standard boiling point-
51.7 ° C) and HFC125 (standard boiling point -48.5)
3C) is shown in FIG.

FIG. 3 shows that the concentration of HFC32 and HFC125 in the remaining liquid phase decreases uniformly as the extraction rate of the liquid phase increases.
It can be seen that the concentration of a (standard boiling point -26.5 ° C) increases, and the composition change becomes remarkable particularly when the extraction rate is 70% to 80% or more.

When a predetermined amount of refrigerant is actually divided into a plurality of refrigeration / air-conditioning devices and transferred and filled in this method, a composition change for each device is inevitable, and the performance of the device is kept within the control limits. In order to do so, when a certain extraction rate is reached, further extraction 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
The change in the composition of FC125 was approximately -0.5 of the original composition.
% By weight. HFC32 and HF
A composition change of -125% by weight of C125 is relative to 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 mixed refrigerant consisting of HFC125 and HFC134a, the present invention relates to the 20%
It will be applied to ％ 30% residual refrigerant R.

In the method of the present invention, the gas phase or the liquid phase of the residual refrigerant R is brought into conduction with the gas phase of the adjusting refrigerant H having the original composition,
The purpose is to bring the composition of the residual refrigerant R closer to the composition of the adjustment refrigerant H by matching the gas-liquid equilibrium relationship in the adjustment container with the gas-liquid equilibrium relationship in the actual use container. Since the change proceeds in a direction approaching the composition having the larger amount, the amount of the adjusting refrigerant as the composition adjusting source needs to be equal to or more than the weight of the residual refrigerant. Further, in order to smoothly and quickly restore the composition of the residual refrigerant to within the allowable range of ± 0.5% by weight, it is preferable that the composition be 2 times or more. As shown in FIG. 3, when the composition of the residual refrigerant contained in the plurality of actually used containers is collectively restored, it is preferable to use the adjusting refrigerant that is at least 2 times the weight of the total amount of the residual refrigerant.

In the method of the present invention, since the gas-liquid equilibrium relationship between the inside of the adjustment container and the inside of the actual use container needs to be matched, it is inevitable that the adjustment container and the actual use container have substantially the same temperature. Put down. It is preferable that the temperature difference between the adjustment container and the actually used container be within 5 ° C., if any. Further, since the temperature during the holding is preferably constant, it is preferable that the temperature change is suppressed within 5 ° C., if any. Actually, it is sufficient to perform the process at room temperature, so that there is no particular need to consider the temperature.

The containers used in applying the method of the present invention are not particularly limited, both for the containers actually used and the containers for adjustment. 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.

According to the method of the present invention, the residual refrigerant having a changed composition remaining after extracting a part of the liquid phase from the container can be restored to the original composition, so that the composition is substantially reduced until the container becomes empty. In addition to being able to extract a refrigerant that does not change, it is possible to suppress a change in composition when replenishing the residual refrigerant with a new refrigerant. Also, if the container is a refrigerant tank attached to refrigeration / air-conditioning equipment, for example, when a part of the highly volatile component of the refrigerant leaks during the cooling operation and the composition changes, the components are adjusted. The method of the present invention can be applied to

[0025]

Examples of the present invention will be described below. In each of the examples, the composition ratios are all by weight. (Example 1) The following standard composition HFC32 / HFC125 / HFC134a = 25/1
A non-azeotropic mixed refrigerant R407E (10 kg) having a ratio of 5/60 was charged into a predetermined container (capacity: 10 liters), and the liquid phase was extracted until the residual refrigerant amount became 2 kg. At this time, the composition of the residual refrigerant R was determined by gas chromatography. HFC32 / HFC125 / HFC134a = 24.2
/14.6/61.2.

Another container for adjustment was filled with R407E (10 kg), and this was used as adjustment refrigerant H. The amount of the adjusting refrigerant H was 5 times by weight the amount of the residual refrigerant R. As a result of analysis, the composition of the adjusting refrigerant H was HFC32 / HFC125 / HFC134a = 25.2.
/15.2/59.6, which is within the allowable range of ± 0.5% with respect to the standard composition.

Next, as shown in FIG. 1, the top of the actually used container 1 and the top of the adjusting container 3 are connected by a conducting tube (flexible hose) 4, and the valves 7 and 8 at the top of each container are closed. The valve 9 of the side pipe was opened to evacuate the inside of the conduit 4 after opening, and after evacuation, the valves 7 and 8 were opened to conduct the gas phase of both vessels. In this state, both containers were allowed to stand in a room at a constant temperature for about 16 hours to stabilize the internal refrigerant temperature. The surface temperature of each container after stabilization was consistent with room temperature.

At this stage, the valve 7 at the top of the actually used container 1 was closed, and the liquid phase extraction valve 10 was opened to collect the liquid phase and analyze the composition. The result is: HFC32 / HFC125 / HFC134a = 25.0
/15.1/59.9, and was restored to the standard composition within an allowable range of ± 0.5% by weight. The increase in the weight of the residual refrigerant R due to this treatment was small. As a result of this processing, the entire amount of the residual refrigerant R in the actually used container 1 could be used up as a refrigerant having a predetermined composition.

