JP2016073972A - Component separation method of mixed refrigerant and component separation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a component separation method of mixed refrigerant besides a distillation method and a component separation device in order to effectively recycle mixed refrigerant recovered from used equipment.SOLUTION: A component separation method of mixed refrigerant, in the method for separating a specified refrigerant component from mixed refrigerant including two kinds or more of refrigerant stored in a pressure container under a pressure exceeding the atmospheric pressure, includes: a preparation process of reducing a pressure in a reaction container in which adsorbent capable of selectively adsorbing the specified refrigerant of the mixed refrigerant is filled into a pressure less than the atmospheric pressure, removing gas existing in the reaction container from the reaction container and, at the same time, removing substances adsorbed by the adsorbent; an adsorption process of supplying the mixed refrigerant from the pressure container to the reaction container due to a height difference of an internal pressure between the pressure container and the reaction container and adsorbing the specified refrigerant component onto the adsorbent; and a desorption process of heating the adsorbent with hot medium and desorbing the specified refrigerant component adsorbed by the adsorbent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a component separation method and component separation device for a mixed refrigerant used in an air conditioner, a refrigerator / refrigerator, and the like, and more particularly, a method for separating at least one refrigerant component from a mixed refrigerant stored in a pressure vessel. And an apparatus for the same.

  For refrigerants used in air conditioners, refrigerators and refrigerators, etc., a mixture of a single composition and two or more refrigerants mixed at a specified ratio in order to obtain performance that cannot be achieved with a single composition. There is a refrigerant. Examples of the mixed refrigerant include “R-410A” which is a mixture of difluoromethane (HFC-32) and pentafluoroethane (HFC-125), pentafluoroethane (HFC-125), 1,1,1-trifluoro. “R-404A”, a mixture of ethane (HFC-143a) and 1,1,1,2-tetrafluoroethane (HFC-134a), difluoromethane (HFC-32), pentafluoroethane (HFC-125) and A refrigerant mixture of chlorofluorocarbons such as “R-407C” or “R-407E”, which is a mixture of 1,1,1,2-tetrafluoroethane (HFC-134a), is widely used. In addition, hydrocarbon-based mixed refrigerants such as propane and isobutane are also used mainly in refrigerators and vending machines.

  On the other hand, from the viewpoint of protecting the global environment, it is obliged to collect chlorofluorocarbons used as refrigerant from used chilled equipment (laws on rationalization and appropriate management of chlorofluorocarbons, recycling of home appliances) Law and Automobile Recycling Law; both abbreviations). Since the recovered chlorofluorocarbons must be destroyed by a prescribed treatment method such as combustion treatment in a combustion furnace, it requires a lot of energy for destruction, not only has a large environmental impact, but also costs processing. Yes. Therefore, it is desired to reuse the recovered refrigerant, and technical development for that purpose is underway.

  In Patent Document 1, after collecting a mixture of refrigerant (2,3,3,3-tetrafluoro-1-propene) having a single composition and refrigerating machine oil from a used device, the refrigerant is removed using an oil separator. An apparatus is described that can be separated and the refrigerant can be reused. Non-Patent Document 1 discloses a regeneration technique for reusing refrigerant collected from used equipment, such as R-12 (dichlorodifluoromethane) and R-22 (chlorodifluoromethane). As for the refrigerant having the single composition, it is described that impurities such as moisture and oil contained in the collected refrigerant are removed by distillation or the like and regenerated as a new product. In addition, for mixed refrigerants composed of a plurality of components, R-404A and R-410A, which are pseudo-azeotropic mixed refrigerants, have relatively little influence on the composition change due to the recovery and refilling operations. It is described that the composition change of such a non-azeotropic refrigerant mixture is likely to occur due to the recovery / refilling operation, and the composition change occurs if the recovery rate is low.

  Further, in Patent Document 2, as a method of restoring the composition of the mixed refrigerant whose composition has changed, the gas phase or liquid phase of the mixed refrigerant whose composition has changed is used as the gas phase of the refrigerant having the original composition equal to or greater than this. And a method of maintaining the composition until the composition is restored has been proposed.

JP 2013-113461 A Japanese Patent Laid-Open No. 11-61110

Masao Kuraji, “Current Status and Challenges of Refrigerant Recovery and Reuse in Japan,” Abstracts of Alternative Refrigerant and Environmental International Symposium 2002, Japan Refrigeration and Air Conditioning Industry Association, December 5, 2002, Internet URL: http: / /www.kankyosoken.co.jp/html/news/20030108/kurachi-report.pdf

  As described in Patent Document 1 and Non-Patent Document 1, for a refrigerant having a single composition, reuse of the processed refrigerant is realized by oil removal by an oil separator or distillation treatment. However, the composition of a non-azeotropic refrigerant mixture changes when it is recovered from equipment or extracted from a cylinder. Therefore, it is necessary to adjust the composition, and it cannot be reused simply by removing impurities such as oil. . Furthermore, even quasi-azeotropic refrigerants such as R-410A and R-404A are used as refrigerants in equipment and the composition gradually changes during repeated phase changes. Similar to the refrigerant, there is a problem that the composition needs to be adjusted for reuse.

  Patent Document 2 proposes a method of restoring the composition of the mixed refrigerant whose composition has changed, but with this method, it is difficult to accurately adjust the composition. There was a problem that a considerable amount of refrigerant was required.

  Therefore, in reusing the recovered mixed refrigerant, if the components constituting the mixed refrigerant can be separated, the separated components can be used as a single composition refrigerant or again at a predetermined ratio with other components. This is effective because it can be mixed to form a mixed refrigerant. However, as described in Non-Patent Document 1, components having a single composition are separated by distillation, but the mixed refrigerant is generally a mixture of compounds having close boiling points. In many cases, it is difficult to separate components by distillation due to differences in boiling points. For example, the boiling point of difluoromethane (HFC-32) contained in R-410A of the mixed refrigerant is −51.65 ° C., the boiling point of pentafluoromethane (HFC-125) is −48.13 ° C., and both have boiling points. Because it is very close, it is difficult to separate the components of R-410A by distillation techniques.

  An object of the present invention is to provide a new component separation method and component separation device for a mixed refrigerant other than the distillation method for effectively reusing the mixed refrigerant collected from used equipment.

  Another object of the present invention is to provide a mixed refrigerant component separation method and component separation apparatus that do not require much energy, have low processing costs, and can efficiently separate mixed refrigerant components. It is in.

  Still another object of the present invention is to provide a mixed refrigerant component separation method and component separation apparatus capable of efficiently exhibiting a function of separating a specific mixed refrigerant component.

  Still another object of the present invention is to provide a mixed refrigerant component separation method and component separation apparatus that can efficiently and continuously maintain the function of separating a specific mixed refrigerant component.

  In order to solve the above problem, the component separation method for mixed refrigerant of the present invention is a method for separating a specific refrigerant component from a mixed refrigerant containing two or more types of refrigerant stored in a pressure vessel under a pressure exceeding atmospheric pressure. , The pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing a specific refrigerant component of the mixed refrigerant is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel and adsorbed. The mixed refrigerant is supplied from the pressure vessel to the reaction vessel and a specific refrigerant component is adsorbed to the adsorbent by the preparation process for removing the substance adsorbed on the agent and the difference in internal pressure between the pressure vessel and the reaction vessel. An adsorption step, and a desorption step of heating the adsorbent with a heat medium and desorbing a specific refrigerant component adsorbed on the adsorbent.

  The present invention provides a new mixed refrigerant component separation method other than the distillation method in which a specific refrigerant component in a mixed refrigerant is selectively adsorbed by an adsorbent and efficiently desorbed. Since the components of the mixed refrigerant can be easily separated, the separated components can be reused as a single composition refrigerant, or mixed with other components at a predetermined ratio to regenerate the mixed refrigerant. . In addition, because of the difference in internal pressure between the pressure vessel and the reaction vessel, a mixed refrigerant is supplied from the pressure vessel to the reaction vessel to adsorb specific components, and the adsorbent is heated to desorb specific refrigerant components. The specific refrigerant component can be separated from the mixed refrigerant only by the physical operation of the pressure change in the specific condition range and the heat transfer in the specific condition range without using a chemical agent or the like. In this way, the specific components of the mixed refrigerant can be selectively separated only by the physical operation of pressure change and heat transfer, so a lot of energy is not required, the processing cost is low, and the efficiency is high. The components of the mixed refrigerant can be separated. In particular, in the present invention, by reducing the pressure in the reaction vessel filled with the adsorbent to less than atmospheric pressure, the air previously contained in the reaction vessel is discharged out of the apparatus, and the adsorption reaction for component separation Can be performed efficiently. In addition, since the components (mainly moisture etc.) adsorbed from the beginning of the adsorbent are also desorbed and discharged outside the apparatus, the adsorbent can be reliably regenerated and the efficiency of the subsequent adsorption reaction can be improved. it can.

  Further, the mixed refrigerant component separation method of the present invention is a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerants stored in a pressure vessel under a pressure exceeding atmospheric pressure. Among them, the pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing a specific refrigerant component is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel and adsorbed by the adsorbent. A preparatory process to remove the substances present, an adsorption process in which a mixed refrigerant is supplied from the pressure vessel to the reaction vessel due to the difference in internal pressure between the pressure vessel and the reaction vessel, and a specific refrigerant component is adsorbed to the adsorbent; By reducing the pressure in the container, among the mixed refrigerant, a recovery process for recovering other components than the specific refrigerant component from the reaction container, and heating the adsorbent with a heat medium and adsorbing the adsorbent Specific cold And a desorption step of the components desorbed.

  Due to the difference in internal pressure between the pressure vessel and the reaction vessel, a mixed refrigerant is supplied from the pressure vessel to the reaction vessel to adsorb specific components, the inside of the reaction vessel is decompressed to collect other components, and adsorbent is added. In order to desorb a specific refrigerant component by heating, the specific refrigerant component is removed from the mixed refrigerant only by a physical operation such as pressure change in a specific condition range and heat transfer in a specific condition range without using a chemical agent or the like. Can be separated. In this way, the specific components of the mixed refrigerant can be selectively separated only by the physical operation of pressure change and heat transfer, so a lot of energy is not required, the processing cost is low, and the efficiency is high. The components of the mixed refrigerant can be separated. In particular, in the present invention, the pressure in the reaction vessel is reduced without heating the adsorbent for other components that are supplied into the reaction vessel and are not selectively adsorbed by the adsorbent and exist in the reaction vessel. Therefore, it can be easily collected.

  Further, the mixed refrigerant component separation method of the present invention is a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerants stored in a pressure vessel under a pressure exceeding atmospheric pressure. Among them, the pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing a specific refrigerant component is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel and adsorbed by the adsorbent. The mixed refrigerant is supplied from the pressure vessel to the reaction vessel at a gas pressure of atmospheric pressure or higher, and a specific refrigerant component is used as the adsorbent. Adsorption process for adsorbing, in the adsorption process, a process for allowing other refrigerant components not adsorbed by the adsorbent to flow out of the reaction vessel and recovering, and for heating the adsorbent with a heat medium and identifying the adsorbed by the adsorbent Cold And a desorption step of the components desorbed.

  Due to the difference in internal pressure between the pressure vessel and the reaction vessel, mixed refrigerant is supplied from the pressure vessel to the reaction vessel to adsorb specific components, while other refrigerant components that have not been adsorbed by the adsorbent flow out of the reaction vessel. By separating and recovering, keeping the adsorbent warm and desorbing specific refrigerant components, without using chemical agents etc., only by physical operation of pressure change in specific condition range and heat transfer in specific condition range, A specific refrigerant component and other refrigerant components can be separated from each other. In particular, in the present invention, other refrigerant components that are not adsorbed by the adsorbent flow out of the reaction vessel and are recovered due to the difference in pressure, and specific refrigerant components that are selectively adsorbed by the adsorbent are recovered by desorption. To be separated.

  Further, the mixed refrigerant component separation method of the present invention is a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerants stored in a pressure vessel under a pressure exceeding atmospheric pressure. Among them, the pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing a specific refrigerant component is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel and adsorbed by the adsorbent. The mixed refrigerant is supplied from the pressure vessel to the reaction vessel at a gas pressure of atmospheric pressure or higher, and a specific refrigerant component is used as the adsorbent. An adsorption process for adsorbing, and a desorption process for heating the adsorbent with a heat medium and desorbing a specific refrigerant component adsorbed on the adsorbent. Components remaining in the container and It is recovered Te.

  Due to the difference in internal pressure between the pressure vessel and the reaction vessel, a mixed refrigerant is supplied from the pressure vessel to the reaction vessel to adsorb specific components, and the adsorbent is heated to desorb specific refrigerant components. A specific refrigerant component can be separated from the mixed refrigerant only by a physical operation of pressure change in a specific condition range and heat transfer in a specific condition range without using a chemical or the like. In this way, the specific components of the mixed refrigerant can be selectively separated only by the physical operation of pressure change and heat transfer, so a lot of energy is not required, the processing cost is low, and the efficiency is high. The components of the mixed refrigerant can be separated. In particular, in the present invention, other refrigerant components that are not adsorbed by the adsorbent are recovered as components remaining in the pressure vessel, and specific refrigerant components that are selectively adsorbed by the adsorbent are recovered by desorption and easily separated. .

  In the mixed refrigerant component separation method of the present invention, the supply of the mixed refrigerant from the pressure vessel to the reaction vessel is performed via a pressure reducing valve provided between the pressure vessel and the reaction vessel. It is also preferable to carry out the pressure so that it is less than 200 kPa. Thereby, since the pressure in a reaction container does not exceed 200 kPa, component separation of a mixed refrigerant can be performed safely. Further, the components of the mixed refrigerant can be separated even if the reaction vessel does not have the pressure resistance performance of the “pressure vessel” in the Industrial Safety and Health Act.

  Furthermore, in the component separation method for a mixed refrigerant of the present invention, it is preferable that the adsorbent is heated in the desorption step by heating the reaction vessel with a heat medium of less than 100 ° C. Thereby, the desorption reaction of the specific refrigerant component adsorbed by the adsorbent can be promoted while preventing thermal decomposition or alteration of the refrigerant component.

  In the method for separating mixed refrigerant components according to the present invention, the desorption of the specific refrigerant component adsorbed by the adsorbent is preferably performed by reducing the pressure in the reaction vessel. Thus, the specific refrigerant component is recovered and the adsorbent is also regenerated, so that it can be prepared for a subsequent adsorption reaction.

