JP5717294B2 - Detoxification equipment for halogenated oil - Google Patents

Description

The present invention relates to non Gaika processor halogen compound-containing oil of the halogen compound in the oil such as PCB contaminated insulating oil harmless 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. Usually, when metal sodium and PCB-containing insulating oil are reacted, metal sodium is added excessively in order to sufficiently reduce the PCB concentration or shorten the reaction time. For this reason, 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.

  Since unreacted metallic sodium is highly active, treated oils containing it are subject to various difficulties in storage, storage, and reuse. For this reason, normally, operation which adds water to processed oil and quenches metallic sodium with water is performed (for example, refer to patent documents 1 and 2). Such a quenching operation is also performed in a process of dechlorinating a polychlorinated aromatic compound in oil using an alkali metal other than sodium metal as a reactant (see, for example, Patent Document 3).

JP 2002-212109 A JP 2005-254147 A JP 2001-206857 A

  Although the method of quenching the remaining unreacted alkali metal by adding water to the treated oil is a simple method, to reuse the treated oil, the added water and the treated oil are separated. There is a need. Separation of water and treated oil can be roughly done by static separation, but distillation operation is required to sufficiently separate the water contained in the treated oil, which requires a lot of energy. . In addition, the apparatus becomes large. There is also a method of quenching alkali metal using alcohol or the like instead of water, but separation of alcohol and treated oil still requires a distillation operation and has the same problems as when water is used. . Further, usually, when quenching with water, the water after quenching needs to be neutralized, and a large amount of waste is generated by performing the neutralization.

  When the treated oil is reused, it is not always necessary to quench the alkali metal as long as the unreacted alkali metal contained in the treated oil can be removed. Since the alkali metal remaining in the treated oil is in a solid state, it can be considered to be mechanically separated. In Patent Document 1 and Patent Document 3, although not intended to remove only unreacted alkali metal, a method for separating unreacted alkali metal and reaction products contained in the treated oil by centrifugal filtration is proposed. Has been. The method of mechanically separating the unreacted alkali metal contained in the treated oil is considered to be one of the effective methods for reusing the treated oil, but the average of the alkali metals used for the decomposition of the PCB Considering that the particle size is usually about 5 to 6 μm, there is a limit to mechanical separation.

An object of the present invention is to make halogen compounds in oils such as PCB-mixed insulating oil harmless with metal sodium and to efficiently remove unreacted metal sodium contained in the resulting dehalogenated oil with less energy to provide a non Gaika processing apparatus containing oil.

The present invention includes a reaction tank for dehalogenating a halogen compound in oil to be treated with metallic sodium to obtain a dehalogenated oil, and an electrostatic adsorption machine for electrostatically adsorbing and separating solid impurities contained in the dehalogenated oil. Incorporating a solid quenching agent consisting of a solid having a hydroxyl group on the surface and insoluble in oil, the solid quenching agent is brought into contact with the dehalogenated oil from which solid impurities have been separated by the electrostatic adsorption machine. , it is reacted with hydroxyl groups of the solid quenching agent and metallic sodium remaining unreacted to dehydration halogen oil, and quenching device for quenching the metallic sodium, only contains the solid quenching agent, granular In the form of pellets or balls, the quenching device is a fluidized bed, and supplies the dehalogenated oil in which unreacted sodium metal remains in the fluidized bed, The body quenching agent was quenched said metallic sodium while fluidized, breakthrough was the solid quenching agent detoxification features and to Ruha androgenic compound-containing oil be withdrawn from the separated fluidized layer by the difference in specific gravity Device.

The halogen compound-containing detoxification treatment apparatus of the present invention comprises an electrostatic adsorption machine that electrostatically adsorbs and separates solid impurities in the dehalogenated oil, and further remains in the dehalogenated oil without being completely removed by electrostatic adsorption. Since it is equipped with a quencher that quenches unreacted metallic sodium with a solid quenching agent, unreacted metallic sodium contained in the dehalogenated oil can be efficiently removed with less energy . In addition , unlike the quenching method using water or alcohol, this method does not require post treatment after quenching. Moreover, since the quenching apparatus used by this invention is accompanied by a chemical reaction, it can quench unreacted metallic sodium reliably.
The quenching apparatus is preferably an apparatus that can efficiently contact the unreacted metallic sodium remaining in the dehalogenated oil and the solid quenching agent from the viewpoint of shortening the quenching time. In this invention, since the quenching apparatus of a fluidized bed form is used for a quenching apparatus, the contact efficiency of an unreacted sodium metal and a solid quenching agent can be made high. Since the sodium hydroxide produced by the reaction between the solid quenching agent and metal sodium is adsorbed on the surface of the solid quenching agent, such a solid quenching agent is an unreacted solid quenching agent. It becomes heavier than As a result, the reacted solid quenching agent utilizing the difference in specific gravity can be extracted, and continuous operation can be performed while supplying a new solid quenching agent.

In addition, the halogen compound-containing oil detoxifying apparatus of the present invention is characterized in that in the halogen compound-containing oil detoxifying apparatus , the solid quenching agent comprises a plant and / or animal-derived solid or synthetic resin. And

  The solid quenching agent used in the present invention is a solid having a hydroxyl group on the surface and insoluble in oil, and it is sufficient that metal sodium and hydroxyl group can be reacted to quench metal sodium. As such a solid quenching agent, Solid quenching agents derived from plants and / or animals, and solid quenching agents composed of synthetic resins can be used.

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

  According to the present invention, since the oil to be treated may contain oxidized and denatured oil, for example, the pole transformer after extracting the PCB trace amount insulating oil is crushed and heated by vacuum to be recovered. A PCB-mixed insulating oil that contains a distillate can also be used as the oil to be treated.

By using the non Gaika processor halogen compound-containing oil of the present invention, a halogen compound in the oil such as PCB contaminated insulating oil detoxified with metallic sodium, less metallic sodium remaining unreacted to dehalogenation oil obtained It can be removed efficiently with energy.

It is a figure which shows schematic structure of the PCB mixing insulation oil detoxification processing apparatus 1 which is one 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 other quenching apparatus 32 used with the PCB mixing insulation oil detoxification processing apparatus 1 of FIG.

  FIG. 1 is a diagram showing a schematic configuration of a PCB-mixed insulating oil detoxification processing apparatus 1 according to an 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.

  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. After solid impurities contained in the chlorinated and dechlorinated insulating oil (treated oil) are separated by electrostatic adsorption, the remaining unreacted metallic sodium is quenched using a solid quenching agent. .

  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. Decomposition confirmation tank 17 for confirming dechlorination of PCB, electrostatic adsorber 21 for separating solid impurities contained in the treated oil, treatment in which solid impurities are separated by electrostatic adsorber 21 A quenching device 31 for quenching unreacted metallic sodium remaining in the finished oil and a treated oil tank 45 for storing treated oil in which the remaining unreacted metallic sodium is quenched are provided.

  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 metallic sodium are solid and dispersed in the treated oil, and these are 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, if it is confirmed that the PCB does not reach the predetermined concentration or less, the treated oil is returned to the reaction tank 15 and the PCB is dechlorinated again. When it is confirmed that the PCB concentration is equal to or lower than a predetermined concentration (confirmation step: step S5), the processed oil is sent to the electrostatic adsorber 21 via the oil feed pump 19. When oil is sent from the decomposition confirmation tank 17 to the electrostatic adsorption machine 21, a temperature adjustment operation such as cooling the treated oil is unnecessary.

  The electrostatic chuck 21 is provided with a pair of electrodes each including a positive electrode 25 and a negative electrode 27 in a casing 23, and a porous collector 29 is provided between the electrodes. A DC high voltage is applied to the electrode from a power supply device (not shown). The solid impurities contained in the treated oil are adsorbed by the positive electrode 25, the negative electrode 27, or the collector 29 in the process of rising in the casing 23 (step S6). Such an electrostatic chuck 21 can use a publicly known electrostatic chuck 21 and, for example, an electrostatic oil purifier manufactured by Cleantech Co., Ltd. is exemplified. Two electrostatic chucks 21 may be installed as necessary, and can be switched alternately. Furthermore, a regeneration device that cleans and regenerates the electrostatic chuck 21 may be provided.