(Embodiment 2) As shown in FIG.
10, 10, 20, 20, and 100 liters respectively)
5 actual containers V₁, V_Two, V_Three, V_FourAnd V_FiveFor
The following standard composition HFC32 / HFC125 / HFC134a = 23/2
The non-azeotropic refrigerant mixture R407C having 5/52
g, 10 kg, 20 kg, 20 kg and 100 kg
These liquid phases were separated by 2kg, 4kg, 5kg,
It was extracted until it reached 6 kg and 15 kg. At this time,
Refrigerant R₁, R_Two, R _Three, R_FourAnd R_FiveThe composition of the gask
As a result of the chromatographic measurement, HFC32 / H
R in the order of FC125 / HFC134a₁: 22.3 / 24.4 / 53.3 R_Two: 22.4 / 24.5 / 53.1 R_Three: 22.1 / 24.2 / 53.7 R_Four: 22.3 / 24.4 / 53.3 and R_Five: 22.3 / 24.2 / 53.5.

Separately, an adjustment container 3 having a capacity of 100 liters
Was filled with R407C (100 kg), and this was used as refrigerant H for adjustment. The amount of the adjusting refrigerant H was about 3 times the total amount of the residual refrigerants R ₁ , R ₂ , R ₃ , R ₄ and R ₅ . As a result of the analysis, the composition of the adjusting refrigerant H was HFC32 / HFC125 / HFC134a = 23.3.
/25.2/51.5, which was within the allowable range of ± 0.5% with respect to the standard composition.

Next, each of the actually used containers V ₁ , V ₂ , V ₃ , V
₄ and V _5, and connected by a connecting pipe (flexible hose) 5 to each other through the valve of the respective top and this connection pipe 5 and the regulating container 3, the conduit through the valve of the top (flexible Hose 6). While the top valves of the containers are closed, the valves of the side pipes provided in the conduits 6 are opened to evacuate the conduits 6 and the connecting pipes 5. The gas phase was conducted. In this state, all containers are allowed to stand in a room at a constant temperature for about 16 hours,
The internal refrigerant temperature was stabilized. The surface temperature of each container after stabilization was consistent with room temperature.

At this stage, the actually used containers V ₁ , V ₂ ,
The top valves of V ₃ , V ₄ and V ₅ were closed, the valves of the liquid phase extraction pipes of the respective containers were opened, and the liquid phase was collected, and the composition was analyzed by gas chromatography. As a result, the measured values of the residual refrigerants R ₁ , R ₂ , R ₃ , R ₄ and R ₅ were almost the same, and HFC32 / HFC125 / HFC134a = 23.1.
/24.9/52.0, and all were restored to the standard composition within an allowable range of ± 0.5% by weight. The increase in the weight of the residual refrigerant due to this treatment was small. As a result of this batch processing, all of the residual refrigerants R ₁ , R ₂ , R ₃ , R ₄ and R ₅ could be used up as a refrigerant of a predetermined composition.

Example 3 A non-azeotropic mixed refrigerant R900JA (0.8 kg) having the following standard composition HFC32 / HFC134a = 30/70 was charged into a predetermined container (1 liter capacity), and this liquid phase was It was extracted and used until the residual refrigerant amount became 0.4 kg. At this time, the composition of the residual refrigerant R was changed to HFC32 / HFC134a = 29.0 / 71.0 as a result of gas chromatography measurement.

Separately, R900JA is used for an adjustment container of the same capacity.
(0.8 kg) was prepared, and this was used as refrigerant H for adjustment. The amount of the adjusting refrigerant H was twice as much as the amount of the residual refrigerant R. The composition of the adjusting refrigerant H is
As a result of the analysis, HFC32 / HFC134a was 30.4 / 69.6, and it was confirmed that the difference was within the allowable range of ± 0.5% with respect to the standard composition.

Next, as shown in FIG. 2, the valve 7 attached to the external terminal of the extension pipe 11 of the actual use container 1 and the adjusting container 3
Is connected to the top valve 8 by a conductive pipe (flexible hose) 4, and while the valves 7 and 8 are closed, the side pipe valve 9 provided in the conductive pipe 4 is opened to exhaust the inside of the conductive pipe 4, Later valve 9
Is closed and the valves 7 and 8 are opened to allow the residual refrigerant R (liquid phase) in the actual use container 1 to communicate with the gas phase of the adjustment refrigerant in the adjustment container 3. In this state, both containers were allowed to stand in a room at a constant temperature for about 24 hours to stabilize the internal refrigerant temperature. The surface temperature of each container after stabilization was consistent with room temperature.

At this stage, the valve 7 at the top of the actually used container 1 was closed, and the liquid phase extraction valve 10 was opened to collect the liquid phase and analyze the composition. The result was HFC32 / HFC134a = 29.9 / 70.1, and the composition was restored to the standard composition within the allowable range of ± 0.5% by weight. The increase in the weight of the residual refrigerant R due to this treatment was small. As a result of this processing, the entire amount of the residual refrigerant R in the actually used container 1 could be used up as a refrigerant having a predetermined composition.

