JP2005111470A - Method for removing chlorinated organic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily and efficiently removing a chlorinated organic compound from a solution which is filled into a vessel and contains low-concentration chlorinated organic compound, particularly from insulating oil which is filled into a pole-mounted transformer member and contains the chlorinated organic compound. <P>SOLUTION: This method for removing the chlorinated organic compound from the solution which is filled into the vessel and contains the chlorinated organic compound comprises the steps of: charging an adsorbing material in the solution or circulating the solution and making the solution pass through an adsorption apparatus arranged outside or inside the vessel to bring the solution into contact with the adsorbing material in the adsorption apparatus, so that the chlorinated organic compound is adsorbed on the adsorbing material and; recovering the adsorbing material together with the chlorinated organic compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a technology for removing organochlorine compounds contained in a solution filled in a container, and in particular, from a solution containing organochlorine compounds at a low concentration such as regenerated insulating oil used in pole transformers (pole transformers). The present invention relates to a method for removing organochlorine compounds.

  Among various organic chlorine compounds, polychlorinated biphenyl (PCB) is extremely harmful to living bodies including the human body. Therefore, it was designated as a specific chemical substance in 1973 and its production, import and use are prohibited. PCB has been used as an insulating oil for high-voltage transformers and high-voltage capacitors in electrical facilities such as power plants, vehicles, and ships. Therefore, insulating oil regeneration treatment is also applied to insulating oil such as pole transformers that did not originally use PCB. There is a possibility that a trace amount of PCB of 5 to 50 ppm which is considered to be mixed in the process is mixed. Since this trace amount of PCB-containing insulating oil may exist in large quantities, a vast area is used for storing them. In addition, many efforts and costs are required, such as rust-proof coating for safety management.

  Also, when processing is attempted at a PCB processing facility, transportation permission is required, and after passing through these procedures, a large amount of samples must be safely transported to the processing facility, requiring a lot of time, labor, and energy. It becomes.

  By the way, the present inventors have found that a small amount of an organic chlorine compound can be adsorbed in a solid-liquid manner by using zeolite or mesoporous silicate as an adsorbent (see Patent Document 1).

  On the other hand, in Japanese Patent Laid-Open No. 10-289824, as a disposal technique for a distribution pole transformer using a recycled insulating oil containing PCB, after the insulating oil is drained from the pole transformer in advance, the transformer members are crushed and separated for cleaning. A method has been proposed in which a cleaning solvent, insulating oil, and PCB are separated into gas and liquid, and then PCB remaining in the exhaust is adsorbed with activated carbon (see Patent Document 2). However, this technology is intended for pole transformers that use PCB-containing insulating oil, and does not require complicated operation and aims to efficiently remove PCB together with insulating oil from the transformer member. It is not possible to solve the problem of storage and transportation.

Japanese Patent Application No. 2003-109091 JP-A-10-289824

  The present invention has been made in view of problems in storage and transportation of pole transformers and the like, and easily and efficiently removes organochlorine compounds from a solution containing organochlorine compounds at a low concentration filled in a container. An object of the present invention is to provide a method for removing an organic chlorine compound easily and efficiently from an insulating oil containing an organic chlorine compound filled in a pole transformer member.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, they have found that the object can be achieved by the following method, and have completed the present invention.

  That is, the method according to the first aspect of the present invention is a method for removing an organochlorine compound from a solution containing an organochlorine compound filled in a container, the adsorbent being introduced into the solution, and the solution and the adsorbent The organic chlorine compound is adsorbed on the adsorbent by contacting the adsorbent, and then the adsorbent is recovered together with the organic chlorine compound.

  A method according to a second aspect of the invention is a method for removing an organochlorine compound from a solution containing an organochlorine compound filled in a container, wherein the solution is circulated and installed outside or in the container. Passing the adsorbent provided with the adsorbent, contacting the solution with the adsorbent, adsorbing the organochlorine compound to the adsorbent, and then recovering the adsorbent together with the organochlorine compound. To do.

In the methods according to the first and second inventions, the solvent of the solution may be either water or oil. Preferably, the container is a pole transformer member, and the solvent of the solution is a pole transformer. Insulating oil for use. When the solution and the adsorbent are brought into contact with each other, they may be brought into contact with stirring and / or heating and / or solvent dilution. In particular, when the solvent is an insulating oil, the organic chlorine compound and the solvent molecule may form a cluster, which may inhibit the adsorption of the organic chlorine compound. Stirring and / or heating and / or to the solvent dilution is considered in addition to the effect of a uniform reaction system, to destroy these clusters, the effect of facilitating undergo adsorption reaction in the exposed organic chlorine compounds It is done.

  In the first and second methods, the adsorbent is preferably at least one selected from zeolite, activated carbon, ion exchange resin, and alkali-modified activated carbon.

  As described above, according to the present invention, the adsorbent is put into the solution containing the organic chlorine compound at a low concentration filled in the container, such as the regenerated insulating oil filled in the pole transformer member, and the container is left to stand. Or after circulating the solution and passing through an adsorbing device provided with an adsorbent outside or inside the container, the organic chlorine compound is adsorbed on the adsorbent by contacting the solution with the adsorbent, Since the organochlorine compound concentration in the solution can be reduced simply by collecting the adsorbent adsorbing the organochlorine compound, the organochlorine compound can be efficiently removed by simultaneous storage and removal.

  If the concentration of organochlorine compound in the solution falls below the reference value during storage, only the collected adsorbent is transported from the storage location to the PCB processing facility and subjected to the prescribed treatment to remove the organochlorine compound. Since it can be collected, the transportation cost and labor can be greatly reduced compared to transporting the pole transformer.

  In the method of the present invention, the solvent of the solution containing the organochlorine compound may be either water or oil. That is, the method of the present invention is applied when a solution containing water or oil containing an organic chlorine compound as a solvent is filled in a container. The type of the oil solvent is not particularly limited, but is preferably a hydrocarbon oil, particularly a hydrocarbon oil having a high boiling point and good thermal stability, such as an electrical insulating oil used in a pole transformer.

  In the present invention, examples of the organic chlorine compound to be adsorbed and removed include at least one compound selected from the group consisting of polychlorinated biphenyls, dioxins, chlorobenzenes, and trichloroethane.

  The method of the present invention is applicable when the organochlorine compound content in the solution is on the order of several ppm to several thousand ppm, but considering the organochlorine compound content per adsorbent weight, a trace amount of 50 ppm or less Especially effective for adsorption of organochlorine compounds. The solution to be treated is preferably substantially free of moisture in order to maximize the adsorption capacity of the adsorbent, but may contain some water as long as it does not affect the adsorption. When moisture is contained in the oil to be treated, it is desirable to perform the adsorption removal treatment according to the present invention after the dehydration treatment. The dehydration treatment method is not particularly limited as long as a conventionally known method is appropriately applied. For example, a method of adsorbing an organic chlorine compound-containing oil that has been dehydrated using a dehydrating agent can be used.

  At the time of the dehydration, it is desirable that the additives (antioxidants and metal deactivators) added to the insulating oil are not adsorbed during the dehydration process in consideration of the reuse of the insulating oil. Examples of the dehydrating agent include A-type zeolite (Na-A type, KA type, Li-A type, Ca-A type), activated alumina, and the like.

  Examples of the container filled with the solution containing the organic chlorine compound include a tank installed in a storage place, a pole transformer member, and the like.

  The adsorbent used in the present invention is not particularly limited as long as it is an adsorbent that adsorbs an organic chlorine compound. For example, at least one selected from zeolite, activated carbon, ion exchange resin and alkali-modified activated carbon can be mentioned. As these adsorbents, those appropriately selected according to the kind of the organic chlorine compound to be treated and the content in the solution can be used alone or in combination of two or more.

  Here, the zeolite may be either natural zeolite or synthetic zeolite. Among the zeolites, those having an Si / Al atomic ratio of 2.0 or less are preferable from the viewpoint of excellent adsorption of organochlorine compounds, and examples thereof include A-type zeolite, X-type zeolite, and Y-type zeolite. The Si / Al atomic ratio of the zeolite is more preferably 1.0 to 1.5, still more preferably 1.0 to 1.2, and particularly preferably 1.0 to 1.1. X-type zeolite is particularly preferred because A-type zeolite has a smaller pore diameter than X-type zeolite, and there is a tendency that sufficient adsorption capacity of an organic chlorine compound cannot be obtained depending on the type of cation selected.

The ion-exchangeable cation contained in the zeolite is not particularly limited. Specific examples include various ions such as alkali metals, alkaline earth metals, transition metals, and group 4B elements. One or more of these ions are contained in the zeolite. Examples of the alkali metal ion include sodium ion (Na ⁺ ), potassium ion (K ⁺ ), lithium ion (Li ⁺ ), rubidium ion (Rb ⁺ ), and the like. Examples of the alkaline earth metal ion include calcium ion (Ca ²⁺ ), magnesium ion (Mg ²⁺ ), strontium ion (Sr ²⁺ ), barium ion (Ba ²⁺ ) and the like. Examples of the transition metal ion include scandium ion (Sc ⁺ ), manganese ion (Mn ³⁺ ), chromium ion (Cr ³⁺ ), iron ion (Fe ³⁺ ), cobalt ion (Co ³⁺ ), nickel ion (Ni ²⁺ ), Examples include copper ions (Cu ⁺ ) and silver ions (Ag ⁺ , Ag ²⁺ ).

  Among the cations, alkali metal ions and alkaline earth metal ions are preferable from the viewpoint of excellent adsorptivity of organochlorine compounds, and belong to the class with the largest crystal window diameter among X-type zeolites, and PCBs can be easily incorporated into crystals. Lithium ions that can permeate are preferred.

  When a small amount of organochlorine compound is adsorbed and removed from a solution that does not substantially contain water, dehydrated zeolite is preferably used as the adsorbent in order to prevent a decrease in adsorption capacity due to moisture adsorption. The dehydration method is not particularly limited, and a known means such as heat treatment or reduced pressure treatment may be appropriately used. In general, the heat treatment can be performed at 250 to 400 ° C., or a decompression treatment can be combined with this.

  The shape of the adsorbent used in the present invention is not particularly limited, and it is used as a molded body having a structure such as a powder, a pellet, a bead, or a honeycomb type, a lattice type, or a spiral type. When using a molded body, for example, an inorganic binder such as clay or silica sol such as kaolin or sepiolite, or an organic binder is added to zeolite powder, and extrusion molding, agitation granulation, sheet molding, corrugated cardboard, etc. It is used after being molded by a commonly used method such as spray coating or zeolite paper molding. The binder used may be a binderless molded body that can be changed to X-type zeolite or the like during the production of the molded body.

  When adsorbing an organic chlorine compound in a solution using an adsorbent, the concentration of the organic chlorine compound in the solution is measured before charging the adsorbent. The concentration of the organic chlorine compound can be measured using, for example, a gas chromatography mass spectrometer (GC-MS), a gas chromatograph / electron capture detector (GC-ECD), or the like.

  Next, the necessary amount of the adsorbent is calculated from the concentration of the organochlorine compound, and the adsorbent in an amount equal to 100 times the theoretical adsorption amount, preferably equal to several tens of times, is charged into the solution. If the concentration exceeds the adsorption capacity of the adsorbent that can be filled in the container because the organochlorine compound concentration is high, the adsorbent is replaced, for example, every day to several months after reaching saturated adsorption. After the adsorbent is charged, the organochlorine compound concentration in the solution is measured at an appropriate time interval, and the adsorbent is added or replaced as necessary. That is, when the organochlorine compound concentration falls below a predetermined reference value after the adsorption treatment, the adsorbent is collected and subjected to an existing decomposition treatment such as hydrothermal treatment, while the organochlorine compound concentration falls below the prescribed reference value. When it exceeds, it is good to exchange adsorption material and to perform adsorption processing again. There is no limit to the number of times the adsorbent can be replaced. Also in the case where the adsorption process is performed using the adsorption apparatus provided inside and outside the container, the adsorption process according to the above is performed.

  The contact time and contact temperature between the adsorbent and the organic chlorine compound-containing solution are not particularly limited. When the organochlorine compound-containing solution and the adsorbent are brought into contact, they may be brought into contact with stirring and / or heating, and the adsorption rate can be increased by bringing them into contact under such conditions. The contact time depends on the initial concentration of the organic chlorine compound, the type of solvent, the contact temperature, the type of adsorbent, etc., but usually under stirring for 1 hour or more (preferably 1 hour or more and 1 week or less), without stirring. It is appropriate to set it for 24 hours or more (preferably 24 hours or more and 6 months or less). If the contact time is too short, the adsorption is insufficient, and if it is too long, the saturated adsorption amount is reached, which is meaningless. Although the contact temperature is in the range of the outside air temperature from the winter to the midsummer in hot weather, it can be carried out indoors and can be heated as necessary to increase the adsorption efficiency. preferable. The heating means is not particularly limited, and examples include heating from the outside such as a ribbon heater, heating from the inside such as a throw-in heater, heating by microwaves and ultrasonic waves, and the like.

  Moreover, when making it contact under stirring, stirring conditions do not have limitation in particular, What is necessary is just the method which can give a convection to an organic chlorine compound containing solution directly or indirectly. For example, (1) a method of stirring an organic chlorine compound-containing solution using a stirring device such as a stirring blade, a magnetic stirrer, or a circulation pump, and (2) a container filled with the organic chlorine compound-containing solution with a vibrating stirrer, vibration A method of vibrating using a table, a shaker, etc. (for example, a method of vibrating in parallel in the vertical and / or horizontal direction, a method of rotating, etc.), (3) In the container using ultrasonic waves, magnets, etc. The method of giving a vibration to the solution filled in can be mentioned.

  As described above, stirring and / or heating and / or solvent dilution has the effect of making the reaction system easier to break, and destroying these clusters and exposing the organic chlorine compounds to facilitate the adsorption reaction. It is believed that there is. The solvent for the solvent dilution is not particularly limited as long as it can destroy the cluster of the organic chlorine compound and the insulating oil. In consideration of ease of compatibility with insulating oil, alkylbenzene, naphthenic mineral oil having 10 or less carbon atoms in the side chain, desirably 5 or less carbonic acid, or paraffinic mineral oil having 10 or less carbon atoms is preferable. These are more preferably short chains than long chains.

  Next, an example of an embodiment of the first invention and the second invention of the present invention will be described with reference to the drawings.

(Embodiment 1)
FIG. 1 is a diagram showing an example of an embodiment of the first invention. A state in which the adsorbent 20 is put into the organic chlorine-containing solution 10 filled in the container 1 and the organic chlorine compound is adsorbed on the adsorbent 20 by bringing the solution 10 and the adsorbent 20 into contact with each other for a long time. Show. 2 is a support rod with a scale for adjusting the position of the adsorbent 20 in accordance with the depth of the container 1, and 3 is a sealing material (for example, a rubber plug).

  The container 1 is provided with sampling ports 5 and 6 for measuring the concentration of the organic chlorine compound in the solution 10. The sampling port 5 is for measuring the organochlorine compound concentration contained in the solution at the bottom of the container 1, and a sampling tube (sample extraction syringe) 4 is connected to the sampling port 5. The sampling port 6 is for measuring the concentration of the organic chlorine compound contained in the solution in the middle part of the container 1. Note that the sampling port may be provided at a necessary position as necessary, and FIG. 1 is merely an example.

  The container 1 may further be provided with a thermometer, stirring means (stirring device, circulation pump, etc.) and heating means (ribbon heater, etc.) as necessary. In order to increase the adsorption efficiency by the adsorbent, it is desirable to provide a stirring means and a heating means.

  When a powder, pellet or bead-shaped adsorbent is used, the adsorbent can be put into the solution as it is, but this method complicates the recovery operation. From the viewpoint of facilitating the recovery operation, it is desirable to place the adsorbent in a container made of a porous material and put the entire container into the solution. The porous material may be any material as long as the adsorbent can come into contact with the solution via the porous material, and examples thereof include paper, woven fabric, knitted fabric, and resin film. A glass column or the like can also be used as the container.

  When using a molded adsorbent such as a honeycomb type, a lattice type, or a spiral type, the adsorbent 20 is fixed to the support rod 2 and is poured into the solution 10. What is necessary is just to use what was shape | molded according to the shape of the container, and the shape of a molded object may be appropriate shapes, such as plate shape, string shape, and sheet shape, for example.

  2 and 3 show an example of the adsorbent charging position and charging mode. FIG. 2A schematically shows a state in which the adsorbent 20 placed in a porous material container is introduced into an intermediate portion of the organochlorine compound-containing solution 10 filled in the container 1. Similarly, FIG. 2 (b) schematically shows a state where the container 1 is put into the bottom. 3 (a) shows the adsorbent 20 contained in a porous material container prepared according to the width of the container, and FIG. 3 (b) shows a porous material container prepared according to the height of the container. The adsorbent 20 put in the container is schematically shown in a state where the adsorbent 20 is put into the organochlorine compound-containing solution 10 filled in the container 1.

  2 and 3 show an example of the adsorbent charging method, and the adsorbent charging position and charging shape can be selected according to the shape of the container and the concentration of the organic chlorine compound. It can also change over time.

(Embodiment 2)
FIG. 4 is a diagram showing an example of an embodiment of the second invention. The organic chlorine-containing solution 10 filled in the container 1 is circulated by a pump, passed through the adsorption device 7 (filled with the adsorbent 20) installed outside the container 1, and the solution 10 and the adsorbent 20 are brought into contact with each other. It shows schematically how the organic chlorine compound is adsorbed to the adsorbent 20 by making it. Reference numeral 3 denotes a sealing material (for example, a rubber plug).

  The container 1 is provided with a sampling port 6 for measuring the organochlorine compound concentration in the solution 10. The sampling port 6 is for measuring the concentration of the organochlorine compound contained in the solution in the middle of the container 1, but the sampling port may be provided at a necessary position as required, and FIG. It is only an indication.

  The container 1 may further be provided with a thermometer, stirring means (stirring device, etc.) and heating means (ribbon heater, etc.) as necessary. In order to increase the adsorption efficiency by the adsorbent, it is desirable to provide a stirring means and a heating means.

  In this method, there is no particular limitation on the contact method between the solution 10 containing an organic chlorine compound and the adsorbent 20, and for example, a granular, bead-shaped, pellet-shaped, or honeycomb-shaped molded body can be used as a rotary adsorption tower or a fixed type. The circulating solution 10 can be brought into contact with the adsorbing device 7 that is filled in or attached to a conventionally known adsorbing device such as an adsorption tower.

(Embodiment 3)
FIG. 5 is a diagram showing another example of the embodiment of the second invention, and is a partially broken front view illustrating a method for removing a trace amount of PCB in the insulating oil filled in the cylindrical pole transformer 30. A pole transformer member composed of the outer box body 31 and the upper lid 32 is filled with an insulating oil 35 containing a small amount of PCB in a gap between the coils 33 and the like. Since there is a gap 34 above the liquid surface of the insulating oil, the adsorbing device 7 attached to the upper lid 32 (filled with the granular adsorbent 36) while circulating the insulating oil 35 by the circulation pump 8 attached to the upper lid 32. The PCB is adsorbed on the adsorbent 36 by bringing the insulating oil 35 and the adsorbent 36 into contact with each other. The arrows in the figure indicate the direction of circulation of the insulating oil. Although FIG. 5 shows an example in which the pump and the adsorption device are installed in the gap 34, the pump and the adsorption device may be installed in oil.

(Embodiment 4)
FIGS. 6 and 7 are views showing another example of the embodiment of the first invention, and are partially broken front views illustrating a method for removing a trace amount of PCB in the insulating oil filled in the cylindrical pole transformer 30. FIG. It is. A pole transformer member composed of the outer box body 31 and the upper lid 32 is filled with an insulating oil 35 containing a small amount of PCB in a gap between the coils 33 and the like. Although the circulation pump is not shown in FIGS. 6 and 7, it can be attached inside and outside the pole transformer such as the upper lid 32 as in FIG. 5.

  In the example of FIG. 6, in accordance with the shape (cylindrical) of the outer box body 31, a ribbon-like adsorbent sheet 37 is introduced in a cylindrical shape, and the insulating oil 35 and the adsorbent sheet 37 are brought into contact with each other, The PCB in the insulating oil is adsorbed on the adsorbent. According to this method, PCB can be efficiently adsorbed when a vertical flow is generated in the insulating oil.

  In the example of FIG. 7, in accordance with the shape (cylindrical shape) of the outer box body 31, a ribbon-like adsorbent sheet 37 is introduced in a vertical bar shape, and the insulating oil 35 and the adsorbent sheet 37 are brought into contact with each other, The PCB in the insulating oil is adsorbed on the adsorbent. According to this method, PCB can be efficiently adsorbed when a laminar flow (lateral flow) occurs in the insulating oil.

  6 and 7 show an example of the adsorbent charging method. The adsorbent sheet charging position, shape, size, number of charging, etc., should be selected according to the container shape and PCB concentration. Can be changed over time. Also, the sheets having the shapes shown in FIGS. 6 and 7 can be used in combination.