  In the mixed refrigerant component separation method of the present invention, the depressurization in the reaction vessel in the desorption of the specific refrigerant component adsorbed by the adsorbent is performed so that the pressure in the reaction vessel is 1 kPa or more and less than 20 kPa. It is also preferable. Thereby, a pressure excellent in desorption efficiency is selected.

  In the method for separating mixed refrigerant components of the present invention, it is also preferable that desorption of a specific refrigerant component adsorbed by the adsorbent is performed by supplying a purge gas to the reaction vessel. Thereby, a desorption method other than the depressurization method is selected.

  The mixed refrigerant component separation device of the present invention is a component separation device that separates a specific refrigerant component from a mixed refrigerant containing two or more types of refrigerant stored in a pressure vessel, and is connected to the pressure vessel, A reaction vessel filled with an adsorbent capable of selectively adsorbing a specific refrigerant component of the mixed refrigerant supplied from the vessel via the pressure reducing valve; and connected to the reaction vessel to reduce the pressure in the reaction vessel A pressure reducing means for discharging the gas present in the reaction vessel and a substance adsorbed by the adsorbent from the reaction vessel, a temperature adjusting means having a heat medium for adjusting the temperature of the reaction vessel, and the reaction vessel, and at least adsorption A recovery container for recovering a specific refrigerant component adsorbed by the agent.

  Utilizing the difference in internal pressure between the pressure vessel and the reaction vessel, supply mixed refrigerant to the reaction vessel, adsorb specific components with the adsorbent, and control the temperature of the reaction vessel to promote the desorption reaction. The specific refrigerant component can be recovered from the mixed refrigerant only by the physical operation of pressure change in the specific condition range and heat transfer in the specific condition range without using chemical agents. A device that can be separated is obtained. In particular, in the present invention, by reducing the pressure in the reaction vessel, the gas present in the reaction vessel and the substance adsorbed by the adsorbent can be discharged from the reaction vessel. The air that has been discharged is discharged out of the apparatus, and an adsorption reaction for separating components can be performed efficiently. In addition, since the components (mainly moisture etc.) adsorbed from the beginning of the adsorbent are also desorbed and discharged outside the apparatus, the adsorbent can be reliably regenerated and the efficiency of the subsequent adsorption reaction can be improved. it can.

  In addition, since the mixed refrigerant stored in the pressure vessel is configured to be supplied to the reaction vessel via the pressure reducing valve, the pressure of the mixed refrigerant can be reduced and supplied to the reaction vessel. In addition, the components of the mixed refrigerant can be separated. In addition, by configuring the supply pressure of the mixed refrigerant to be at least less than 200 kPa with a pressure reducing valve, the reaction container does not need to have the pressure resistance performance of the “pressure container” in the Industrial Safety and Health Act, and the apparatus can be manufactured at low cost. It is possible to produce with.

  Moreover, it is also preferable that the heat medium of the temperature control means in the mixed refrigerant component separation device of the present invention is water, and is configured so that at least the reaction vessel can be heated. As a result, the reaction vessel is not heated above 100 ° C., and the desorption reaction of the specific refrigerant component adsorbed on the adsorbent can be promoted while preventing the thermal decomposition or alteration of the refrigerant component. it can.

Moreover, it is also preferable that the heat conduction area of the reaction vessel in the mixed refrigerant component separation device of the present invention is configured to be 0.1 m ² / L or more per adsorbent filling volume. Thereby, the heat exchange efficiency of the reaction vessel is increased, and the efficiency of the adsorption reaction and the desorption reaction is remarkably improved.

ADVANTAGE OF THE INVENTION According to this invention, the component separation method and component separation apparatus of a mixed refrigerant which have the following outstanding effects can be provided.
(1) A specific component of the mixed refrigerant can be selectively separated only by a physical operation such as pressure change and heat transfer. Therefore, a large amount of energy is not required, the processing cost is low, and the components of the mixed refrigerant can be efficiently separated.
(2) Since the constituent components of the mixed refrigerant can be separated, the separated components can be reused as a single composition refrigerant, or mixed again with other components at a predetermined ratio to regenerate the mixed refrigerant. it can.
(3) Since the air previously contained in the reaction vessel is discharged to the outside by the reduced pressure, the adsorption reaction for component separation can be exhibited efficiently.
(4) Since the components adsorbed from the beginning by the reduced pressure are desorbed and discharged out of the apparatus, the adsorbent is reliably purified and the adsorption reaction can be maintained efficiently and continuously.

It is the schematic of the component separation apparatus of the typical mixed refrigerant | coolant which concerns on the 1st Embodiment of this invention. It is a flowchart which shows roughly the component separation method of the mixed refrigerant | coolant which concerns on 1st Embodiment. In the component separation method of the mixed refrigerant | coolant using the apparatus shown in FIG. 1, it is explanatory drawing which shows the place which decompressed the reaction container before the adsorption reaction of a refrigerant | coolant component. In the component separation method of the mixed refrigerant using the apparatus shown in FIG. 1, it is explanatory drawing which shows the place where the mixed refrigerant is supplied to the reaction vessel and the specific refrigerant component is adsorbed by the adsorbent. In the component separation method of the mixed refrigerant | coolant using the apparatus shown in FIG. 1, it is explanatory drawing which shows the place which decompressed the reaction container and collect | recovered other refrigerant components. It is explanatory drawing which shows the place which isolate | separates and collect | recovers the specific refrigerant | coolant components adsorbed by adsorption agent in the component separation method of the mixed refrigerant | coolant using the apparatus shown in FIG. It is the schematic of the component separation apparatus of the mixed refrigerant | coolant which concerns on the 2nd Embodiment of this invention. It is a flowchart which shows roughly the component separation method of the mixed refrigerant | coolant which concerns on 2nd Embodiment. It is explanatory drawing which shows the place which is depressurizing the reaction container before adsorption | suction of a refrigerant | coolant component in the component separation method of the mixed refrigerant | coolant using the apparatus shown in FIG. In the component separation method of the mixed refrigerant using the apparatus shown in FIG. 7, a specific refrigerant component of the mixed refrigerant is adsorbed on the adsorbent and another refrigerant component that is not selectively adsorbed on the adsorbent is recovered. It is explanatory drawing shown. It is explanatory drawing which shows the place which isolate | separates and collect | recovers the specific refrigerant | coolant components adsorb | sucked by adsorption agent in the component separation method of the mixed refrigerant | coolant using the apparatus shown in FIG. It is the schematic of the component separation apparatus of the typical refrigerant mixture which concerns on the 3rd Embodiment of this invention. It is a flowchart which shows roughly the component separation method of the mixed refrigerant | coolant which concerns on 3rd Embodiment. FIG. 13 is an explanatory diagram showing a pretreatment by depressurizing a reaction container before adsorption of a refrigerant component in the mixed refrigerant component separation method using the apparatus shown in FIG. 12. FIG. 13 is an explanatory diagram showing a specific refrigerant component of a mixed refrigerant adsorbed on an adsorbent in the mixed refrigerant component separation method using the apparatus shown in FIG. 12. FIG. 13 is an explanatory diagram showing a state where a specific refrigerant component adsorbed by an adsorbent is desorbed and recovered in the mixed refrigerant component separation method using the apparatus shown in FIG. 12. 3 is a graph showing an adsorption result of a mixed refrigerant R-410A gas in a ZMS adsorbent in Example 1. FIG. It is a graph which shows the desorption result from ZMS adsorbent of mixed refrigerant R-410A gas in Example 2. It is a graph which shows the desorption result from ZMS adsorbent of mixed refrigerant R-410A gas in Example 3. It is a graph which shows the adsorption | suction result to ZMS adsorbent of mixed refrigerant R-407C gas in Example 4. It is a graph which shows the adsorption | suction result to the MSC adsorbent of mixed refrigerant R-410A gas in Example 5. It is a graph which shows the desorption result from the MSC adsorbent of mixed refrigerant R-410A gas in Example 6.

  Hereinafter, the mixed refrigerant component separation apparatus 1 according to the first embodiment of the present invention shown in FIG. 1 will be described.

  As shown in FIG. 1, the mixed refrigerant component separation device 1 according to this embodiment includes a pressure vessel 2 in which a mixed refrigerant G is stored and a reaction vessel filled with an adsorbent 42 that adsorbs a specific refrigerant component. 41, the temperature adjusting means 5 for adjusting the temperature of the reaction vessel 41 and the adsorbent 42, the pressure reducing means (vacuum pumps 6a and 6b) for reducing the pressure inside the reaction vessel 41, and collecting each separated refrigerant component And a recovery unit 8 that performs the above-described operation.

  First, the pressure vessel 2 in which the mixed refrigerant G is stored will be described. The pressure vessel 2 may be a vessel in which the mixed refrigerant G is liquefied and filled under a certain pressure. For example, the pressure vessel 2 is composed of a CFC collection container, a product cylinder, a drum can, or a service can in which used refrigerant is collected. The In the present embodiment, a chlorofluorocarbon recovery container in which used refrigerant is recovered is used. As the CFC recovery container, containers of various capacities from about 1 L to over 100 L are generally used, and the pressure resistance test pressure of the container is in the range of 3 MPa to 5 MPa depending on the type of refrigerant to be recovered. It is stipulated in. Moreover, the pressure vessel 2 of this embodiment is arrange | positioned on mass meters M1, such as an electronic balance, and is comprised so that the outflow amount (supply amount) of the mixed refrigerant G stored can be measured.

  The pressure vessel 2 is connected to a reaction vessel 41 of the adsorption unit 4 described later by a flow path. Specifically, as shown in FIG. 1, the pressure vessel 2 is connected to the reaction vessel 41 of the adsorption unit 4 through the outlet valve V1, the pressure reducing valve 3, the flow meter F1, and the inlet valve V2 in detail. A pressure gauge P1 is provided in the flow path between the outlet valve V1 and the pressure reducing valve 3, and a pressure gauge P2 is provided in the flow path between the pressure reducing valve 3 and the flow meter F1.

  The pressure reducing valve 3 is provided to adjust a supply pressure when supplying the mixed refrigerant G in the pressure vessel 2 to the adsorption unit 4. The supply pressure of the mixed refrigerant G is not constant because it changes according to the change in pressure in the pressure vessel 2. Therefore, it is preferable to adjust the supply pressure to be constant so that the adsorption reaction can be performed under stable conditions. Furthermore, since the pressure vessel 2 is normally at a high pressure, if the mixed refrigerant G is supplied to the reaction vessel 41 as it is by opening the outlet valve V1, the pressure in the reaction vessel 41 is similarly increased. Therefore, the pressure in the reaction vessel 41 can be adjusted to a suitable pressure by decreasing the gas supply pressure of the mixed refrigerant G to a predetermined pressure or less with the pressure reducing valve 3. In this embodiment, the predetermined pressure is preferably atmospheric pressure or lower, that is, 100 kPa or lower. By setting the predetermined pressure to be equal to or lower than the atmospheric pressure, the adsorption reaction can be performed safely even if the reaction vessel 41 is not a pressure vessel. When the reaction vessel 41 is a pressure vessel, the gas supply pressure is not particularly limited, and can be a pressure exceeding the atmospheric pressure.

  In the present embodiment, the mixed refrigerant G stored in the pressure vessel 2 is composed of a specific refrigerant component Ga that is selectively adsorbed by an adsorbent 42 described later and other refrigerant components Gb other than that. Yes. Although the refrigerant component Gb is not selectively adsorbed by the adsorbent 42, the adsorbent 42 is saturated with a specific refrigerant component Ga depending on conditions such as temperature and pressure as a result of supplying a certain amount of the mixed refrigerant G to the adsorbent 42. In the case of sufficient adsorbability, the refrigerant component Gb adheres to the adsorbent 42. In the present specification, the adsorption means a state in which the adsorptive binding force is stronger than the adhesion described later, and means a state in which the adsorbing component is not easily desorbed from the adsorbent unless temperature rise and pressure reduction (or purge) are used. Adhesion refers to a state where the surface is simply in contact with the surface of the adsorbent, or a state where the adsorptive binding force is very weak compared to the above-described adsorption, and refers to a state where it can be easily recovered only by decompression (or purge). . The mixed refrigerant component is not limited to one composed of two types of refrigerant components, and may be composed of more types of refrigerant components. The mixed refrigerant G is not limited to chlorofluorocarbons and may be any substance used as a refrigerant, and naturally includes a hydrocarbon-based mixed refrigerant.

  Next, the structure of the adsorption | suction part 4 in this embodiment is demonstrated. The adsorbing unit 4 is roughly composed of a plurality of reaction vessels 41 and an adsorbent 42 filled therein, and adsorption and desorption reactions by the adsorbent 42 are performed. The reaction vessel 41 includes a gas inflow portion 410 connected to the pressure vessel 2 via an inlet valve V2, and a gas outflow portion 411 connected to a vacuum pump 6a (described later) via a valve V3. ing. The reaction vessel 41 is filled with an adsorbent 42 that can selectively adsorb a specific refrigerant component Ga from the mixed refrigerant G.

The reaction vessel 41 may have any configuration as long as it can perform the adsorption and desorption reaction by the adsorbent 42. From the viewpoint of heat exchange efficiency, the heat transfer area per packed volume of the adsorbent 42 is small. What was comprised so that it might become large was preferable. When the specific refrigerant component Ga is adsorbed on the adsorbent 42, heat of adsorption (exotherm) is generated by the adsorption reaction, and when desorbing, heat of desorption (endotherm) is generated by the desorption reaction. Since the object of adsorption and desorption is a refrigerant, the amount of generated heat of adsorption and desorption is large. Since these heats reduce the adsorption and desorption efficiency of the refrigerant component, the adsorption reaction and desorption reaction can be promoted by exchanging the generated heat with the external environment. Therefore, the reaction vessel 41 is preferably configured so that the heat exchange efficiency of the adsorbent 42 is high. Specifically, it is preferable that the heat transfer area per filling volume of the adsorbent 42 is 0.1 m ² / L or more. In this embodiment, the reaction vessel 41 is formed of a stainless steel tube (length: about 80 cm, inner diameter: about 3 cm), and the heat transfer area per packed volume of the adsorbent 42 is 0.1 m ² / L or more. It is comprised so that it may become. In the present embodiment, the adsorption unit 4 is configured by arranging 19 reaction vessels 41 in parallel at a predetermined interval.

  Further, the component separation apparatus 1 according to the present embodiment is configured to be used by reducing the gas pressure at the time of supply by the pressure reducing valve 3 so that the pressure in the reaction vessel 41 becomes a predetermined pressure or less. Therefore, the reaction vessel 41 is provided with a safety valve 412 for adjusting the pressure so that the pressure inside the vessel does not exceed a predetermined pressure. In the present embodiment, the predetermined pressure is preferably atmospheric pressure or lower, that is, 100 kPa or lower.

  As the adsorbent 42 filled in the reaction vessel 41, an adsorbent 42 having a function of separating substances according to the molecular size of the separation target component can be used. Specific examples include, but are not limited to, MSC (Molecular Sieve Carbon), ZMS (Zeolite Molecular Sieve), activated carbon, alumina, natural zeolite, and the like, and are selected according to the specific refrigerant component to be separated. . As a specific example, difluoromethane (boiling point: −51.65 ° C., molecular weight: 52 g / mol) and pentafluoroethane (boiling point: −48.13 ° C., molecular weight: 120 g / mol) constituting R-410A The molecular diameters are different because the boiling points are approximately equal, but the molecular weights are about 2.3 times different. The molecular weights of pentafluoroethane, 1,1,1-trifluoroethane and 1,1,1,2-tetrafluoroethane constituting R-404A are 120 g / mol, 84 g / mol and 102 g / mol, respectively. , Each has a different molecular diameter. A specific refrigerant component Ga can be selectively adsorbed and separated using such a difference in molecular diameter. Therefore, it is preferable to select an adsorbent in which a compound having a predetermined molecular diameter enters the pores of the adsorbent and is adsorbed, and other compounds having a molecular diameter hardly enter the pores and are difficult to adsorb.

  Regarding the adsorbent 42, the inventors have shown that R-410A, which is a mixture of difluoromethane (HFC-32) and pentafluoroethane (HFC-125), can be adsorbed by both MSC (molecular sieve carbon). It was found that the molecular sieve 4A, which is ZMS (zeolite molecular sieve), has a clear difference in the adsorptivity of both, and is suitable for separation because it has a certain difference. Furthermore, for R-407C, which is a mixture of difluoromethane (HFC-32), pentafluoroethane (HFC-125) and 1,1,1,2-tetrafluoroethane (HFC-134a), HFC-32 and It was found that separation from HFC-125 and HFC-134a was possible with ZMS molecular sieve 4A. Specific examples of MSC include, but are not limited to, granular white birch (registered trademark) X2M (product of Osaka Gas Chemical Co., Ltd.). As an example of ZMS, molecular sieve 4A 3.2 pellets (Union Showa Co., Ltd.) Product). In addition, the separation target in the present invention is not limited to the refrigerant component constituting the above-described mixed refrigerant, and it is possible to separate specific components by appropriately selecting an adsorbent for other mixed refrigerants.

  Next, the temperature control means 5 will be described. The temperature control means 5 mainly removes the heat of reaction generated by the adsorption reaction or desorption reaction in the reaction vessel 41, and is preliminarily decompressed in the reaction vessel and contained in the adsorbent 42 and the reaction vessel 41. It is provided to warm the reaction vessel 41 at that time to ensure the removal. In the present embodiment, the temperature adjustment means 5 includes a water W that is a heat medium, a temperature adjustment jacket 51 that covers the reaction vessel 41 and accommodates the water W that is a heat medium, and a hot water production apparatus that is a heating means 52. 52a and a hot water circulation pump 52b, and a chilled water production device 53a and a chilled water circulation pump 53b which are cooling means 53. Specifically, the reaction vessel 41 is configured to be cooled by the cooling unit 53 because heat is generated during the adsorption reaction, and the endotherm is generated during the desorption reaction. It is comprised so that 41 may be heated. As a preparatory step, when the adsorbent 42 or the air or water contained in the reaction vessel 41 is removed by reducing the pressure in the reaction vessel, a reaction by the heating means 52 is performed to promote regeneration of the adsorbent 42. The container 41 is configured to be heated. The temperature adjustment means 5 includes a cooling means 53 as in the component separation apparatus 1 according to the present embodiment, and it is desirable to remove adsorption heat by the cooling means 53 from the viewpoint of reaction efficiency. It is also possible to omit the cooling means 53 by configuring so as to facilitate heat dissipation. On the other hand, regarding the heating means 52, the inventors not only remarkably slow the desorption reaction rate but also the reaction vessel 41 when the desorption heat is not supplemented by the heating means 52 during the desorption reaction. It has been found that troubles occur in the operation of the component separation device 1 due to frost adhering to the outer periphery. Therefore, the temperature adjustment means 5 needs to have at least the heating means 52. Note that if only the heating means 52 is activated in a state where the vacuum pump 6a or 6b described later is not activated, the pressure in the reaction vessel 41 may increase. Therefore, the operation of the hot water circulation pump 52b is performed by the vacuum pump 6a or 6b. It is preferable to be configured to be interlocked with the operation.

  In the present embodiment, the heat medium used in the temperature adjustment means 5 is water W. The water W is accommodated in the temperature control jacket 51, and the reaction vessel 41 is immersed in the water W. During the preparation step and the desorption reaction, the water W is heated by the warm water production device 52a of the warming means 52 and circulated between the temperature control jacket 51 and the warm water production device 52a by the warm water circulation pump 52b. The hot water transferred into the temperature control jacket 51 exchanges heat with the reaction vessel 41 that is cooled by the elimination reaction, and warms the reaction vessel 41. On the other hand, at the time of the adsorption reaction, the water W is cooled by the cold water production apparatus 53a of the cooling means 53 and circulated between the temperature control jacket 51 and the cold water production apparatus 53a by the cold water circulation pump 53b. The cold water transferred into the temperature control jacket 51 exchanges heat with the reaction vessel 41 in which an adsorption reaction has occurred and heat is generated, thereby cooling the reaction vessel 41. In this embodiment, water W is used as the heat medium, but other known materials used for cooling and heating, such as other heat storage compositions and Peltier elements, can be applied. Moreover, when the temperature control means 5 is comprised only by a heating means, it is also possible to use a heating wire, a heat lamp, etc. as a heat medium.

  Regarding the temperature of the heat medium during the desorption reaction, the present inventors have found that when the desorption reaction temperature exceeds 100 ° C., the refrigerant component itself is decomposed to generate harmful components. As an example, Table 1 below shows the desorption reaction temperature when difluoromethane (HFC-32) is adsorbed on an adsorbent and then desorbed, and the concentration of formaldehyde contained in the recovered desorbed gas. From this result, it is preferable that the temperature of the heat medium supplied into the temperature control jacket 51 during the desorption reaction is 100 ° C. or less. In this embodiment, since the water W is used as a heat medium, the reaction vessel 41 is not heated above 100 ° C. and can be suitably used. In addition, when the reaction vessel 41 is heated in another aspect, it is preferable to adjust the temperature so that the desorption reaction temperature is 100 ° C. or lower.

  On the other hand, the temperature of the heat medium during the adsorption reaction may be room temperature or lower, preferably about 0 to 30 ° C, particularly preferably about 5 to 20 ° C. If the temperature of the heat medium is too low, there is a risk of causing trouble in the operation of the component separation apparatus 1, and therefore a temperature in the above range is preferable. In the present embodiment, since water W is used as a heat medium, the reaction vessel 41 is not cooled beyond 0 ° C. and can be suitably used.

  Next, the decompression means will be described. The decompression means is provided for decompressing the inside of the reaction vessel 41, and in the present embodiment, is composed of vacuum pumps 6a and 6b. Among these, the vacuum pump 6a is connected to the outflow part 411 of the reaction vessel 41 via the valve V3, and a pressure gauge P3 is provided in the flow path between the valve V3 and the vacuum pump 6a. The vacuum pump 6a is connected to the intermediate tank 81a of the recovery unit 8 through a three-way valve V4. On the other hand, the vacuum pump 6b is connected to the outflow part 411 of the reaction vessel 41 via the valve V5, and a pressure gauge P3 is provided in the flow path between the valve V5 and the vacuum pump 6b. The vacuum pump 6b is connected to the intermediate tank 81b of the recovery unit 8 through a three-way valve V5. By operating the vacuum pump 6a or 6b, the inside of the reaction vessel 41 is depressurized, the components selectively adsorbed by the adsorbent 42 are desorbed, the components adhering to the adsorbent 42 and the gas in the reaction vessel 41 are exhausted. It is possible to recover the components contained as Further, as will be described in detail in a method of using the present component separation device 1 described later, before the specific refrigerant component Ga is adsorbed to the adsorbent 42, the reaction vessel 41 is depressurized with the vacuum pump 6a or 6b in advance. It is possible to remove substances such as moisture adsorbed on the adsorbent 42 and air in the reaction vessel 41 and improve the efficiency of the adsorption reaction performed later. As the vacuum pump 6a or 6b, in view of the desorption rate of the refrigerant component adsorbed by the adsorbent 42, one that can be depressurized so that the pressure in the reaction vessel 41 is 1 kPa to less than 20 kPa is preferable.

  Next, the collection means 8 will be described. In the present embodiment, the recovery means 8 is provided in two series so that the refrigerant components separated by the adsorption unit 4 can be recovered, respectively. The intermediate tanks 81a and 81b, the pressurized liquefiers 82a and 82b, the recovery container 83a, 83b is schematically configured. The intermediate tank 81a is connected in series with the vacuum pump 6a via the three-way valve V4. Further, the intermediate tank 81a is connected to the recovery container 83a via a pressurized liquefying device 82a. Further, the intermediate tank 81a is provided with a pressure gauge P4 for monitoring the amount of the refrigerant component Gb flowing into the intermediate tank 81a. The recovered refrigerant component Gb flows into the intermediate tank 81a via the three-way valve V4, and then is liquefied by the pressurized liquefier 82a and recovered in the recovery container 83a. On the other hand, the intermediate tank 81b is connected in series with the vacuum pump 6b via a three-way valve V6. The intermediate tank 81b is connected to the recovery container 83b via the pressurized liquefying device 82b. Further, the intermediate tank 81b is provided with a pressure gauge P5 for monitoring the amount of the refrigerant component Ga flowing into the intermediate tank 81b. The desorbed refrigerant component Ga flows into the intermediate tank 81b via the three-way valve V6, and then is liquefied by the pressurized liquefier 82b and recovered in the recovery container 83b. In the present embodiment, the intermediate tanks 81a and 81b are provided, and are configured such that the pressurized liquefaction treatment by the pressurized liquefaction devices 82a and 82b is performed when a certain amount of refrigerant components are collected by monitoring of the pressure gauge. However, the intermediate tank may be omitted, and only the pressurized liquefier and the recovery container may be used. As the intermediate tank and the recovery container, those having the same configuration as the pressure container 2 described above can be used, and containers such as a CFC recovery container, a product cylinder, a drum can, or a service can can be used. In the present embodiment, the recovery containers 83a and 83b are arranged on mass meters M2 and M3 such as an electronic balance, respectively, so that the recovery amount can be measured.

  Next, based on FIGS. 2-6, the component separation method of the mixed refrigerant using the component separation apparatus 1 which concerns on this embodiment is demonstrated.

  As shown in FIG. 2, the mixed refrigerant component separation method according to the present embodiment includes a preparation step S <b> 1 for reducing the pressure and heating in the reaction vessel 41, a supply step S <b> 2 for supplying the mixed refrigerant into the reaction vessel 41, a reaction An adsorption step S3 for adsorbing a specific refrigerant component to the adsorbent 42 in the container 41, a recovery step S4 for depressurizing the inside of the reaction vessel 41 to collect other refrigerant components, and depressurizing and heating the inside of the reaction vessel 41 for identification The desorption step S5 for desorbing the refrigerant component, the specific component recovery step S6 for recovering the desorbed specific refrigerant component, and determining whether or not the separation of the mixed refrigerant is almost finished, and the separation is not almost finished In the case of (NO), the process returns to the supply step S2, and the steps S2 to S6 are repeated, and when the separation is almost completed (in the case of YES), the determination step S7 is completed. In the present embodiment, the mixed refrigerant G stored in the pressure vessel 2 includes a specific refrigerant component (a component that is selectively adsorbed by the adsorbent 42) Ga and another refrigerant component Gb (the adsorbent 42 that is selectively used). For example, when the mixed refrigerant G is R-410A, the adsorbent 42 is a molecular sieve 4A, and is selectively selected by the adsorbent 42. The specific refrigerant component Ga to be adsorbed is HFC-32, and the other refrigerant component Gb is HFC-125.

(Reduced pressure in the reaction vessel)
First, based on FIG. 3, the preparatory process S1 which decompresses the inside of reaction container is demonstrated. While the valve V2 on the inflow portion 410 side of the reaction vessel 41 and the valve V5 connected to the outflow portion 411 are closed, the valve V3 connected to the outflow portion 411 is opened. And the three-way valve V4 provided between the vacuum pump 6a and the collection | recovery part 8 is switched so that the air etc. which were attracted | sucked with the vacuum pump 6a are exhausted out of an apparatus. When the vacuum pump 6a is operated in this state, suction is performed and the inside of the reaction vessel 41 becomes a reduced pressure environment. Since the adsorption of the refrigerant component Ga to the adsorbent 42 in the adsorption step S3 described later is affected by the air pressure previously contained in the reaction vessel 41, in order to reduce this air pressure effect, It is preferable to reduce the pressure of the air so that it is 1/5 or less of the atmospheric pressure, that is, 20 kPa or less. Further, according to the present inventors, compared with the case where the pressure in the reaction vessel 41 is 20 kPa, the time until the adsorbent 42 is purified and the weight becomes constant by reducing the pressure to 10 kPa or less is 3 minutes. Has been found to be 1 or less. Therefore, the pressure reduction by the vacuum pump 6a is preferably performed so that the pressure in the reaction vessel 41 is 1 kPa to less than 20 kPa, and more preferably 1 kPa to 10 kPa. The pressure in the reaction vessel 41 is confirmed by a pressure gauge P3 provided in the flow path between the outflow portion 411 and the valve V3.

  Furthermore, it is preferable to heat the reaction vessel 41 by operating the heating means 52 of the temperature adjustment means 5. Thereby, since the component previously adsorbed by the adsorbent 42 is more reliably desorbed, impurities can be removed and the adsorbent 42 is regenerated. The temperature of the heat medium W of the heating means 52 is preferably set to 100 ° C. or lower because cooling takes time if the temperature exceeds 100 ° C. In the present embodiment, since water is used as the heat medium, the reaction vessel 41 is not heated above 100 ° C. Depending on the state of the adsorbent 42, it is possible to perform only the pressure reduction in the reaction vessel 41 at a normal temperature of 15 to 25 ° C. without operating the heating means 52.

  By the above-described operation, the air previously contained in the reaction vessel 41 is discharged out of the apparatus. In general, air contains moisture, and this moisture prevents adsorption of the specific refrigerant component Ga onto the adsorbent 42. Therefore, by removing the air contained in the reaction vessel 41, the adsorption reaction performed in the subsequent process can be performed efficiently. In addition, since the components (mainly moisture and the like) that have already adhered or adsorbed to the adsorbent 42 are removed and discharged out of the apparatus, the adsorbent 42 itself is also reliably regenerated and the efficiency of the subsequent adsorption reaction is improved. Can be made. Furthermore, since the pressure in the reaction vessel 41 is reduced to less than the atmospheric pressure by performing this preparatory step S1, in the next supply step S2, the mixed refrigerant G easily flows into the reaction vessel 41 due to the pressure difference. To do. In the present embodiment, the pressure in the reaction vessel 41 is reduced mainly using the vacuum pump 6a and the three-way valve V4. However, the present invention is not limited to this, and the vacuum pump 6b and the three-way valve V6 may be used.

(Supply of mixed refrigerant)
Next, the mixed refrigerant supply step S2 will be described with reference to FIG. The operation of the vacuum pump 6a is stopped, and the valves V3 and V5 connected to the outflow part 411 of the reaction vessel 41 are closed. Next, the pressure reducing valve 3 is adjusted to adjust the gas pressure of the mixed refrigerant G supplied from the pressure vessel 2 to a predetermined pressure. In this embodiment, it adjusts so that the pressure of gas may become higher than the pressure in the reaction container 41 pressure-reduced by preparatory process S1. Then, the valve V2 on the inflow portion 410 side of the reaction vessel 41 and the valve V1 of the pressure vessel 2 are opened, and the gas of the mixed refrigerant G is supplied from the pressure vessel 2 to the inflow portion 410 of the reaction vessel 41. The supply pressure of the mixed refrigerant G before and after the pressure reduction by the pressure reducing valve 3 is confirmed by pressure gauges P1 and P2 provided between the pressure vessel 2 and the reaction vessel 41, respectively. Further, the gas supply amount of the mixed refrigerant G is confirmed by the flow meter F1 and the mass meter M1. The supply amount of the mixed refrigerant G is preferably adjusted so that the amount of the specific refrigerant component Ga contained in the supplied gas is less than the saturated adsorption amount of the adsorbent 42. Note that the gas supply pressure of the mixed refrigerant G is preferably adjusted to be equal to or lower than the atmospheric pressure. However, when the reaction vessel 41 is a pressure vessel, it can be adjusted to a pressure exceeding the atmospheric pressure. is there.

  The gas of the mixed refrigerant G is easily introduced into the reaction vessel 41 due to the difference in pressure because the pressure in the reaction vessel 41 is reduced to less than atmospheric pressure in the preparation step S1. The supply of the gas of the mixed refrigerant G is stopped when the supply pressure adjusted by the pressure reducing valve 3 and the pressure in the reaction vessel 41 become equal. By setting the gas supply pressure of the mixed refrigerant G to the atmospheric pressure or lower, that is, about 100 kPa or lower by the pressure reducing valve 3, the pressure in the reaction vessel 41 does not exceed the atmospheric pressure, and the components of the mixed refrigerant G can be safely Separation can be performed. The adsorption step S3 described later is performed substantially simultaneously with the supply of the mixed refrigerant G in the main supply step S2, and when the specific refrigerant component Ga of the mixed refrigerant G is adsorbed to the adsorbent 42, the specific refrigerant component Ga is vaporized. And the pressure in the reaction vessel 41 decreases. Therefore, the gas is supplied while the adsorption reaction of the specific refrigerant component Ga proceeds in the reaction vessel 41.

(Adsorption of specific refrigerant components)
In the main adsorption step S3, of the mixed refrigerant G gas supplied into the reaction vessel 41, a specific refrigerant component Ga is adsorbed by an adsorbent 42 that selectively adsorbs the refrigerant component Ga. As an example, when the mixed refrigerant G is R-410A, the molecular sieve 4A is preferably used as the adsorbent 42, and the specific refrigerant component Ga that is selectively adsorbed on the molecular sieve 4A is HFC-32. In other words, the other refrigerant component Gb that is not adsorbed becomes HFC-125. The adsorption step S3 is performed substantially simultaneously with the supply of the mixed refrigerant G in the supply step S2 described above. Since the adsorption reaction generates heat of adsorption and the temperature in the reaction vessel 41 rises, the cooling means 53 of the temperature adjusting means 5 can be operated to cool the reaction vessel 41, thereby promoting the adsorption reaction. The The temperature of the heat medium W of the cooling means 53 is preferably 5 to 20 ° C. It is also possible to measure the temperature of the reaction vessel 41, grasp the progress of the adsorption reaction and the amount of adsorption based on the change in temperature, and control the operation of the component separation apparatus 1. On the other hand, in this embodiment, since the supply pressure of the refrigerant component G is set to atmospheric pressure or less, the inside of the reaction vessel 41 is in a non-pressurized condition, and the amount of the mixed refrigerant G supplied into the reaction vessel 41 is also limited. Therefore, the other refrigerant component Gb attracts the adsorbent 42 with a very weak force and adheres to the adsorbent 42, or exists as a gas in a space in the reaction vessel 41 that is not filled with the adsorbent 42.

(Recovery of other refrigerant components by decompression)
Next, another refrigerant component recovery step S4 will be described with reference to FIG. In this recovery step S4, other refrigerant components Gb that are not selectively adsorbed by the adsorbent 42 are recovered and separated. As described above, the other refrigerant component Gb is attached to the adsorbent 42 with a very weak force in the reaction vessel 41 or exists as a gas in a space not filled with the adsorbent 42. Therefore, when the pressure in the reaction vessel 41 is reduced at room temperature of 15 to 25 ° C. without raising the temperature, the refrigerant component Ga selectively adsorbed on the adsorbent 42 is not desorbed, but only the other refrigerant component Gb is absorbed. It flows out of the reaction vessel 41 and is collected. Specifically, first, the valve V1 of the pressure vessel 2 and the valve V2 on the inflow portion 410 side of the reaction vessel 41 are closed. Next, the valve V5 connected to the outflow part 411 of the reaction vessel 41 is closed, the valve V3 is opened, and the vacuum pump 6a is fed so that the refrigerant component Gb sucked by the vacuum pump 6a is sent to the intermediate tank 81a of the recovery means 8. And the three-way valve V4 provided between the recovery unit 8 is switched. When the vacuum pump 6a is operated in this state, the vacuum pump 6a sucks the inside of the reaction vessel 41 and makes the inside of the reaction vessel 41 a reduced pressure environment. The pressure reduction in the vacuum pump 6a is preferably 1 kPa to less than 20 kPa, more preferably 1 kPa to 10 kPa, from the viewpoint of desorption efficiency. The pressure in the reaction vessel 41 can be confirmed by a pressure gauge P3. The refrigerant component Gb that has flowed out is stored in the intermediate tank 81a of the recovery unit 8 to a certain extent, is sent to the pressurized liquefier 82a, is liquefied, and is stored in the recovery container 83a. The refrigerant component Gb stored in the intermediate tank 81a is confirmed by the pressure gauge P4. Further, the amount of the refrigerant component Gb recovered in the recovery container 83a is measured by the mass meter M2. Note that the intermediate tank 81a may be omitted, and the pressurized liquefying device 82a and the recovery container 83a may be configured. Further, in the present embodiment, the other refrigerant component Gb was recovered by the decompression in the reaction vessel 41. However, a purge gas vessel 70 shown in the second embodiment to be described later is attached to the component separation device 1, and the inside of the reaction vessel 41 It is also possible to recover and separate the other refrigerant component Gb by supplying a purge gas.

(Desorption of specific refrigerant components by decompression and heating)
Next, a specific refrigerant component desorption process S5 will be described with reference to FIG. In this embodiment, the desorption reaction of the specific refrigerant component Ga adsorbed on the adsorbent 42 is performed by reducing the pressure in the reaction vessel 41 and heating. First, it is confirmed that the valve V1 of the pressure vessel 2 and the valve V2 on the inflow portion 410 side of the reaction vessel 41 are closed. Next, the valve V3 connected to the outflow part 411 of the reaction vessel 41 is closed, and the valve V5 is opened. Further, the three-way valve V6 provided between the vacuum pump 6b and the recovery unit 8 is switched so that the refrigerant component Ga sucked by the vacuum pump 6b is sent to the intermediate tank 81b of the recovery means 8. Furthermore, the heating means 52 of the temperature adjustment means 5 is operated to heat the reaction vessel 41. When the vacuum pump 6b is operated in this state, the vacuum pump 6b sucks the inside of the reaction vessel 41 and makes the inside of the reaction vessel 41 a reduced pressure environment. The pressure reduction in the vacuum pump 6b is preferably 1 kPa to less than 20 kPa, more preferably 1 kPa to 10 kPa, from the viewpoint of desorption efficiency. The pressure in the reaction vessel 41 can be confirmed by a pressure gauge P3. Further, if the temperature of the heat medium W of the heating means 52 exceeds 100 ° C., the refrigerant component may be decomposed and toxic components may be generated. In the present embodiment, since water is used as the heat medium, the reaction vessel 41 is not heated above 100 ° C., and the refrigerant component can be safely separated. Even if the inside of the reaction vessel 41 is sucked by the vacuum pump 6b, the pressure in the reaction vessel 41 is large because the refrigerant component Ga comes out in the gas phase while the desorption of the refrigerant component Ga is in progress. It does not decrease, and the pressure decreases greatly when the desorption of the refrigerant component Ga ends. This change in pressure can be detected by the pressure gauge P3 to confirm the desorption state. Further, while the desorption of the refrigerant component Ga is proceeding, desorption heat is generated and the temperature is remarkably lowered. However, when the desorption reaction approaches the end, the temperature change is weakened. By detecting the temperature change of the reaction vessel 41, the desorption state can be confirmed.

  The specific refrigerant component Ga desorbed from the adsorbent 42 is sent to the intermediate tank 81b of the recovery unit 8 by the vacuum pump 6b. Thus, by desorbing the specific refrigerant component Ga from the adsorbent 42, the adsorbent 42 can be regenerated, and the reaction vessel 41 can be in a reduced pressure environment. Supply and adsorption.

(Recovery of desorbed refrigerant components)
The recovery process S6 of the desorbed refrigerant component will be described with reference to FIG. In this step, the specific refrigerant component Ga that has been desorbed by heating under reduced pressure in the desorption step S5 is recovered. The specific refrigerant component Ga sent by the vacuum pump 6b is stored in the intermediate tank 81b, and is sent to the pressurized liquefier 82b at a stage where it is stored to a certain extent, and is liquefied and stored in the recovery container 83b. The refrigerant component Ga stored in the intermediate tank 81b is confirmed by the pressure gauge P5. Further, the amount of the refrigerant component Ga recovered in the recovery container 83b is measured by the mass meter M3. Note that the intermediate tank 81b may be omitted, and only the pressurized liquefier 82b and the recovery container 83b may be configured.

(Repeat steps S2 to S6)
Next, the determination step S7 will be described. In the determination step S7, based on the remaining amount of the mixed refrigerant G in the pressure vessel 2 or the like, it is determined whether or not the separation of the mixed refrigerant component is almost finished, and when the separation is not finished (in the case of NO). Returns to the supply step S2 and repeats steps S2 to S6, and ends when the separation is almost completed (in the case of YES). When the component separation device 1 according to FIG. 1 is a small device, or when the amount of the mixed refrigerant G stored in the pressure vessel 2 is larger than the amount that can be adsorbed by the adsorbent 42, the entire amount is obtained in one batch. Since it is difficult to separate, the steps S2 to S6 are repeated. By measuring the change in the mass meter M1 installed in the pressure vessel 2, it is possible to confirm whether or not the component separation of the mixed refrigerant G has been substantially completed.

  As a result of the above-described steps, the component separation of the mixed refrigerant G is almost completed, so that the separated refrigerant components are accommodated in the recovery containers 83a and 83b. Since each separated refrigerant component is contained in a container, it is in a state where it can be easily reused. As a refrigerant composition mainly containing the refrigerant component Ga or the refrigerant component Gb, a mixed refrigerant is prepared again at an appropriate ratio. Or can be effectively used as a refrigerant having a single composition.

  In this embodiment, the specific refrigerant component Ga is desorbed from the adsorbent 42 by the pressure reduction and heating of the reaction vessel 41. However, the purge gas vessel 70 shown in the second embodiment to be described later is added to the component separation apparatus 1. It is also possible to desorb the specific refrigerant component Ga from the adsorbent 42 by supplying a purge gas into the reaction vessel 41.

  Hereinafter, the mixed refrigerant component separation apparatus 10 according to the second embodiment of the present invention shown in FIG. 7 will be described.

  As shown in FIG. 7, the mixed refrigerant component separation device 10 according to the present embodiment reduces the pressure of the pressure vessel 2 in which the mixed refrigerant G is stored and the pressure of the mixed refrigerant G supplied from the pressure vessel 2. The valve 3, the adsorbing part 4 having a reaction vessel 41 filled with an adsorbent 42 that adsorbs a specific refrigerant component, the temperature adjusting means 5 for adjusting the temperature of the reaction vessel 41, and the pressure reducing means (vacuum) for reducing the pressure inside the reaction vessel 41 The pump 60), a purge gas container 70 containing a purge gas for desorbing a specific refrigerant component, and a recovery unit 80 for recovering each separated refrigerant component. In the present embodiment, the same components as those in the first embodiment will be described using the same reference numerals.

  First, the pressure vessel 2 in which the mixed refrigerant G is stored will be described. The pressure vessel 2 having the same configuration as the pressure vessel 2 in the first embodiment can be used. The pressure vessel 2 is connected to the reaction vessel 41 of the adsorption unit 4 through a flow path. That is, as shown in FIG. 7, the pressure vessel 2 is connected to the reaction vessel 41 of the adsorption unit 4 through the valve V1, the pressure reducing valve 3, the flow meter F1, and the three-way valve V20 in detail. A pressure gauge P1 is provided in the flow path between the valve V1 and the pressure reducing valve 3, and a pressure gauge P2 is provided in the flow path between the pressure reducing valve 3 and the flow meter F1.

  The pressure reducing valve 3 is provided to adjust a supply pressure when supplying the mixed refrigerant G in the pressure vessel 2 to the adsorption unit 4. In the present embodiment, by reducing the pressure of the gas of the mixed refrigerant G to less than 200 kPa with the pressure reducing valve 3, the pressure in the reaction vessel 41 becomes less than 200 kPa, and even if the reaction vessel 41 is not a pressure vessel, it can be safely An adsorption reaction can be performed. In the present embodiment, the mixed refrigerant G stored in the pressure vessel 2 is composed of a specific refrigerant component Ga that is selectively adsorbed by the adsorbent 42 and other refrigerant components Gb. The mixed refrigerant component is not limited to one composed of two types of refrigerant components, and may be composed of more types of refrigerant components.

  Next, the structure of the adsorption | suction part 4 in this embodiment is demonstrated. The adsorbing unit 4 is generally composed of a reaction vessel 41 and an adsorbent 42 filled therein, and adsorption and desorption reactions by the adsorbent 42 are performed. The reaction vessel 41 includes a gas inflow portion 410 connected to the pressure vessel 2 via a three-way valve V20, and a gas outflow portion connected to the vacuum pump 6 and recovery means 80 described later via a valve V30. 411. The reaction vessel 41 is filled with an adsorbent 42 that selectively adsorbs a specific refrigerant component Ga from the mixed refrigerant G.

  In the present embodiment, the reaction vessel 41 corresponds to a “pressure vessel” in the Industrial Safety and Health Act when the pressure in the vessel is 200 kPa or more due to the mixed refrigerant supplied from the inflow portion 410. In terms of pressure resistance and the like, it is necessary to have a configuration that satisfies the structural standards based on the regulations. However, when adjusting the pressure in the reaction vessel 41 to be less than 200 kPa, it is not subject to the above regulation, and therefore the reaction vessel 41 does not need to have special pressure resistance performance. Therefore, the component separation apparatus 10 according to the present embodiment is configured to be used by reducing the gas pressure with the pressure reducing valve 3 so that the pressure in the reaction vessel 41 is less than 200 kPa. The reaction vessel 41 is provided with a safety valve 412 so that the pressure inside the vessel does not exceed 200 kPa. In addition, it is also possible to make the reaction vessel 41 and other members have pressure resistance required for the “pressure vessel” in the Industrial Safety and Health Act, and to set the pressure in the reaction vessel 41 to 200 kPa or more.

  Next, the decompression means will be described. The decompression means is provided for decompressing the inside of the reaction vessel 41, and is constituted by a vacuum pump 60 in the present embodiment. The vacuum pump 60 is connected to the outflow portion 411 of the reaction vessel 41 through a three-way valve V40 and a valve V30. A pressure gauge P3 is provided in the flow path between the valve V30 and the three-way valve V40. The vacuum pump 60 is connected to the intermediate tank 801 of the recovery unit 80 via a three-way valve V40. By operating the vacuum pump 60, before the specific refrigerant component Ga is adsorbed by the adsorbent 42, the inside of the reaction vessel 41 is placed in a reduced pressure environment, and substances such as moisture adsorbed on the adsorbent 42 in advance and the reaction vessel It is possible to remove the air in 41 and improve the efficiency of the adsorption reaction performed later.

  Next, the purge gas container 70 will be described. The purge gas container 70 is provided for causing a desorption reaction in the reaction container 41. In the present embodiment, nitrogen gas is used as the purge gas, and this nitrogen gas is pressurized and stored in the purge gas container 70. The purge gas container 70 is connected to the inlet 410 of the reaction container 41 via the flow meter F2 and the three-way valve V20. The supply flow rate of the purge gas to the reaction vessel 41 can be confirmed by the flow meter F2. By supplying the purge gas stored in the purge gas container 70 to the reaction container 41, the specific refrigerant component Ga can be expelled from the adsorbent 42 and desorbed. As the purge gas container 70, one having the same configuration as that of the pressure container 2 described above can be used. The purge gas may be any purge gas that can expel the component adsorbed on the adsorbent 42, and argon gas or the like can be used in addition to nitrogen gas.

  Next, the collection means 80 will be described. In the present embodiment, the recovery means 80 is generally configured by an intermediate tank 81, a pressurized liquefier 802, and recovery containers 803 and 804. In the recovery means 80, each refrigerant component of the mixed refrigerant G separated in the adsorption unit 4 is recovered. The intermediate tank 81 is connected to the outflow part 411 of the reaction vessel 41 through a three-way valve V40 and a valve V30. A pressure gauge P3 is provided in the flow path between the valve V30 and the three-way valve V40. The intermediate tank 801 is connected to the recovery container 804 and the recovery container 805 via a pressurized liquefaction device 802 and a three-way valve V50. Further, the intermediate tank 801 is provided with a pressure gauge P4 for monitoring the amount of the refrigerant component Ga or Gb flowing into the intermediate tank 801. The separated refrigerant component flows into the intermediate tank 801 through the valve V30 and the three-way valve V40, and then is liquefied by the pressurized liquefier 802 and collected in the collection container 803 (or 804). In the present embodiment, an intermediate tank 801 is provided, and the pressurized liquefaction process is performed by the pressurized liquefier 802 when a certain amount of refrigerant components are collected by monitoring of the pressure gauge P4. Alternatively, the intermediate tank 801 may be omitted and only the pressurized liquefaction device 802 and the recovery containers 803 and 804 may be configured. In the present embodiment, the recovery containers 803 and 804 are arranged on mass meters M2 and M3 such as an electronic balance, respectively, and configured to measure the refrigerant recovery amount.

  Other explanations about the configuration of the pressure vessel 2, the pressure reducing valve 3, the adsorption unit 4, the vacuum pump 60, and the recovery unit 80 are as follows. The pressure vessel 2, the pressure reducing valve 3, the adsorption unit 4, and the vacuum pump in the first embodiment described above. 6 and the collection unit 8 are the same, and the functions and effects thereof are also the same. The configuration of the temperature control means 5 is also the same as the configuration of the temperature control means 5 in the first embodiment described above, and the functions and effects thereof are also the same.

  Next, based on FIGS. 8-11, the component separation method of the mixed refrigerant | coolant using the component separation apparatus 10 which concerns on this embodiment is demonstrated.

  As shown in FIG. 8, the mixed refrigerant component separation method according to the present embodiment includes a depressurization step S10 for depressurizing the reaction vessel 41, a supply step S20 for supplying the mixed refrigerant into the reaction vessel 41, and the reaction vessel 41 interior. An adsorption step S30 for adsorbing a specific refrigerant component to the adsorbent 42, a recovery step S40 for other refrigerant components, a desorption step S50 for desorbing a specific refrigerant component by purging, and a desorbed specific refrigerant component It is comprised from collection | recovery process S60 to collect | recover. In this embodiment, the mixed refrigerant G stored in the pressure vessel 2 is selected as a specific refrigerant component (component that is selectively adsorbed by the adsorbent 42) Ga and another refrigerant component (adsorbent 42) as an example. However, the mixed refrigerant components are not limited to those composed of two types of refrigerant components, and are composed of more types of refrigerant components. May be.

(Reduced pressure in the reaction vessel)
First, the decompression step S10 in the reaction vessel will be described based on FIG. While the three-way valve V20 on the inflow portion 410 side of the reaction vessel 41 is closed, the valve V30 on the outflow portion 411 side is opened, and the three-way valve V40 is switched so that air sucked by the vacuum pump 60 is exhausted outside the apparatus. When the vacuum pump 60 is operated in this state, suction is performed and the inside of the reaction vessel 41 becomes a reduced pressure environment. For the pressure reduction by the vacuum pump 60, the pressure in the reaction vessel 41 is preferably 1 kPa to less than 20 kPa, and more preferably 1 kPa to 10 kPa. The pressure in the reaction vessel 41 is confirmed by a pressure gauge P3 provided in the flow path between the valve V30 and the vacuum pump 60. Moreover, it is also preferable to heat the reaction vessel 41 by operating the heating means 52 of the temperature adjusting means 5. Thereby, since the component previously adsorbed by the adsorbent 42 is more reliably desorbed, impurities can be removed and the adsorbent 42 is regenerated.

  By this operation, the air previously contained in the reaction container 41 is discharged out of the apparatus, and the adsorption reaction performed in the subsequent process can be performed efficiently. Further, by this operation, the components (mainly moisture etc.) previously adsorbed on the adsorbent 42 are also desorbed and discharged out of the apparatus, so that the adsorbent 42 itself is also reliably regenerated, and the subsequent adsorption reaction Efficiency can be improved. Furthermore, since the pressure in the reaction vessel 41 is reduced to less than atmospheric pressure by performing this decompression step S10, even when the mixed refrigerant G flows into the reaction vessel 41 in the next supply step S20, the reaction vessel 41 It is easy to control the pressure inside 41 to less than 200 kPa (0.2 MPa), and even when the reaction vessel 41 is not a “pressure vessel” in the Industrial Safety and Health Act, the refrigerant component can be separated efficiently.

(Supply of mixed refrigerant)
Next, the mixed refrigerant supply step S20 will be described with reference to FIG. The operation of the vacuum pump 60 is stopped, and the three-way valve V40 is switched so that the gas flowing out from the outflow part 411 of the reaction vessel 41 is supplied to the recovery part 80. In addition, the three-way valve V <b> 20 is switched so that the mixed refrigerant G in the pressure vessel 2 is supplied from the inflow portion 410 of the reaction vessel 41. Next, after adjusting the pressure reducing valve 3 so that the pressure of the mixed refrigerant G gas supplied from the pressure vessel 2 is equal to or higher than atmospheric pressure and lower than 200 kPa, the valve V1 of the pressure vessel 2 is opened, and the mixed refrigerant G gas is supplied. The reaction vessel 41 is supplied. The supply pressure of the mixed refrigerant G before and after the pressure reduction by the pressure reducing valve 3 is confirmed by pressure gauges P1 and P2 provided between the pressure vessel 2 and the reaction vessel 41, respectively. Further, the gas supply amount of the mixed refrigerant G is confirmed by the flow meter F1 and the mass meter M1. The supply amount of the mixed refrigerant G is preferably adjusted so that the amount of the specific refrigerant component Ga contained in the supplied gas is equal to or less than the saturated adsorption amount of the adsorbent 42.

  The gas of the mixed refrigerant G is easily introduced into the reaction vessel 41 due to the pressure difference because the pressure in the reaction vessel 41 is reduced to less than atmospheric pressure in the decompression step S10. By setting the gas supply pressure of the mixed refrigerant G to less than 200 kPa by the pressure reducing valve 3, the pressure in the reaction vessel 41 does not exceed 200 kPa, and the component separation of the mixed refrigerant G can be performed safely. Note that the adsorption step S30 described later is performed substantially simultaneously with the supply of the mixed refrigerant G in the main supply step S20, and the refrigerant component Gb that is not selectively adsorbed by the adsorbent 42 has an atmospheric pressure of atmospheric pressure. Exceeds the flow rate, it flows out from the outflow part 411 and is transferred to the recovery part 80. In addition, the supply pressure of the gas of the mixed refrigerant G is not limited to less than 200 kPa, and can be adjusted to a pressure of 200 kPa or more by the pressure resistance performance of the reaction vessel 41 or the like.

(Adsorption of specific refrigerant components)
In the main adsorption step S30, the specific refrigerant component Ga out of the mixed refrigerant G gas supplied into the reaction vessel 41 is adsorbed by the adsorbent 42 that selectively adsorbs the refrigerant component Ga. This adsorption step S30 is performed substantially simultaneously with the supply of the mixed refrigerant G in the supply step S20 described above. The temperature of the reaction vessel 41 and the pressure in the vessel are measured, and by these changes, the progress of the adsorption reaction and the amount of adsorption can be grasped, and the operation of the component separation apparatus 10 can be controlled. When a specific refrigerant component Ga in the mixed refrigerant G is adsorbed by the adsorbent 42 in the reaction vessel 41, the partial pressure of the refrigerant component Ga in the reaction vessel 41 decreases. While the adsorption reaction of the component Ga is in progress, the gas of the mixed refrigerant G is supplied. In the present embodiment, the supply pressure of the refrigerant component G is set higher than the atmospheric pressure, so that the reaction vessel 41 is pressurized to a pressure higher than the atmospheric pressure, and a selective adsorption reaction is likely to occur. Since the amount of the mixed refrigerant G supplied into the reaction vessel 41 is also supplied in a ventilated state, the amount of the other refrigerant component Gb attached to the adsorbent 42 is small as compared with the first embodiment. Therefore, the refrigerant component Gb that is not selectively adsorbed by the adsorbent 42 flows out from the reaction vessel 41 to the recovery unit 80.

(Recovery of other refrigerant components)
In this recovery step S40, the other refrigerant component Gb that is not adsorbed by the adsorbent 42 is recovered. As described above, the other refrigerant component Gb that is not selectively adsorbed by the adsorbent 42 moves from the outflow part 411 of the reaction container 41 to the intermediate tank 801 of the recovery part 80 due to the difference in pressure between the containers. The refrigerant component Gb that has flowed out is stored in the intermediate tank 801 of the recovery unit 80 to a certain extent, and is sent to the pressurized liquefier 802 and liquefied and stored in the recovery container 803 before the desorption step S50 by the purge to be performed later. . The refrigerant component Gb stored in the intermediate tank 801 is confirmed by the pressure gauge P4. Further, the amount of the refrigerant component Gb recovered in the recovery container 803 is measured by the mass meter M2. Note that the intermediate tank 801 may be omitted, and the pressurized liquefaction apparatus 802 and the collection containers 803 and 804 may be configured.

(Desorption of specific refrigerant components by purging)
Next, a specific refrigerant component desorption process S50 will be described with reference to FIG. In this embodiment, the desorption reaction of the specific refrigerant component Ga adsorbed on the adsorbent 42 is performed by purging with a purge gas. First, the outlet valve V1 of the pressure vessel 2 is closed, and the three-way valve V20 is switched so that the purge gas of the purge gas vessel 70 is supplied into the reaction vessel 41. When nitrogen gas, which is purge gas, is supplied from the purge gas container 70 to the reaction container 41 in this state, the refrigerant component Ga adsorbed by the adsorbent 42 is expelled from the adsorbent 42. The flow rate of nitrogen gas can be confirmed with the flow meter F2. If a large amount of nitrogen gas is supplied into the reaction vessel 41, the concentration of the specific refrigerant component Ga is lowered. Therefore, it is preferable to perform the desorption reaction with as small a gas amount as possible. Also in the desorption reaction by purging, heat of desorption occurs and the temperature in the reaction vessel 41 decreases, so the heating means 52 of the temperature adjusting means 5 is operated to keep the reaction vessel 41 warm. As a result, the elimination reaction is promoted, and it is possible to prevent troubles such as frost adhering due to excessive cooling of the reaction vessel 41. Further, while the desorption of the refrigerant component Ga is proceeding, desorption heat is generated and the temperature is remarkably lowered. However, when the desorption reaction approaches the end, the temperature change is weakened. By detecting the temperature change of the reaction vessel 41, the desorption state can be controlled. The specific refrigerant component Ga desorbed from the adsorbent 42 moves from the outflow part 411 of the reaction container 41 to the intermediate tank 801 of the recovery part 80 due to the difference in pressure between the containers. In this manner, by desorbing the specific refrigerant component Ga from the adsorbent 42, the adsorbent 42 can be regenerated and prepared for the next adsorption. Further, in this embodiment, the desorption of the specific refrigerant component Ga is performed by purging. However, as described in the first embodiment described above, by depressurizing the inside of the reaction vessel 41 under the heating condition. It is also possible to desorb the specific refrigerant component Ga from the adsorbent 42.

(Recovery of desorbed refrigerant components)
The recovery process S60 of the desorbed refrigerant component will be described with reference to FIG. In this step, the specific refrigerant component Ga desorbed by the purge in the desorption step S50 is recovered. The specific refrigerant component Ga moved from the outflow part 411 of the reaction container 41 to the intermediate tank 801 of the recovery part 80 due to the difference in pressure between the containers is sent to the pressurized liquefaction device 802 when it is stored to a certain extent. It is liquefied and stored in the collection container 804. At the stage of being stored in the intermediate tank 801, nitrogen gas that is a purge gas is included in addition to the specific refrigerant component Ga, but the specific pressure is increased by a predetermined pressure in the pressure liquefaction device 802. Only the refrigerant component Ga is liquefied and stored in the recovery container 804. The refrigerant component Ga flowing out of the reaction vessel 41 and stored in the intermediate tank 801 is confirmed by the pressure gauge P4. Further, the amount of the refrigerant component Ga recovered in the recovery container 804 is measured by the mass meter M3. Note that the intermediate tank 801 may be omitted, and the pressurized liquefaction apparatus 802 and the collection containers 803 and 804 may be configured.

  When the component separation device 10 according to the present embodiment is a small device, or when the amount of the mixed refrigerant G stored in the pressure vessel 2 is larger than the amount that the adsorbent 42 can adsorb, the adsorption is performed once. In the desorption, the mixed refrigerant G remains in the pressure vessel 2. In that case, similarly to the first embodiment, the recovery amount can be increased by repeating the steps S20 to S60 until the component separation of the mixed refrigerant G in the pressure vessel 2 is almost completed. In this embodiment, as shown in FIG. 11, when the component separation of the mixed refrigerant G is almost completed, the pressure vessel 2 reaches about 1 kPa, and each refrigerant component is accommodated in the collection vessels 803 and 804. . This state can be confirmed by measuring the masses of the mass meters M1 to M3 installed in the pressure vessel 2 and the recovery vessels 803 and 804.

  In the present embodiment, each refrigerant component constituting the mixed refrigerant G is collected in the collection containers 803 and 804, respectively. Since each separated refrigerant component is accommodated in the container, it is in a state where it can be easily reused, and it is possible to make a mixed refrigerant again at an appropriate ratio or use it as a single composition refrigerant.

  Furthermore, the other description regarding the usage method of the component separation apparatus 10 which concerns on this embodiment is the same as that of the case of 1st Embodiment mentioned above, and the effect is also the same. In the present embodiment, as a method of using the component separation device 10, in the mixed refrigerant supply step S 2 and the adsorption step S 3, the valve V 30 on the outflow part 411 side of the reaction vessel 41 is opened and ventilated with the recovery part 80. However, as described in the first embodiment, the supply of the mixed refrigerant and the adsorption reaction are performed in a state where the valve V30 is closed and the recovery unit 80 is not vented. Is also possible.

  Next, a mixed refrigerant component separation apparatus 100 according to a third embodiment of the present invention shown in FIG. 12 will be described.

  As shown in FIG. 12, the mixed refrigerant component separation device 100 according to this embodiment includes a pressure vessel 2 in which a mixed refrigerant G is stored, and a reaction vessel filled with an adsorbent 42 that adsorbs a specific refrigerant component. 41, the temperature adjusting means 5 for adjusting the temperature of the reaction vessel 41, the pressure reducing means (vacuum pump 600) for reducing the pressure inside the reaction vessel 41, and the recovery portion 800 for recovering the separated specific refrigerant component. It is roughly structured.

  First, the pressure vessel 2 in which the mixed refrigerant G is stored will be described. As this pressure vessel 2, one having the same configuration as the pressure vessel 2 in the first embodiment can be used. The pressure vessel 2 is connected to the reaction vessel 41 of the adsorption unit 4 through a flow path. That is, as shown in FIG. 12, the pressure vessel 2 is connected to the reaction vessel 41 of the adsorption unit 4 through the valve V1, the pressure reducing valve 3, the flow meter F1, and the valve V2 in detail. A pressure gauge P1 is provided in the flow path between the valve V1 and the pressure reducing valve 3, and a pressure gauge P2 is provided in the flow path between the pressure reducing valve 3 and the flow meter F1.

  The pressure reducing valve 3 is provided to adjust a supply pressure when supplying the mixed refrigerant G in the pressure vessel 2 to the adsorption unit 4. In the present embodiment, by reducing the gas supply pressure of the mixed refrigerant G to less than 200 kPa with the pressure reducing valve 3, the pressure in the reaction vessel 41 becomes less than 200 kPa, and even if the reaction vessel 41 is not a pressure vessel, it is safe. An adsorption reaction can be performed. In the present embodiment, the mixed refrigerant G stored in the pressure vessel 2 is composed of a specific refrigerant component Ga that is selectively adsorbed by an adsorbent 42 described later and other refrigerant components Gb other than that. Yes. The mixed refrigerant component is not limited to one composed of two types of refrigerant components, and may be composed of more types of refrigerant components. The mixed refrigerant G is not limited to chlorofluorocarbons and may be any substance used as a refrigerant, and naturally includes a hydrocarbon-based mixed refrigerant.

  Next, the structure of the adsorption | suction part 4 in this embodiment is demonstrated. The adsorbing unit 4 is generally composed of a reaction vessel 41 and an adsorbent 42 filled therein, and adsorption and desorption reactions by the adsorbent 42 are performed. The reaction vessel 41 includes a gas inflow portion 410 connected to the pressure vessel 2 via a valve V2, and a gas outflow portion 411 connected to a vacuum pump 600 described later via a valve V30. Yes. The reaction vessel 41 is filled with an adsorbent 42 that selectively adsorbs a specific refrigerant component Ga from the mixed refrigerant G.

  In the present embodiment, the reaction vessel 41 corresponds to a “pressure vessel” in the Industrial Safety and Health Act when the mixed refrigerant supplied from the inflow portion 410 causes the pressure in the vessel to be 200 kPa (0.2 MPa) or more. Therefore, it is necessary to have a configuration that satisfies the structural standard based on the regulation with respect to pressure resistance and the like. However, when adjusting the pressure in the reaction vessel 41 to be less than 200 kPa, it is not subject to the above regulation, and therefore the reaction vessel 41 does not need to have special pressure resistance performance. Therefore, the component separation apparatus 100 according to the present embodiment is configured to be used by reducing the gas pressure with the pressure reducing valve 3 so that the pressure in the reaction vessel 41 is less than 200 kPa. The reaction vessel 41 is provided with a safety valve 412 so that the pressure inside the vessel does not exceed 200 kPa. In addition, it is also possible to make the reaction vessel 41 and other members have pressure resistance required for the “pressure vessel” in the Industrial Safety and Health Act, and to set the pressure in the reaction vessel 41 to 200 kPa or more.

  Next, the decompression means will be described. The decompression means is provided for decompressing the inside of the reaction vessel 41, and is constituted by a vacuum pump 600 in the present embodiment. This vacuum pump 600 is connected to the outflow part 411 of the reaction vessel 41 via a valve V30. A pressure gauge P3 is provided in the flow path between the valve V30 and the vacuum pump 600. The vacuum pump 600 is connected to the intermediate tank 81c of the recovery unit 800 via the three-way valve V400. By operating the vacuum pump 600, the inside of the reaction vessel 41 is depressurized, and the components adsorbed on the adsorbent 42 can be desorbed. In addition, before adsorbing the specific refrigerant component Ga to the adsorbent 42, the inside of the reaction vessel 41 is depressurized to remove moisture and other substances adsorbed on the adsorbent 42 in advance and air in the reaction vessel 41. It is possible to improve the efficiency of the adsorption reaction performed later. The vacuum pump 600 is preferably one that can be depressurized so that the pressure in the reaction vessel 41 is 1 kPa to less than 20 kPa from the viewpoint of the desorption rate of the refrigerant component adsorbed by the adsorbent 42.

  Next, the collection means 800 will be described. In the present embodiment, the recovery means 800 is generally configured by an intermediate tank 81c, a pressurized liquefier 82c, and a recovery container 83c. In the recovery means 800, the refrigerant component separated by the adsorption unit 4 is recovered. The intermediate tank 81c is connected to the vacuum pump 600 via the three-way valve V400. The intermediate tank 81c is connected to the recovery container 83c via the pressurized liquefying device 82c. Furthermore, the intermediate tank 81c is provided with a pressure gauge P4 for monitoring the amount of the refrigerant component Ga flowing into the intermediate tank 81c. The desorbed refrigerant component flows into the intermediate tank 81c via the three-way valve V400, and then is liquefied by the pressurized liquefier 82c and collected in the collection container 83c. In the present embodiment, an intermediate tank 81c is provided, and the pressurized liquefaction process is performed by the pressurized liquefier 82c when a certain amount of refrigerant component is collected by monitoring of the pressure gauge P4. The intermediate tank 81c may be omitted, and only the pressurized liquefier 82c and the recovery container 83c may be configured. In the present embodiment, the collection container 83c is arranged on a mass meter M2 such as an electronic balance, and is configured to measure the collection amount.

  Next, a mixed refrigerant component separation method using the component separation device 100 according to the present embodiment will be described with reference to FIGS.

  As shown in FIG. 13, the mixed refrigerant component separation method according to the present embodiment includes a depressurization step S <b> 100 for reducing the pressure in the reaction vessel 41, a supply step S <b> 200 for supplying the mixed refrigerant into the reaction vessel 41, and the reaction vessel 41. Adsorption step S300 for adsorbing a specific refrigerant component to the adsorbent 42, desorption step S400 for desorbing the specific refrigerant component by reducing the pressure in the reaction vessel 41, and recovering the desorbed specific refrigerant component Specific component recovery step S500, determine whether or not the separation of the specific refrigerant component from the mixed refrigerant is almost finished, and if the separation is not almost finished (in the case of NO), return to the supply step S200 and repeat steps S200 to S500, When the separation is almost completed (in the case of YES), it includes a determination step S600 for proceeding to the next step, and another component recovery step S700 for recovering other refrigerant components. In this embodiment, the mixed refrigerant G stored in the pressure vessel 2 includes, as an example, a specific refrigerant component (component adsorbed on the adsorbent 42) Ga and another refrigerant component Gb (component not adsorbed on the adsorbent 42). However, the mixed refrigerant component is not limited to one composed of two types of refrigerant components, and may be composed of more types of refrigerant components.

(Reduced pressure in the reaction vessel)
First, the decompression step S100 in the reaction vessel will be described based on FIG. While the valve V2 on the inflow portion 410 side of the reaction container 41 is closed, the valve V30 on the outflow portion 411 side is opened, and the vacuum pump 600 and the recovery portion 800 are exhausted so that air sucked by the vacuum pump 600 is exhausted outside the apparatus. The three-way valve V400 provided between is switched. When the vacuum pump 600 is operated in this state, suction is performed and the inside of the reaction vessel 41 becomes a reduced pressure environment. The pressure reduction by the vacuum pump 600 is preferably 1 kPa to less than 20 kPa, and more preferably 1 kPa to 10 kPa. The pressure in the reaction vessel 41 is confirmed by a pressure gauge P3 provided in the flow path between the valve V30 and the vacuum pump 600. Moreover, it is also preferable to heat the reaction vessel 41 by operating the heating means 52 of the temperature adjusting means 5. Thereby, since the component previously adsorbed by the adsorbent 42 is more reliably desorbed, impurities can be removed and the adsorbent 42 is regenerated.

  By this operation, the air previously contained in the reaction container 41 is discharged out of the apparatus, and the adsorption reaction performed in the subsequent process can be performed efficiently. Further, by this operation, the components (mainly moisture etc.) previously adsorbed on the adsorbent 42 are also desorbed and discharged out of the apparatus, so that the adsorbent 42 itself is also reliably regenerated, and the subsequent adsorption reaction Efficiency can be improved. Furthermore, since the pressure in the reaction vessel 41 is reduced to less than atmospheric pressure by performing this decompression step S100, even when the mixed refrigerant G flows into the reaction vessel 41 in the next supply step S200, the reaction vessel 41 It is easy to control the pressure inside 41 to less than 200 kPa (0.2 MPa), and even when the reaction vessel 41 is not a “pressure vessel” in the Industrial Safety and Health Act, the refrigerant component can be separated efficiently.

(Supply of mixed refrigerant)
Next, the mixed refrigerant supply step S200 will be described with reference to FIG. The operation of the vacuum pump 600 is stopped, and the valve V30 on the outflow portion 411 side of the reaction vessel 41 is closed. Next, the pressure reducing valve 3 is adjusted so that the gas pressure of the mixed refrigerant G supplied from the pressure vessel 2 is equal to or higher than atmospheric pressure and lower than 200 kPa. Then, the inlet valve V2 on the inflow portion 410 side of the reaction vessel 41 and the outlet valve V1 of the pressure vessel 2 are opened, and the gas of the mixed refrigerant G is supplied from the pressure vessel 2 to the inflow portion 410 of the reaction vessel 41. The supply pressure of the mixed refrigerant G before and after the pressure reduction by the pressure reducing valve 3 is confirmed by pressure gauges P1 and P2 provided between the pressure vessel 2 and the reaction vessel 41, respectively. Further, the gas supply amount of the mixed refrigerant G is confirmed by the flow meter F1 and the mass meter M1. It is preferable to adjust the supply amount of the mixed refrigerant G so that the amount of the specific refrigerant component Ga included in the supplied gas exceeds the saturated adsorption amount of the adsorbent 42.