(Example 4) The following standard composition HC290 / HCFC22 / FC218 = 5/56/3
A non-azeotropic mixed refrigerant R403B (10 kg) having the following formula 9 was charged into a predetermined container (capacity: 10 liters), and this liquid phase was extracted and used until the residual refrigerant amount became 2.5 kg. At this time, the composition of the residual refrigerant R was determined by gas chromatography as follows: HC290 / HCFC22 / FC218 = 4.8 / 5
7.0 / 38.2.

Separately, an R403B
(10 kg) was prepared, and this was used as refrigerant H for adjustment. The amount of the adjusting refrigerant H was 4 times the weight of the amount of the residual refrigerant R. As a result of analysis, the composition of the adjusting refrigerant H was determined to be HC290 / HCFC22 / FC218 = 5.1 / 5.
5.6 / 39.3, which was confirmed to be within the allowable range of ± 0.5% with respect to the standard composition.

Next, as shown in FIG. 1, the top of the actually used container 1 and the top of the adjusting container 3 are connected by a conductive tube (flexible hose) 4, and the valves 7, 8 at the top of each container are closed. While the valve 9 of the side pipe was opened, the inside of the conduit 4 was evacuated. After the evacuation, the valves 7 and 8 were opened to conduct the gas phase of both vessels.
In this state, both containers were allowed to stand in a room at a constant temperature for about 16 hours to stabilize the internal refrigerant temperature. The surface temperature of each container after stabilization was consistent with room temperature.

At this stage, the valve 7 at the top of the actually used container 1 was closed, and the liquid phase extraction valve 10 was opened to collect the liquid phase and analyze the composition. The result is: HC290 / HCFC22 / FC218 = 5.0 / 5
5.9 / 39.1, and was restored to the standard composition within an allowable range of ± 0.5% by weight. The increase in the weight of the residual refrigerant R due to this treatment was small. As a result of this processing, the entire amount of the residual refrigerant R in the actually used container 1 could be used up as a refrigerant having a predetermined composition.

[0041]

According to the method for regenerating the residual refrigerant of the present invention, the gaseous phase or the liquid phase of the residual refrigerant of the non-azeotropic mixed refrigerant is converted into the vapor of the conditioning refrigerant having substantially the same original composition as that of the residual refrigerant. Phase and maintain this state of conduction until the composition of the residual refrigerant is restored within the allowable range of ± 1% by weight. Residual refrigerants that have been varied in composition can also be restored to the original original composition at once without removing them from the container, and the entire amount of the refrigerant in the actual use container can be used up while maintaining the original composition. Become like In addition, when the mixed refrigerant having the original composition is replenished to the actually used container including the residual refrigerant, the refrigerant composition in the container is restored by applying the regeneration method of the present invention, so that the filling operation is greatly simplified. . Furthermore, if the method of the present invention is applied to an attached refrigerant tank for refrigeration / air-conditioning equipment in which a part of highly volatile components of the refrigerant leaks during the cooling operation and the cooling performance is deteriorated, the refrigerant does not need to be replaced. Function can be restored.

[Brief description of the drawings]

FIG. 1 is a combined diagram showing an embodiment of the present invention.

FIG. 2 is a combined view showing another embodiment of the present invention.

FIG. 3 is a connection diagram showing still another embodiment of the present invention.

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

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Actual use container 2 ... Liquid phase extraction pipe 3 ... Adjustment container 4 ... Conducting pipe 5 ... Connecting pipe 6 ... Conducting pipe 7, 8 ... Valve at the top of container 9 ... Valve of side pipe 10 ... Liquid phase extraction valve 11 ... extension pipe R ... residual refrigerant H ... adjusting refrigerant _{R 1, R 2, R 3} , R n ... residual refrigerant _{V 1, V 2, V 3} , V n ... actual use containers

Claims (5)

[Claims] 1. A method of adjusting a gaseous phase or a liquid phase of a non-azeotropic mixed refrigerant remaining in a container and having a changed composition to have an equivalent weight or more of a composition substantially equivalent to the original composition of the residual refrigerant. A method for regenerating a residual refrigerant, wherein the residual refrigerant is conducted until the composition of the residual refrigerant is restored within a permissible range of ± 1% by weight. 2. The method for regenerating a residual refrigerant according to claim 1, wherein the amount of the adjusting refrigerant is at least 2 times the weight of the residual refrigerant. 3. The method according to claim 1, wherein the composition of the residual refrigerant is ±
The method for regenerating residual refrigerant according to claim 1, wherein the residual refrigerant is held until it is restored within an allowable range of 0.5% by weight. 4. The non-azeotropic mixed refrigerant according to claim 1, wherein the non-azeotropic mixed refrigerant comprises two or more selected from the group consisting of hydrochlorofluorocarbon, hydrofluorocarbon, hydrocarbon, fluorocarbon, hydrofluoroether, fluoroether, and fluoroiodocarbon. The method for regenerating a residual refrigerant according to claim 1, wherein the method is a boiling mixture. 5. The non-azeotropic mixture refrigerant is a non-azeotropic mixture of two or more selected from the group consisting of difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane. The method for regenerating a residual refrigerant according to claim 1, wherein: