JP5744684B2 - Detoxification treatment method and detoxification treatment apparatus for halogen-containing oil - Google Patents

Description

  The present invention relates to a detoxification treatment method and a detoxification treatment apparatus for a halogen compound-containing oil that detoxifies a halogen compound in oil such as PCB mixed insulating oil with metallic sodium.

  PCB (polychlorinated biphenyl) is nonflammable and excellent in chemical stability and electrical insulation, so it was conventionally used as an insulating oil for electrical equipment, but its use is now prohibited and stored due to its harmfulness. PCBs and waste oils containing PCBs, etc., by July 2016, according to the “Special Measures Law for Promotion of Proper Treatment of Polychlorinated Biphenyl Waste (PCB Special Measures Law)” enacted in 2001 Completion of processing is required.

  Many methods have been proposed for PCB dechlorination techniques, and several methods have been put to practical use. The method of dechlorinating PCB by reacting sodium metal with PCB is used for detoxification treatment of PCB-containing insulating oil, and the treatment plant is also in operation. When metallic sodium and PCB-containing insulating oil are reacted, a treated oil in which PCB is dechlorinated is obtained.

  In the treated oil, unreacted metallic sodium remains in addition to reaction products such as sodium chloride, biphenyl, biphenyl polymer, sodium hydroxide and the like produced by the reaction between metallic sodium and PCB. Furthermore, when impurities to be treated include impurities other than PCB-containing insulating oil, for example, oxidized modified oil, reaction products generated by reacting these with metallic sodium are also included. For this reason, treated oils containing solid impurities such as reaction products are added with water or solvent, and solid impurities are extracted into water or solvent, and then separated by standing and further distilled. Water is removed and purified (for example, see Patent Document 1). Such a refined operation of the treated oil is similarly performed in a process of dechlorinating polychlorinated aromatic compounds in oil using an alkali metal other than sodium metal as a reactant (for example, patents). Reference 2).

JP 2006-193482 A JP-A-10-156174

  The conventional method for refining treated oil that removes solid impurities by adding water to the treated oil requires a distillation operation to remove the water contained in the treated oil after stationary separation, and consumes a large amount of energy. The equipment is also large. The same applies when a solvent is used instead of water. Further, usually, when water is added to refine the treated oil, a large amount of water is added. Therefore, if the water after oil-water separation is discarded as it is, the amount of waste increases. For this reason, water is added to the treated oil to extract solid impurities and then neutralized by adding a neutralizing agent, followed by oil-water separation. The water after oil-water separation is recovered by evaporation in a dryer. Solid impurities contained in the waste are solid waste. Such a method is a preferable method in that water can be reused. However, the energy consumption is large, and the amount of waste increases because the neutralizing agent becomes waste.

  An object of the present invention is to provide a detoxification treatment method and a detoxification treatment apparatus for a halogen compound-containing oil that can efficiently remove solid impurities in a dehalogenated oil with less energy and obtain a refined oil. is there.

The present invention includes a reaction step of dehalogenating a halogen compound in oil to be treated with metallic sodium in a reaction tank to obtain a dehalogenated oil, a coagulant adding step of adding seed crystals as a coagulant to the dehalogenated oil, the includes a coagulation step of the solid impurities contained in the dehalogenation oil to aggregate the seeds as nuclei, and separation step of separating the aggregated the solid impurities from the dehalogenation oil, wherein the halogen compound is poly biphenyl chloride, the seed crystal is the solid impurities aggregated are separated in the separation step, the halogen compound-containing oil in which the solid impurities, characterized in that it consists of metallic sodium in the reaction products and unreacted This is a detoxification method.

In the method for detoxifying a halogen compound-containing oil of the present invention, a seed crystal is added to the dehalogenated oil, and solid impurities such as reaction products are aggregated and separated to obtain a purified oil. Unlike the conventional method of refining dehalogenated oil using water, this method does not use water to separate solid impurities, so it does not require energy to separate water, consumes less energy, and has a neutralizing agent. The amount of waste is also small. Since seed solid crystals can use aggregated solid impurities separated in the separation step, it is preferable that the seed crystals need not be prepared separately.