  The gas of the mixed refrigerant G is easily introduced into the reaction container 41 due to the difference in pressure because the pressure in the reaction container 41 is reduced to less than atmospheric pressure in the decompression step S100. The supply of the gas of the mixed refrigerant G is stopped when the supply pressure adjusted by the pressure reducing valve 3 and the pressure in the reaction vessel 41 become equal. By setting the gas supply pressure of the mixed refrigerant G to less than 200 kPa by the pressure reducing valve 3, the pressure in the reaction vessel 41 does not exceed 200 kPa, and the component separation of the mixed refrigerant G can be performed safely. Further, even when the supply pressure of the mixed refrigerant G is set to the same pressure as the atmospheric pressure by the pressure reducing valve 3, the pressure in the reaction vessel 41 is reduced to less than the atmospheric pressure. The gas of the mixed refrigerant G is smoothly introduced into the gas 41, and the gas of the mixed refrigerant G is supplied until the pressure in the reaction vessel 41 reaches the same pressure as the atmospheric pressure. An adsorption step S300 described later is performed substantially simultaneously with the supply of the mixed refrigerant G in the main supply step S200, and when a specific refrigerant component Ga of the mixed refrigerant G is selectively adsorbed to the adsorbent 42, the specific refrigerant component Ga. Is lost from the gas phase and the pressure in the reaction vessel 41 decreases. Therefore, the gas is supplied while the adsorption reaction of the specific refrigerant component Ga proceeds in the reaction vessel 41. In addition, the supply pressure of the gas of the mixed refrigerant G is not limited to less than 200 kPa, and can be adjusted to a pressure of 200 kPa or more by the pressure resistance performance of the reaction vessel 41 or the like.

(Adsorption of specific refrigerant components)
In the main adsorption step S300, among the mixed refrigerant G gas supplied into the reaction vessel 41, a specific refrigerant component Ga is adsorbed by the adsorbent 42 that selectively adsorbs the refrigerant component Ga. When a specific refrigerant component Ga in the mixed refrigerant G is adsorbed on the adsorbent 42 in the reaction vessel 41, the partial pressure of the refrigerant component Ga in the reaction vessel 41 is reduced. Therefore, the gas of the mixed refrigerant G supplied from the pressure vessel 2 during the adsorption reaction is mainly composed of the gas of the refrigerant component Ga in which the difference in partial pressure is generated. Therefore, when the component separation by the adsorption of the refrigerant component Ga is completed, the other refrigerant component Gb that has not been adsorbed and separated mainly remains in the pressure vessel 2, and therefore the other refrigerant component Gb is It collect | recovers in the state accommodated in the pressure vessel 2 (refer FIG. 16). In the present embodiment, since the supply pressure of the refrigerant component G is set higher than the atmospheric pressure, the reaction vessel 41 is pressurized to a pressure higher than the atmospheric pressure and a selective adsorption reaction is likely to occur. Since the amount of the mixed refrigerant G supplied into the container 41 is also supplied such that the adsorbent 42 is substantially saturated, other refrigerant components Gb adhere to the adsorbent 42 as compared with the first embodiment. The amount to be considered is considered to be small.

(Desorption of specific refrigerant components by decompression and heating)
Next, a specific refrigerant component desorption process S400 will be described with reference to FIG. In this embodiment, the desorption reaction of the specific refrigerant component Ga adsorbed on the adsorbent 42 is performed by reducing the pressure in the reaction vessel 41 and heating. First, the valve V1 of the pressure vessel 2 and the valve V2 on the inflow portion 410 side of the reaction vessel 41 are closed. Next, the valve V30 on the outflow part 411 side of the reaction vessel 41 is opened. Further, the three-way valve V400 provided between the vacuum pump 600 and the recovery unit 800 is switched so that the refrigerant component Ga sucked by the vacuum pump 600 is sent to the intermediate tank 81c of the recovery means 800. Furthermore, the heating means 52 of the temperature adjustment means 5 is operated to heat the reaction vessel 41. When the vacuum pump 600 is operated in this state, the vacuum pump 600 sucks the inside of the reaction vessel 41 and makes the inside of the reaction vessel 41 a reduced pressure environment. The reduced pressure in the vacuum pump 600 is preferably 1 kPa to less than 20 kPa, more preferably 1 kPa to 10 kPa, from the viewpoint of desorption efficiency. The pressure in the reaction vessel 41 can be confirmed by a pressure gauge P3. Further, if the temperature of the heat medium W of the heating means 52 exceeds 100 ° C., the refrigerant component may be decomposed and toxic components may be generated. In the present embodiment, since water is used as the heat medium, the reaction vessel 41 is not heated above 100 ° C., and the refrigerant component can be safely separated. Even if the reaction vessel 41 is sucked by the vacuum pump 600, the pressure in the reaction vessel 41 is large because the refrigerant component Ga comes out into the gas phase while the desorption of the refrigerant component Ga is in progress. It does not decrease, and the pressure decreases greatly when the desorption of the refrigerant component Ga ends. This change in pressure can be detected by the pressure gauge P3 to confirm the desorption state.

  The specific refrigerant component Ga desorbed from the adsorbent 42 is sent to the intermediate tank of the recovery unit 800 by the vacuum pump 600. Thus, by desorbing the specific refrigerant component Ga from the adsorbent 42, the adsorbent 42 can be regenerated, and the reaction vessel 41 can be in a reduced pressure environment. Supply and adsorption.

(Recovery of desorbed refrigerant components)
The recovery process S500 for the desorbed refrigerant component will be described with reference to FIG. In this step, the specific refrigerant component Ga desorbed by heating and depressurization in the desorption step S400 is collected. The specific refrigerant component Ga sent by the vacuum pump 600 is stored in the intermediate tank 81c, and is sent to the pressurized liquefaction device 82c when it is stored to a certain extent, and is liquefied and stored in the recovery container 83c. The amount of the refrigerant component Ga stored in the intermediate tank 81c is confirmed by the pressure gauge P4. Further, the amount of the refrigerant component Ga recovered in the recovery container 83 is measured by the mass meter M2. When the component separation by the adsorption of the refrigerant component Ga is completed, the other refrigerant component Gb that has not been adsorbed and separated mainly remains in the pressure vessel 2, so that the other refrigerant component Gb is the pressure vessel 2. It is collected in the state stored in. Note that the intermediate tank 81c may be omitted, and only the pressurized liquefier 82c and the recovery container 83c may be configured.

(Repetition of steps S200 to S500)
Next, the determination step S600 will be described. In the determination step S600, it is determined whether or not the separation of the specific refrigerant component from the mixed refrigerant is almost completed. If the separation is not completed (in the case of NO), the process returns to the supply step S200 and the steps S200 to S500 are repeated. When separation is almost completed (in the case of YES), the process proceeds to the next step. When the component separation device 100 according to FIG. 12 is a small device, or when the amount of the mixed refrigerant G stored in the pressure vessel 2 is larger than the amount that the adsorbent 42 can adsorb, In the desorption, the pressure vessel 2 is in a state in which the mixed refrigerant G (Ga + Gb) remains and still contains a separable refrigerant component Ga. Therefore, the steps S200 to S500 are repeated until the component separation of the mixed refrigerant G in the pressure vessel 2 is almost completed. When the specific refrigerant component Ga remains in the pressure vessel 2, adsorption and desorption reactions with the adsorbent 42 occur, so that the temperature change of the reaction vessel 41 occurs. By detecting this temperature change, it is possible to confirm whether or not the component separation of the mixed refrigerant G is almost completed. It is also possible to confirm whether or not the component separation of the mixed refrigerant G has been substantially completed by measuring changes in mass of the mass meters M1 and M2 installed in the pressure vessel 2 and the recovery vessel 83c. .

(Recovery of other refrigerant components)
As a result of the above-described steps, the component separation of the mixed refrigerant G is almost completed, so that the refrigerant container Gb remains in a high ratio in the pressure vessel 2 and is not subject to adsorption separation. Can be recovered. The recovered material can be reused as a refrigerant composition mainly containing the refrigerant component Gb.

  In this way, each refrigerant component constituting the mixed refrigerant G is collected in the pressure vessel 2 and the collection vessel 83. Since each separated refrigerant component is accommodated in the container, it is in a state where it can be easily reused, and it is possible to make a mixed refrigerant again at an appropriate ratio or use it as a single composition refrigerant. In the present embodiment, as a method of using the component separation apparatus 100, in the mixed refrigerant supply step S200 and the adsorption step S300, the valve V30 on the outflow portion 411 side of the reaction vessel 41 is closed and the recovery portion 800 is not vented. As described in the second embodiment, the mixed refrigerant supply and the adsorption reaction are performed with the valve V30 opened and ventilated with the recovery unit 800 as described in the second embodiment. Is also possible.

  In the present embodiment, the specific refrigerant component Ga is desorbed from the adsorbent 42 by the pressure reduction and heating of the reaction container 41. However, the purge gas container 70 described in the second embodiment is added to the component separation apparatus 100. It is also possible to desorb the specific refrigerant component Ga from the adsorbent 42 by supplying a purge gas into the reaction vessel 41.

  Hereinafter, the present invention will be described in detail with reference to examples.

1. Adsorption of Mixed Refrigerant R-410A Gas onto ZMS Adsorbent In the component separation apparatus 100 according to the third embodiment of the present invention shown in FIG. 12, a reaction vessel 41 made of stainless steel and having an inner diameter of 3 cm and a length of 35 cm. Was used. The reaction vessel 41 is filled with 186 g (about 230 mL, filling height about 33 cm) of zeolite molecular sieve 4A (product of Union Showa Co., Ltd., molecular sieve 4A 3.2 pellets) as an adsorbent 42, and the reaction vessel is filled with a vacuum pump 6. The pressure in 41 was reduced to about 2 kPa to remove the air in the reaction vessel 41, and the adsorbent 42 was purified. The valve V3 on the outflow part 411 side of the reaction vessel 41 is closed, and R-410A gas (HFC-32 (difluoromethane): HFC-125 (pentafluoroethane)) = 50 as a mixed refrigerant G from the pressure vessel 2 in a non-ventilated state: 50) was fed to the reaction vessel 41. The supply pressure of the R-410A gas was adjusted by the pressure reducing valve 3 so as to be about 150 kPa, and the flow rate in terms of 1 atm was 1.04 L / min. Moreover, the temperature control means 5 was not operated and the test was performed in a room temperature environment of 20 ° C. The time after starting the supply of the R-410A gas was taken as the adsorption time, and the adsorption amount of each refrigerant component gas for each predetermined adsorption time was measured.

  The results are shown in FIG. The vertical axis represents the integrated adsorption amount (g / kg), and the horizontal axis represents the adsorption time (min). Up to about 18 minutes of adsorption time, a linear increase in adsorption of HFC-32 to the zeolitic molecular sieve 4A was observed, indicating that about 140 g per 1 kg of adsorbent was adsorbed. Thereafter, the adsorption rate of HFC-32 decreased and the increase in adsorption amount gradually decreased, but the adsorption amount increased to about 160 g per kg of adsorbent. On the other hand, HFC-125 was not adsorbed at all on the zeolitic molecular sieve 4A. From this result, it was shown that the zeolitic molecular sieve 4A selectively adsorbs HFC-32.

2. Desorption of Mixed Refrigerant R-410A Gas from ZMS Adsorbent Using the apparatus described in Example 1, mixed refrigerant R-410A gas (HFC-32: HFC-125 = 50: 50) from pressure vessel 2 in a non-ventilated state. ) Was supplied to the reaction vessel 41, and HFC-32 was adsorbed on the zeolite-based molecular sieve 4A at room temperature. The supply pressure of R-410A gas was about 200 kPa, and the adsorption time was 30 minutes. Thereafter, the heating means 52 is operated, and while the reaction vessel 41 is kept warm with 95 ° C. hot water, the inside of the reaction vessel 41 is sucked and depressurized by the vacuum pump 6, and the HFC-32 adsorbed on the adsorbent is depressurized and removed. Released. The pressure during desorption was 4.5 kPa. The time from the start of suction with a vacuum pump was taken as the desorption time, and the desorption amount of each refrigerant component gas for each predetermined desorption time was measured.

  The results are shown in FIG. The vertical axis represents the accumulated desorption amount (g / kg), and the horizontal axis represents the desorption time (min). It was shown that HFC-32 adsorbed on the zeolite molecular sieve 4A was desorbed in a certain amount in several minutes, and then desorbed to about 83 g per kg of adsorbent in 60 minutes. Thereafter, the amount of desorption continued to increase, but the desorption rate gradually decreased. On the other hand, no desorption of HFC-125 was observed, and it was confirmed that HFC-32 and HFC-125 were almost completely separated. From this result, it was found that the zeolitic molecular sieve 4A was suitably used for separating the components of R-410A.

3. Examination of the heat transfer area of the reaction vessel As the reaction vessel 41, a vessel made of stainless material having an inner diameter of 5 cm and a length of 14 cm is used, and as the adsorbent 42, zeolite-based molecular sieve 4A (product of Union Showa Co., Ltd., molecular sieve 4A 3) .2 pellets) was subjected to an adsorption / desorption test under the same conditions as in Examples 1 and 2, except that 189 g (about 230 mL, filling height: about 12 cm) were filled. The time from the start of suction with a vacuum pump was taken as the desorption time, and the desorption amount of each refrigerant component gas for each predetermined desorption time was measured.

The results are shown in FIG. The vertical axis represents the accumulated desorption amount (g / kg), and the horizontal axis represents the desorption time (min). In Example 2, about 80 g of HFC-32 was desorbed at a desorption time of 50 minutes. In this example, it took twice as long as 100 minutes to desorb the same amount. I understood that. This is because the heat transfer area of the reaction vessel used in Example 2 was 0.134 m ² per liter of the adsorbent, whereas in this example, it was 0.080 m ² , and the adsorbent 41 at the time of desorption. This is probably because the heat exchange was not sufficient. From this, in order to improve reaction efficiency, it is preferable that the heat transfer area of the reaction vessel is 0.1 m ² / L or more.

4). Adsorption of mixed refrigerant R-407C gas to ZMS adsorbent In the component separation apparatus 1 according to the third embodiment of the present invention shown in FIG. 42, 172 g (about 215 mL) of zeolite-based molecular sieve 4A (product of Union Showa Co., Ltd., molecular sieve 4A 3.2 pellets) is filled, and the pressure in the reaction vessel 41 is reduced to about 2 kPa with the vacuum pump 6. The air in 41 was removed and the adsorbent 42 was purified. The valve V3 on the outflow part 411 side of the reaction vessel 41 is closed, and R-407C gas (difluoromethane (HFC-32): pentafluoroethane (HFC-125): 1, as mixed refrigerant G from the pressure vessel 2 in a non-ventilated state. 1,1,2-tetrafluoroethane (HFC-134a) = 23: 25: 52) was supplied to the reaction vessel 41. The supply pressure of the R-407C gas was adjusted by the pressure reducing valve 3 so as to be about 150 kPa, and the flow rate in terms of 1 atm was 2.18 L / min. Moreover, the temperature control means 5 was not operated and the test was performed in a room temperature environment of 22 ° C. The time from the start of the supply of R-407C gas was taken as the adsorption time, and the adsorption amount of each refrigerant component gas for each predetermined adsorption time was measured.