  As described above, the adsorbent adsorbed with the organic chlorine compound by the method of the present invention is recovered together with the organic chlorine compound and then transported to the PCB processing facility. Although the processing method of the adsorbent which adsorb | sucked the organic chlorine compound is not specifically limited, For example, it processes with eluents, such as alcohol. As a result, the adsorbed material is eluted and the adsorbent is regenerated. On the other hand, the organochlorine compound in the eluent is concentrated to a high concentration and recovered. Since the desorbed organochlorine compound can be recovered as a high-concentration solution, post-treatment is easy. The post-treatment method includes a chemical decomposition method and the like, and the method is not particularly limited. Examples thereof include hydrothermal treatment, oxidative decomposition, reductive decomposition, ultraviolet light irradiation and microwave photolysis. .

  Oil such as insulating oil from which organochlorine compounds have been removed will satisfy the treatment standard value (0.5 ppm or less) stipulated in the “Law on Waste Disposal and Cleaning” and insulation of transformers, capacitors, etc. Can be reused as oil.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only the following Examples.

(Example 1)
An adsorption test was performed using an Erlenmeyer flask as a model of the pole transformer member. A 2 ppm PCB-containing solution was prepared, and two kinds of solvents, insulating oil 7 type 4 (mineral oil, alkylbenzene) and insulating oil 2 type (1-4 mixed, alkylbenzene) were used. Put 100ml of each 2ppm PCB solution into a 200ml Erlenmeyer flask, add 5g of activated carbon (Mitsubishi Chemical "Dia Hope 008", raw material: coal, shape: crushed), warm at 40 ° C, ultrasonic (8 hours / day) ( Yamato BRANSON-8210, ultrasonic output 200W), shaken horizontally at 100 rpm with a shaker, analyzed the concentration of PCB in liquid every time of Table 1 below, and the degree of adsorption to activated carbon Was measured. The experiment was carried out at three points for both types of insulating oil. Table 1 shows the PCB concentration in the liquid over time, and FIG. 8 shows the relationship between the adsorption time and the PCB concentration (average of three times each).

  From the results in Table 1, it can be seen that the longer the adsorption time, the lower the PCB concentration in the solution. Moreover, it can be seen from the results of FIG. 8 that the PCB concentration becomes 0.5 ppm or less after the adsorption time of about 100 hours.

It is a front view which shows one Embodiment of the organochlorine compound removal method which concerns on this invention. It is a front view which shows one Embodiment of the organochlorine compound removal method which concerns on this invention. It is a front view which shows one Embodiment of the organochlorine compound removal method which concerns on this invention. It is a front view which shows one Embodiment of the organochlorine compound removal method which concerns on this invention. It is a partially broken front view explaining the removal method of trace PCB in the insulating oil with which the pole transformer was filled. It is a partially broken front view explaining the removal method of trace PCB in the insulating oil with which the pole transformer was filled. It is a partially broken front view explaining the removal method of trace PCB in the insulating oil with which the pole transformer was filled. It is a graph which shows the result of the adsorption test by activated carbon.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container 2 Support rod 3 Sealing material 4 Sampling pipes 5, 6 Sampling port 7 Adsorbing device 8 Pump 10 Solution 20 Adsorbing material
30 Pole transformer 31 Pole transformer outer box body 32 Pole transformer upper lid 33 Coil etc. 34 Upper gap 35 Insulating oil 36 Granular adsorbent 37 Sheet adsorbent

Claims (6)

A method of removing an organochlorine compound from a solution containing an organochlorine compound filled in a container, wherein an adsorbent is introduced into the solution, and the solution and adsorbent are brought into contact with each other to remove the organochlorine compound. A method comprising recovering the adsorbent together with an organic chlorine compound after adsorbing the adsorbent. A method for removing an organochlorine compound from a solution containing an organochlorine compound filled in a container, wherein the solution is circulated and passed through an adsorbing device including an adsorbent disposed outside or inside the container. A method of recovering the adsorbent together with the organic chlorine compound after adsorbing the organic chlorine compound to the adsorbent by bringing the solution into contact with the adsorbent. The method according to claim 1 or 2, wherein the solvent of the solution is water or oil. The method according to claim 1, wherein the container is a pole transformer member, and the solvent of the solution is an insulating oil for a pole transformer. The method according to any one of claims 1 to 4, wherein the solution and the adsorbent are brought into contact under stirring and / or heating and / or solvent dilution. The method according to any one of claims 1 to 5, wherein the adsorbent is at least one selected from zeolite, activated carbon, ion exchange resin, and alkali-modified activated carbon.

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