  In the method for detoxifying a halogen compound-containing oil of the present invention, even if unreacted metallic sodium remains in the dehalogenated oil, the unreacted metallic sodium also aggregates with the reaction product as a seed crystal. Thus, unreacted metallic sodium can be separated from the dehalogenated oil. For this reason, the operation which quenches unreacted metallic sodium separately is unnecessary. Even if a quenching operation is performed, most of the unreacted metallic sodium is separated and can be easily performed.

  The halogen compound-containing oil detoxifying method of the present invention is the halogen compound-containing oil detoxifying method, wherein the oil to be treated contains an oxidized denatured oil, and the solid impurities include the oxidized denatured oil. A reaction product produced by a reaction between oil and metallic sodium is also included.

  The method for detoxifying a halogen compound-containing oil of the present invention can be applied even when an oxidized and denatured oil is mixed in, for example, a PCB-containing insulating oil. The reaction product produced by the reaction of the oil-oxidized denatured product with metallic sodium or further a reaction accelerator is highly polar and easily adheres to the metal surface, etc., so if a seed crystal is added, it easily aggregates with the seed crystal as a nucleus. .

The detoxification method of the halogen compound-containing oil of the invention, the detoxification method of the halogen compound-containing oil, wherein the seed crystals is, instead of the solid impurities aggregated are separated in the separation step, cellulose It consists of the granular material which has as a main component.

  In the method for detoxifying a halogen compound-containing oil of the present invention, a granule containing cellulose as a main component can be used as a seed crystal. Granules mainly composed of cellulose have a large specific surface area and have many hydroxyl groups on the surface, so that they easily adsorb reaction products and unreacted metallic sodium, and are easily available and inexpensive. Therefore, it is preferable as a seed crystal.

The detoxification method of the halogen compound-containing oil of the present invention, in the flocculant addition step, the pre-Symbol seed crystals was added a small amount of water as flocculants, in the aggregation step, included in the dehalogenation oil the solid impurities are aggregated in the previous SL seeds and water, the amount of water added is in an amount of not the solid impurities and the solution, and added water does not remain in the dehalogenation oil It is characterized by that.

When the reaction product, unreacted metallic sodium comes into contact with water, water adsorbs to the reaction product and reacts with unreacted metallic sodium. The reaction product immediately after water is adsorbed, sodium metal after reaction, rather easily aggregated because of the unstable, easily agglomerated seed crystals as nuclei and grow. Here, a small amount of water functions as a flocculant. If a large amount of water is added and the reaction product adsorbed with water dissolves to form a solution, or if excess water remains in the dehalogenated oil, these separate operations are required. The amount of is such that the reaction product does not become a solution and the added water does not remain in the dehalogenated oil.

  Moreover, the method for detoxifying a halogen compound-containing oil according to the present invention is characterized in that, in the method for detoxifying a halogen compound-containing oil, the seed crystal is added to a reaction vessel immediately after the completion of the reaction step.

The reaction product immediately after the dehalogenation is in a state of being easily aggregated. For this reason seed, reaction step Ru can be more effectively flocculate the solid impurities such as the reaction product be added to a reaction vessel immediately after.

The present invention also provides a reaction vessel for dehalogenating a halogen compound in oil to be treated with metallic sodium to obtain a dehalogenated oil, and adding a seed crystal or a seed crystal and water as a flocculant to the dehalogenated oil to remove it. the seed crystals of the solid impurities halogen oil, or a cohesive product tank to aggregate in seed and water, the dehalogenation oil free of agglomerated said solid impurities solid impurities precipitated separated and recovered a settling tank to a concentration tank for further concentrating the solid impurities aggregated discharged from the precipitation tank, the part of the solid impurities concentrated is discharged from the thickening tank as the seed crystals includes a seed return line for returning the aggregate production tank, and the halogen compound, polychlorinated biphenyls der is, the solid impurities, characterized in that it consists of metallic sodium in the reaction products and unreacted c A detoxification unit Gen compound-containing oils.

  The detoxification treatment apparatus for halogen compound-containing oil according to the present invention includes a seed crystal return line for returning a part of the concentrated solid impurities (sludge) to the agglomeration tank, so that a purified dehalogenated oil can be easily obtained. be able to.