  The results are shown in FIG. The vertical axis represents the integrated adsorption amount (g / kg), and the horizontal axis represents the adsorption time (min). R-407C has a mixing ratio of HFC-32 that is 1/2 or less than that of R-410A. However, it was found that the amount of adsorption was approximately the same when the flow rate was doubled. This indicates that HFC-32 is selectively adsorbed on the molecular sieve 4A without being affected by the coexistence of HFC-125 and HFC-134a. On the other hand, no adsorption of HFC-125 or HFC-134a was observed in this example.

5. Adsorption of Mixed Refrigerant R-410A Gas to MSC Adsorbent As a reaction vessel 41, a vessel made of stainless steel with an inner diameter of 3 cm and a length of 20 cm is used. As the adsorbent 42, molecular sieve carbon X2M [Osaka Gas Chemical Co., Ltd.] The adsorption test was conducted under the same conditions as in Example 1 except that 65 g (about 125 mL) of the product, granular white birch (registered trademark) X2M] was charged. The supply pressure of the R-410A gas was adjusted by the pressure reducing valve 3 so as to be about 150 kPa, and the flow rate in terms of 1 atm was 0.5 L / min. Moreover, the temperature control means 5 was not operated and the test was performed in a room temperature environment of 20 ° C. The time after starting the supply of the R-410A gas was taken as the adsorption time, and the adsorption amount of each refrigerant component gas for each predetermined adsorption time was measured.

  The results are shown in FIG. The vertical axis represents the integrated adsorption amount (g / kg), and the horizontal axis represents the adsorption time (min). For molecular sieve carbon X2M, HFC-32 adsorbs about 3 times the amount of HFC-125 until the adsorption time is around 10 minutes, but the difference decreases with the passage of time. It was found that the integrated adsorption amount of -32 was about 100 g / kg, and that of HFC-125 was about 80 g / kg. From this, it was found that there is a possibility that HFC-32 can be recovered about three times as much as HFC-125 by setting the adsorption time to about 10 minutes.

6). Desorption of Mixed Refrigerant R-410A Gas from MSC Adsorbent Using the component separation apparatus described in Example 5, the mixed refrigerant R-410A gas is discharged from the pressure vessel 2 in a non-vented state in the same manner as in Example 5 in the reaction vessel 41. And adsorbed onto molecular sieve carbon X2M [Osaka Gas Chemical Co., Ltd. product, granular white birch (registered trademark) X2M]. The supply pressure of R-410A gas was about 150 kPa, and the adsorption time was 30 minutes. Thereafter, a container containing nitrogen gas as a purge gas is connected to the inflow portion 410 of the reaction container 41, and a small amount of nitrogen gas is supplied into the reaction container 41 to purge the substance adsorbed by the MSC adsorbent with nitrogen. Was removed. The flow rate of nitrogen gas was about 0.2 mL / min. The desorption reaction was performed by operating the heating means 52 and keeping the reaction vessel 41 warm with 95 ° C. hot water. The time after the supply of nitrogen gas was taken as the desorption time, and the desorption amount of each refrigerant component gas for each predetermined desorption time was measured.

  The results are shown in FIG. The vertical axis represents the accumulated desorption amount (g / kg), and the horizontal axis represents the desorption time (min). HFC-32 was almost completely desorbed in about 15 minutes from the start of desorption, whereas HFC-125 was not completely desorbed even after about 60 minutes had elapsed. Therefore, if the difference in adsorption capacity and adsorption rate shown in Example 5 and the difference in desorption rate shown in this Example are utilized, it is considered that HFC-32 and HFC-125 can be separated into components. It is done.

7). Component Separation of Mixed Refrigerant R-410A In the component separation apparatus 1 according to the first embodiment of the present invention shown in FIG. 1, component separation of the mixed refrigerant R-410A that entered the pressure vessel 2 was performed. As the pressure vessel 2, one containing 10 to 15 kg of mixed refrigerant R-410A was used. As the reaction vessel 41, 19 tubes made of stainless steel and having an inner diameter of 31 mm and a length of 80 cm were used. The total capacity of the reaction vessel 41 is about 13L. A total of 7.822 kg of zeolite molecular sieve 4A (product of Union Showa Co., Ltd., molecular sieve 4A 3.2 pellets) was filled in the reaction vessel 41 as the adsorbent 42. The component separation step was performed as shown in steps S1 to S6 in the flowchart shown in FIG. Specifically, the pressure reduction in the reaction vessel 41, which is the preparation step S1, is performed using the vacuum pump 6a and the three-way valve V4, and ends when 5 minutes have elapsed after the pressure in the reaction vessel 41 shows 1 kPa or less. It was. In the next mixed refrigerant G supply step S2 and specific refrigerant component adsorption step S3, the pressure of the gas is adjusted by the pressure reducing valve 3 so that the liquid in the mixed refrigerant G is extracted and the pressure in the reaction vessel 41 does not exceed atmospheric pressure. It was adjusted. Moreover, the cooling means 53 was operated and the reaction vessel 41 in which the heat of adsorption was generated was cooled with water. The mixed refrigerant G was supplied under these conditions, and a specific refrigerant component was adsorbed on the adsorbent 42. The weight reduction at the mass meter M1 of the pressure vessel 2 reached 150 g, and the time when 1 minute passed after the internal temperature of the reaction vessel 41 became 20 ° C. or less was regarded as the end of the supply step S2 and the adsorption step S3. Next, as the recovery step S4, the pressure in the reaction vessel 41 was reduced by the vacuum pump 6a, and other components that were not selectively adsorbed by the adsorbent 42 were recovered in the intermediate tank 81a. The internal pressure of the intermediate tank 81a was monitored with a pressure gauge P4, liquefied with a pressurized liquefier 82a, and recovered in a recovery container 83a. Moreover, in this process S4, the temperature control means 5 was not operated but it performed at normal temperature of 18-22 degreeC. The time point when 5 minutes passed after the pressure in the reaction vessel 41 showed 1 kPa or less was regarded as the end of the recovery step S4. Next, as the desorption step S <b> 5, the heating means 52 was operated to supply hot water to the temperature adjustment jacket 51, and the adsorbent 42 was heated via the reaction vessel 41. The vacuum pump 6b was operated to reduce the pressure in the reaction vessel 41, and the specific refrigerant component selectively adsorbed on the adsorbent 42 was desorbed. The end of the desorption step S5 was defined as the time when 60 minutes passed after the internal temperature of the reaction vessel 41 reached 93 ° C. or higher and 1 minute passed after the pressure in the reaction vessel 41 showed 1 kPa or less. The desorbed specific refrigerant component was recovered in the intermediate tank 81b. The internal pressure of the intermediate tank 81b was monitored by the pressure gauge P5, liquefied by the pressurized liquefier 82b and stored in the recovery container 83b, and the specific refrigerant component recovery step S6 was completed.

  The test was performed twice. The results are shown in Table 2 below. The R-410A composition in the pressure vessel in Table 2 is a value obtained by measuring the blending ratio of the refrigerant component of R-410A accommodated in the pressure vessel 2 at the start of the test using gas chromatography. In addition, the amount recovered at normal temperature and reduced pressure is a value obtained by measuring the weight in the recovery container 83a with the mass meter M2 at the end of the fifth batch of the recovery step S4. The recovered amount by heating and depressurization is a value obtained by measuring the weight in the recovery container 83b with the mass meter M3 at the end of 5 batches of the desorption and recovery step S6. Moreover, the mixture ratio of each refrigerant | coolant component contained in the pressure vessel 2 and the collection containers 83a and 83b is the value measured using the gas chromatography.

  From the above results, the mixing ratio of HFC-32 and HFC-125 of the mixed refrigerant R-410A contained in the pressure vessel was about 1: 1. However, by performing the component separation process, It was found that -125 was separated with a very high purity of 99.9%. HFC-125 is a component Gb that is not selectively adsorbed by the other component, that is, the adsorbent 42. From this, in the reaction vessel 41, the adsorbent 42 selectively adsorbs a specific refrigerant component Ga when the mixed refrigerant G is supplied, and the selectively adsorbed component Ga is almost desorbed at room temperature and reduced pressure. I found out that it was not. Moreover, it turned out that HFC-32 is isolate | separated with a purity of about 90% after heating pressure reduction. The HFC-32 after heating and depressurization in this example contains about 10% of HFC-125 as an impurity. The amount of HFC-125 depends on the depressurization time and recovery time of the recovery step S4 performed earlier. It is considered that the temperature can be reduced by adjusting the temperature condition or pressure reduction time of the separation and recovery step S6. Thus, according to the present invention, it was found that the components of the mixed refrigerant can be easily and safely separated, and that the components separated and recovered have high purity.

  The present invention is not limited to the above-described embodiments or examples, and various design changes within the scope not departing from the gist of the invention described in the claims are also included in the technical scope. .

DESCRIPTION OF SYMBOLS 1, 10, 100 Component separation apparatus of mixed refrigerant 2 Pressure vessel 3 Pressure reducing valve 4 Adsorption part 41 Reaction container 410 Inflow part 411 Outflow part 412 Safety valve 42 Adsorbent 5 Temperature control means 51 Temperature control jacket 52 Heating means 52a Hot water production apparatus 52b Hot water circulation pump 53 Cooling means 53a Cold water production apparatus 53b Cold water circulation pump 6a, 6b, 60, 600 Vacuum pump 70 Purge gas container 8, 80, 800 Recovery unit 81a, 81b, 801, 81c Intermediate tank 82a, 82b, 802, 82c Pressurized liquefaction device 83a, 83b, 803, 804, 83c Recovery container G Mixed refrigerant Ga Specific refrigerant component (component that is selectively adsorbed by the adsorbent)
Gb Other refrigerant components (components that are not selectively adsorbed by the adsorbent)
F1, F2 Flow meter M1, M2, M3 Mass meter P1-P5 Pressure gauge V1-V3, V5, V30 Valve V4, V6, V20, V40, V50, V400 Three-way valve W Heat medium (water)

Claims (10)

In a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerant stored in a pressure vessel under a pressure exceeding atmospheric pressure,
The pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing the specific refrigerant component of the mixed refrigerant is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel. And a preparatory step of removing the substance adsorbed on the adsorbent;
An adsorption step of supplying the mixed refrigerant from the pressure vessel to the reaction vessel due to a difference in internal pressure between the pressure vessel and the reaction vessel, and adsorbing the specific refrigerant component to the adsorbent;
A desorbing step of heating the adsorbent with a heat medium and desorbing a specific refrigerant component adsorbed on the adsorbent. In a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerant stored in a pressure vessel under a pressure exceeding atmospheric pressure,
The pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing the specific refrigerant component of the mixed refrigerant is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel. And a preparatory step of removing the substance adsorbed on the adsorbent;
An adsorption step of supplying the mixed refrigerant from the pressure vessel to the reaction vessel due to a difference in internal pressure between the pressure vessel and the reaction vessel, and adsorbing the specific refrigerant component to the adsorbent;
A recovery step of recovering from the reaction vessel other components than the specific refrigerant component of the mixed refrigerant by reducing the pressure in the reaction vessel;
A desorbing step of heating the adsorbent with a heat medium and desorbing a specific refrigerant component adsorbed on the adsorbent. In a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerant stored in a pressure vessel under a pressure exceeding atmospheric pressure,
The pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing the specific refrigerant component of the mixed refrigerant is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel. And a preparatory step of removing the substance adsorbed on the adsorbent;
Due to the difference in internal pressure between the pressure vessel and the reaction vessel, the mixed refrigerant is supplied from the pressure vessel to the reaction vessel at a gas pressure equal to or higher than atmospheric pressure, and the specific refrigerant component is adsorbed by the adsorbent. An adsorption process;
In the adsorption step, a recovery step of recovering other refrigerant components that have not been adsorbed by the adsorbent by flowing out of the reaction vessel;
And a desorption step of heating the adsorbent with a heat medium and desorbing the specific refrigerant component adsorbed on the adsorbent. In a method for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerant stored in a pressure vessel under a pressure exceeding atmospheric pressure,
The pressure in the reaction vessel filled with an adsorbent capable of selectively adsorbing the specific refrigerant component of the mixed refrigerant is reduced to less than atmospheric pressure, and the gas present in the reaction vessel is removed from the reaction vessel. And a preparatory step of removing the substance adsorbed on the adsorbent;
Due to the difference in internal pressure between the pressure vessel and the reaction vessel, the mixed refrigerant is supplied from the pressure vessel to the reaction vessel at a gas pressure equal to or higher than atmospheric pressure, and the specific refrigerant component is adsorbed by the adsorbent. An adsorption process;
A desorption step of heating the adsorbent with a heat medium and desorbing the specific refrigerant component adsorbed on the adsorbent,
Components other than the specific refrigerant component are recovered as components remaining in the pressure vessel.   The mixing according to any one of claims 1 to 4, wherein heating of the adsorbent in the desorption step is performed by heating the reaction vessel with a heat medium of less than 100 ° C. Refrigerant component separation method.   The component of the mixed refrigerant according to any one of claims 1 to 5, wherein the desorption of the specific refrigerant component in the desorption step is performed by reducing the pressure in the reaction vessel. Separation method.   6. The component separation method for mixed refrigerant according to claim 1, wherein the desorption of the specific refrigerant component in the desorption step is performed by supplying a purge gas to the reaction vessel. . A component separation device for separating a specific refrigerant component from a mixed refrigerant containing two or more kinds of refrigerant stored in a pressure vessel,
A reaction vessel that is connected to the pressure vessel and filled with an adsorbent capable of selectively adsorbing the specific refrigerant component of the mixed refrigerant supplied from the pressure vessel via a pressure reducing valve;
A depressurization means connected to the reaction vessel and for discharging the gas present in the reaction vessel and the substance adsorbed on the adsorbent by depressurizing the pressure in the reaction vessel;
Temperature control means comprising a heat medium for adjusting the temperature of the reaction vessel;
A mixed refrigerant component separation apparatus comprising: a recovery container connected to the reaction container and recovering at least a specific refrigerant component adsorbed by the adsorbent.   The mixed refrigerant component separation apparatus according to claim 8, wherein the heat medium of the temperature adjusting means is water, and is configured so as to at least heat the reaction vessel. The mixed refrigerant component separation device according to claim 8 or 9, wherein a heat conduction area of the reaction vessel is configured to be 0.1 m ² / L or more per packed volume of the adsorbent. .

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