  The detoxification treatment method and the detoxification treatment apparatus of the halogen compound-containing oil of the present invention add seed crystals as a flocculant to dehalogenated oil and agglomerate solid impurities such as reaction products using the seed crystals as nuclei. The refined oil can be obtained by easily separating solid impurities by a precipitation operation or the like. Moreover, the detoxification treatment method and the detoxification treatment apparatus of the halogen compound-containing oil of the present invention do not require the energy for separating water since water is not used for separation of solid impurities from dehalogenated oil as in the prior art. There is little energy consumption.

It is a figure which shows schematic structure of the PCB mixing insulation oil detoxification processing apparatus 1 which is 1st Embodiment of this invention. It is a flowchart which shows the process sequence of the PCB mixing insulation oil detoxification processing apparatus 1 of FIG. It is a figure which shows the result of having analyzed the insulating oil containing paper wood dry matter and the insulating oil which does not contain paper wood dry matter by Fourier-transform infrared spectroscopy FTIR. It is a figure which shows schematic structure of the PCB mixing insulation oil detoxification processing apparatus 2 which is 2nd Embodiment of this invention. It is a flowchart which shows the process sequence of the PCB mixing insulation oil detoxification processing apparatus 2 of FIG.

  FIG. 1 is a diagram showing a schematic configuration of a PCB-mixed insulating oil detoxification processing apparatus 1 according to a first embodiment of the present invention. FIG. 2 is a flowchart showing a processing procedure of the PCB-mixed insulating oil detoxification processing apparatus 1. Hereinafter, a mixture of the PCB trace mixed insulating oil extracted from the pole transformer and the distillate collected by crushing the column transformer after extracting the PCB trace insulating oil and vacuum heating it. Taking the case of using the oil to be treated as an example, the configuration and processing procedure of the PCB-mixed insulating oil detoxification processing apparatus 1 will be described. In the first and second embodiments, the solid impurity includes a reaction product and unreacted sodium metal.

  The PCB-mixed insulating oil detoxification treatment device 1 is a device that detoxifies PCB-mixed insulating oil by using an SP process (soduim pulverulent dispersion) method. The PCB is removed by reacting metallic sodium and PCB mixed in the insulating oil. Chlorine. Further, purified impurities are produced by separating solid impurities contained in the dechlorinated insulating oil.

  The PCB-mixed insulating oil detoxification treatment apparatus 1 includes a storage tank 11 for storing the oil to be treated, a vacuum distillation tank 13 for removing water contained in the oil to be treated, and a reaction tank 15 for reacting the PCB with metal sodium to dechlorinate. A decomposition confirmation tank 17 for confirming dechlorination of PCB, an agglomeration production tank 19 for aggregating solid impurities contained in the treated oil, a precipitation tank 21 for precipitating and separating the agglomerated solid impurities, and a precipitation A concentration tank 23 is provided to concentrate the aggregated solid impurities separated in the tank 21.

  The oil to be treated consists of the PCB trace mixed insulating oil extracted from the pole transformer, and the distillate recovered by crushing the column transformer after extracting the PCB trace mixed insulating oil and heating it in vacuum. These are stored in the storage tank 11 (accepting step: step S1) and then sent to the vacuum distillation tank 13. Note that the oil to be treated is not limited to this, and only the PCB trace-mixed insulating oil extracted from the pole transformer may be used as the oil to be treated, and the insulating oil containing a large amount of PCB may be referred to as the oil to be treated. can do.

  The vacuum distillation tank 13 is a jacketed stirring tank, and heats the oil to be treated by supplying a heated heat medium to the jacket. The vacuum distillation tank 13 includes a pressure reducing device (not shown) that depressurizes the inside of the tank and evaporates, condenses, and recovers water contained in the oil to be processed. The oil to be processed sent from the storage tank 11 is here. It is heated to about 90 ° C. and depressurized to about 0.0142 Mpa to remove water contained in the oil to be treated (dehydration step: step S2). The treated oil from which moisture has been removed in the vacuum distillation tank 13 is sent to the reaction tank 15.

  The reaction tank 15 is a jacketed stirring tank in which metal sodium is added to the oil to be treated from which water has been removed in the vacuum distillation tank 13. The metallic sodium is added to the reaction vessel 15 as a metallic sodium dispersion (SD: soduim dispersion) in which fine particles of metallic sodium are dispersed in insulating oil. As for the size of metallic sodium in SD, the average particle size is about 6 μm. Here, in order to sufficiently dechlorinate PCB and increase the decomposition rate (dechlorination rate), an amount of metal sodium exceeding the amount of metal sodium necessary for dechlorination of PCB is added. The oil to be treated and sodium metal are heated to about 90 ° C. by a heated heating medium supplied to the jacket while being stirred, and the PCB reacts with metal sodium to dechlorinate and the oil to be treated is rendered harmless (reaction Process: Step S3). A predetermined amount of water is added as a reaction accelerator after the metal sodium dispersion is added and a predetermined time elapses.

In the present embodiment, since the column transformer after the PCB trace mixed insulating oil is extracted from the oil to be treated is contained and the distillate collected by vacuum heating is collected, the C = O bond is contained in the oil to be treated. And oxidized modified oils containing C—O bonds. The reason why the oxidized modified oil containing C═O bond and C—O bond is included is that the pole transformer includes paper and wood, and these dry-distilled products are included in the recovered insulating oil. FIG. 3 is a diagram showing the results of analysis by Fourier transform infrared spectroscopy FTIR of insulating oil containing paper-wood dry matter and insulating oil not containing paper-wood dry matter. A peak of 1750 cm ^{−1 of} C═O appears strongly in the insulating oil containing the paper tree dry matter. Examples of the oxidized modified oil containing a C═O bond include carboxylic acid, ester, aldehyde, and ketone. Therefore, in this embodiment, in addition to the reaction between PCB and metallic sodium, oxidized and altered oil reacts with metallic sodium and further the reaction accelerator. Hereinafter, typical reactions in the reaction tank 15 will be shown.

  As can be seen from the above reaction formula, to-be-treated oil from which PCB has been dechlorinated (treated oil) includes reaction products such as sodium chloride, sodium hydroxide, biphenyl, polybiphenyl, and oxidized modified oil. The reaction product produced by the reaction of metallic sodium and further with the reaction accelerator is included. Furthermore, since sodium metal is excessively added to the reaction tank 15, unreacted metal sodium remains in the treated oil. The reaction product and unreacted sodium metal are solid and dispersed in the treated oil.

  Oil to be treated is a mixture of the PCB trace insulating oil extracted from the pole transformer and the pillar transformer after the PCB trace insulating oil is extracted and vacuum heated to recover the distillate recovered. An example of the size of solid impurities contained in the treated oil sampled at the outlet of the decomposition confirmation tank 17 in the case of the filter medium having a particle diameter of 2 to 11 μm, an average particle diameter of 9 μm, and an opening of 1 μm And 95% or more can be separated by filtration with a 0.1 μm filter medium. The concentration of solid impurities in the treated oil is about 0.2% by weight, and unreacted metallic sodium is about 10% of the solid impurities.

  The treated oil from which PCB has been dechlorinated in the reaction tank 15 is sent to the decomposition confirmation tank 17 and sampled through the sampling line 18 to confirm whether the PCB concentration in the treated oil is equal to or lower than a predetermined concentration. (Confirmation step: Step S4). Here, when it is confirmed that the PCB does not reach the predetermined concentration or less, the treated liquid is returned to the reaction tank 15 and the PCB is dechlorinated again. The treated oil is sent to the agglomeration tank 19 when it is confirmed that the PCB concentration is equal to or lower than a predetermined concentration (confirmation step: step S5). When oil is sent from the decomposition confirmation tank 17 to the agglomeration tank 19, a temperature adjustment operation such as cooling the treated oil is unnecessary.

  The agglomeration tank 19 is a stirring tank, where a flocculant is added to the treated oil to agglomerate solid impurities in the treated oil (aggregation step: step S6). Water and sludge returned from the concentration tank 23 are used as the flocculant. The sludge returned from the concentration tank 23 is obtained by agglomerating and concentrating solid impurities in the treated oil. When sludge is added to the treated oil, the sludge becomes seed crystals, and solid impurities contained in the treated oil aggregate and grow using the seed crystals as nuclei. On the other hand, when a small amount of water is added to the treated oil, the water is adsorbed on the reaction product and reacts with unreacted sodium metal. As described above, the reaction product immediately after the water adsorption and the metallic sodium immediately after the reaction are in an unstable state, and thus easily aggregate, and easily aggregate and grow with sludge as a nucleus. Here, a small amount of water functions as a flocculant. The size of the sludge is preferably about several hundred μm to several millimeters in consideration of the precipitation separation operation in the subsequent process.

  Even if water is not added, the reaction product contained in the treated oil, unreacted metallic sodium, aggregates and grows with sludge as a core, but it becomes easier to aggregate and grow by adding water. The amount of water added here is such that all of the added water is adsorbed on the reaction product and is consumed by reacting with unreacted metallic sodium, so that no excess water remains. If water is added excessively, the reaction product completely dissolves in water and does not become solid, making separation difficult. Further, when water is mixed into the treated oil, it is not preferable because an operation for separating water from the treated oil is required separately.

  The flocculant is not limited to the sludge as long as it has a function of aggregating and growing the reaction product and unreacted metallic sodium contained in the treated oil. For example, a granular material mainly composed of cellulose can be used as the flocculant. Since cellulose has many hydroxyl groups on its surface, it is preferable as a seed crystal because it easily adsorbs reaction products and unreacted metallic sodium, and is easily available and inexpensive. In particular, a granule mainly composed of cellulose having a large specific surface is preferable. Considering the precipitation separation operation in the subsequent step, the size of the granule mainly composed of cellulose is preferably about several millimeters. Moreover, it is good also considering the granule which has a cellulose as a main component, and a small amount of water as a flocculant.

  The sedimentation tank 21 is a so-called thickener, and separates agglomerated solid impurities in the treated oil sent from the agglomeration production tank 19 (separation step: step S7). Since the solid impurities in the treated oil sent from the agglomeration production tank 19 are agglomerated and grown and become large, they can be easily separated by mechanical separation utilizing the specific gravity difference. Naturally, it is possible to separate solid impurities by using a filter, centrifuge, etc. instead of thickener, but solid impurities are aggregated and grown, so they can be easily separated by sedimentation. Can be separated. The size of the sedimentation tank 21 can be appropriately determined based on the sedimentation rate of solid impurities.

  The treated oil from which solid impurities have been separated in the precipitation tank 21 is recovered as a refined oil. On the other hand, the solid impurities settled and separated are extracted through a sludge extraction pump 22 and sent to the concentration tank 23 for further concentration of the solid impurities. The sludge extraction pump 22 is preferably a screw pump capable of pumping solid impurities without crushing.

  The concentration tank 23 is a so-called thickener, and concentrates the solid impurities sent from the precipitation tank 21 by sedimentation and separation (sludge concentration step: step S8). The magnitude | size of the concentration tank 23 can be suitably determined according to the density | concentration, magnitude | size, and concentration degree of a solid-state impurity. The concentrated solid impurities are extracted from the bottom as sludge, and a part of the sludge is sent to the agglomeration tank 19 through the sludge extraction pump 24 and the seed crystal return line 26. The sludge extraction pump 24 is preferably a screw pump that can pump the sludge without crushing it. When only a specific size of sludge is used as a seed crystal, a classification device is provided at the outlet of the sludge extraction pump 24 and the classified sludge may be sent to the agglomeration tank 19. On the other hand, the processed oil from which solid impurities have been separated is sent to the agglomeration tank 19 through the processed oil return line 28. As a result, the small solid impurities contained in the treated oil can be aggregated, grown and separated again. The treated oil return line 28 is connected to the sedimentation tank 21 like the PCB mixed insulating oil detoxification treatment device 2 described later, and here, small solid impurities contained in the treated oil are aggregated and grown again, It may be separated.

  As described above, the PCB-mixed insulating oil detoxification treatment apparatus 1 uses sludge condensed and concentrated with solid impurities and a small amount of water as a flocculant, and reacts reaction products in the treated oil, unreacted metallic sodium. After agglomeration and growth, this is precipitated and separated to obtain a refined oil. Therefore, unlike conventional methods for refining dehalogenated oil using water, energy for separating water is unnecessary and energy consumption is low. Furthermore, since no neutralizer is used, the amount of waste is small. In the case of the conventional method for purifying dehalogenated oil using water, since a large amount of water is used, a vacuum dryer is used to circulate the water, but problems are likely to occur. In contrast, the agglomeration tank 19, the precipitation tank 21, and the concentration tank 23 have a simple structure and are less likely to cause trouble and are inexpensive.

  FIG. 4 is a diagram showing a schematic configuration of the PCB-mixed insulating oil detoxification processing apparatus 2 according to the second embodiment of the present invention. FIG. 5 is a flowchart showing a processing procedure of the PCB-mixed insulating oil detoxification processing device 2. The same components as those in the PCB-mixed insulating oil detoxification processing apparatus 1 of the first embodiment shown in FIG.

  Similarly to the PCB-containing insulating oil detoxification treatment device 1 of the first embodiment, the PCB-containing insulating oil detoxification treatment device 2 adds sludge as a seed crystal to the treated oil, and the solid impurities contained in the treated oil Coagulates and grows with sludge as the core. The sludge to be used is the same as the PCB-mixed insulating oil detoxification treatment apparatus 1 of the first embodiment except that solid impurities in the treated oil separated in the concentration tank 23 are aggregated and concentrated. Place and timing of addition are different. Moreover, the point which does not use water for a flocculant also differs from the PCB mixing insulation oil detoxification processing apparatus 1. FIG.

  In the PCB-containing insulating oil detoxification treatment apparatus 2, the seed crystal return line 26 is connected to the reaction tank 15, and sludge is returned to the reaction tank 15. The reaction product produced by the reaction of PCB with metallic sodium and further water as a reaction accelerator, the reaction product produced by the reaction of oxidized modified oil with metallic sodium and further the water as a reaction accelerator Immediately after generation, the state is unstable and is easily attached to the seed crystal. For this reason, in the PCB-mixed insulating oil detoxification treatment apparatus 2, after adding PCB and metallic sodium, and further water as a reaction accelerator (reaction step: step S13), the sludge is immediately introduced and the sludge is reacted as a seed crystal. Immediately after, solid impurities are aggregated using sludge as seed crystals (aggregation step: step S14).

  The reason why water is not added as a flocculant to the reaction tank 15 is that if water adheres to the reaction tank 15 or if water remains in the reaction tank 15, the metal sodium reacts with water in the next reaction step, and is wasted. It is because it is consumed. Moreover, in the PCB-mixed insulating oil detoxification treatment device 2, the treated oil after completion of the reaction is sent to the decomposition confirmation tank 17, and when it is confirmed that the PCB concentration does not reach a predetermined concentration or less (confirmation step: Steps S15 and S16), the treated oil is returned to the reaction tank 15, so that if there is water in the reaction tank 15 at this time, a problem occurs. Furthermore, since the reaction product immediately after the reaction is rich in cohesiveness, it is sufficiently agglomerated without adding water.

  The treated oil to which the sludge has been added is sent to the decomposition confirmation tank 17 as in the case of the PCB-mixed insulating oil detoxification treatment apparatus 1, where the PCB concentration is confirmed (confirmation process: steps S15 and S16). Since the processed oil stops in the decomposition confirmation tank 17 until the confirmation of the PCB concentration is completed, the decomposition confirmation tank 17 also functions as an agglomeration production tank for aggregating solid impurities. . Therefore, unlike the PCB-mixed insulating oil detoxification processing apparatus 1, the PCB-mixed insulating oil detoxification processing apparatus 2 is not provided with the agglomeration tank 19. When the time necessary for aggregating solid impurities exceeds the time required for confirming the PCB concentration, the size of the decomposition confirmation tank 17 is set so that the time necessary for aggregating solid impurities can be obtained. May be determined. However, since solid impurities aggregate even after being sent to the precipitation tank 21, it is not necessary to make the decomposition confirmation tank 17 larger than necessary.

  The treated oil is sent from the decomposition confirmation tank 17 to the precipitation tank 21 where the refined oil is recovered (separation process: step S17) and the sludge is recovered from the concentration tank 23 (concentration process: step S18). This is the same as the PCB mixed insulating oil detoxification treatment apparatus 1. In addition, it is possible to use classified sludge, and further to use sludge as a flocculant, granule mainly composed of cellulose, granule mainly composed of cellulose and a small amount of water. It is the same as the processing apparatus 1.

  In the PCB-mixed insulating oil detoxification treatment apparatus 2, the flocculant is charged into the reaction tank 15, but it may be charged into the decomposition confirmation tank 17. However, considering that the cohesiveness of the reaction product is high immediately after generation, the reaction tank 15 is preferable to the decomposition confirmation tank 17.

  As mentioned above, although the PCB mixing insulation oil detoxification processing apparatus 1 and 2 was shown as an embodiment of the present invention, the present invention is a treated oil using a solid seed crystal or a solid seed crystal and a small amount of water as a flocculant. Is characterized in that the treated oil is refined by agglomerating and separating the reaction product and unreacted metallic sodium contained in the product. In addition to the insulating oil mixed with PCB, the oil containing a halogen compound is made of metallic sodium. The present invention can be preferably used in a process for dehalogenation. In the above embodiment, the size of metallic sodium in SD and the size and amount of solid impurities in the treated oil are shown as numerical values, but this is an example, and the present invention is limited to these numerical values. It is not something.

DESCRIPTION OF SYMBOLS 1 PCB mixing insulation oil detoxification processing apparatus 2 PCB mixing insulation oil detoxification processing apparatus 11 Storage tank 13 Vacuum distillation tank 15 Reaction tank 17 Decomposition | disassembly confirmation tank 18 Sampling line 19 Aggregation generation tank 21 Precipitation tank 22 Sludge extraction pump 23 Concentration tank 24 Sludge extraction pump 26 Seed crystal return line 28 Treated oil return line

Claims (6)

A reaction step of dehalogenating a halogen compound in the oil to be treated with sodium metal in a reaction tank to obtain a dehalogenated oil;
A flocculant addition step of adding seed crystals as a flocculant to the dehalogenated oil;
An agglomeration step of aggregating solid impurities contained in the dehalogenated oil with the seed crystals as nuclei;
The aggregated the solid impurities comprises a separation step of separating from the dehalogenation oil,
Wherein said halogen compound is polychlorinated biphenyls, the seed crystal is the solid impurities aggregated are separated in the separation step, and wherein the solid impurities comprises a metal sodium in the reaction products and unreacted Detoxifying treatment method for halogen-containing oil. The treated oil comprises an oxidation deterioration oil, wherein the solid impurities to claim 1, characterized in that said oxide alteration oil and the metallic sodium also include the reaction product produced by the reaction The method for detoxifying a halogen-containing oil as described. The seed crystals are said separated in the separation step instead of aggregated the solid impurities, the halogen compound-containing oil according to claim 1 or 2, characterized in that it consists of granules consisting mainly of cellulose Detoxification treatment method. In the flocculant addition step, the addition of a small amount of water as a coagulant in conjunction with prior Symbol seeds, in the aggregation step to coagulate the solid impurities contained in the dehalogenation oil in the previous SL seeds and water ,
The amount of water added, the solid impurities not a solution, and claims 1, the added water is characterized in that the amount does not remain in the dehalogenation oil to any one of the 3 The method for detoxifying a halogen-containing oil as described. The method for detoxifying a halogen-containing oil according to any one of claims 1 to 3 , wherein the seed crystal is added to a reaction tank immediately after the reaction step. A reaction tank for dehalogenating a halogen compound in oil to be treated with metallic sodium to obtain a dehalogenated oil;
An agglomeration tank for adding seed crystals or seed crystals and water as a flocculant to the dehalogenated oil, and aggregating solid impurities in the dehalogenated oil with the seed crystals or seed crystals and water;
A settling tank for collecting the dehalogenation oil free of agglomerated the solid impurities were settling solid impurities,
A concentration tank for further concentrating the solid impurities aggregated discharged from the sedimentation tank,
Anda seed return line for returning to the aggregated product tank as the seed crystal a part of the solid impurities concentrated is discharged from the concentrate tank,
Wherein said halogen compound is polychlorinated biphenyl der is, the solid impurities reaction products and detoxification apparatus halogen compound-containing oil characterized by comprising a metal unreacted sodium.

Images