  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. It is preferable if solid impurities contained in such treated oil can be quickly and completely separated by the electrostatic adsorber 21, but there is a limit to the particle size that can be separated by the electrostatic adsorber 21. Considering the processing speed and the like, it is not realistic to completely separate the solid impurities contained in the processed oil by the electrostatic adsorption machine 21 alone.

  This PCB-mixed insulating oil detoxification treatment apparatus 1 removes unreacted metallic sodium contained in the treated oil by the electrostatic adsorber 21 and the quenching device 33 disposed at the subsequent stage of the electrostatic adsorber 21. The unreacted metallic sodium having a large particle size can be quickly removed and more efficiently separated by the electrostatic adsorber 21 than by quenching by the quencher 33. On the other hand, considering the particle size and adsorption rate that can be adsorbed by the electrostatic adsorber 21, unreacted metallic sodium having a small particle size is quenched by the quencher 33 rather than separated by the electrostatic adsorber 21. Is efficient. As described above, since the electrostatic adsorption machine 21 and the quenching machine 33 have different characteristics, the particle size and concentration of unreacted metallic sodium contained in the treated oil, and the particle size of the reaction product as necessary. In consideration of the concentration, the specifications of the two apparatuses should be determined, and the characteristics of these apparatuses should be utilized so that the unreacted sodium metal can be completely removed within a short time as a whole.

  When the treated oil containing solid impurities is passed through the electrostatic adsorber 21, the solid impurities can be almost separated. However, if the treated oil is reused, unreacted metallic sodium is completely removed. It is desirable to do. Therefore, in the PCB-mixed insulating oil detoxification processing apparatus 1 of the present embodiment, the electrostatic adsorption machine 21 passes through the electrostatic adsorption machine 21 to remove unreacted metallic sodium remaining in the treated oil without being separated by the electrostatic adsorption machine 21. The treated oil is sent to the quenching device 31. When oil is supplied from the electrostatic adsorption machine 21 to the quenching device 31, a temperature adjustment operation such as cooling the treated oil is unnecessary. In the treated oil sent to the quenching device 31, unreacted metallic sodium remaining in the treated oil is quenched here (quenching step: step S7), and then sent to the treated oil tank 45 ( Storage step: Step S8).

  The quenching device 31 quenches unreacted metallic sodium remaining in the treated oil using a solid quenching agent. The quenching device 31 includes a quenching device 33 and an oil feed pump 35 that pumps the treated oil to the quenching device 33. The quenching device 33 includes a circulation line 39 that connects the outlet portion and the suction portion of the liquid feeding pump 35 in addition to the outlet line 37 that connects to the treated oil tank 45, and a pressure detection is provided at the inlet portion of the quenching device 33. A container 41 is attached.

  The quencher 33 is a filter-type device, and contains a filter-shaped solid quenching agent 43 therein. The solid quenching agent 43 is formed of a cotton nonwoven fabric in a cylindrical shape with a bottom, allows the treated oil to pass through, and allows the unreacted metallic sodium remaining in the treated oil to contact the solid quenching agent 43. Have Since the cotton nonwoven fabric forming the solid quenching agent 43 has a hydroxyl group (OH group) on the surface, unreacted metallic sodium remaining in the treated oil when the treated oil passes through the solid quenching agent 43. Metal sodium reacts with a hydroxyl group to form sodium hydroxide. The treated oil is a paraffinic oil and does not react with the solid quenching agent 43.

  In the present invention, the solid quenching agent 43 and unreacted metallic sodium are brought into contact, and the hydroxyl group on the surface of the solid quenching agent 43 is reacted with metallic sodium to quench the unreacted metallic sodium. For this reason, the solid quenching agent 43 may be a solid material that does not dissolve in the treated oil and has a hydroxyl group (OH group) on the surface, and considering the reactivity with metallic sodium, many hydroxyl groups are formed on the surface of the material. What has is more preferable. Furthermore, if the solid quenching agent 43 is made into a filter shape as in this embodiment, it is possible to efficiently contact the solid quenching agent 43 and metal sodium, and in addition to the nonwoven fabric, woven fabric, paper, porous Materials can be used. In addition, the reinforcing material for maintaining the shape of the solid quenching agent 43 may be provided, and the shape of the filter is not limited to a specific shape.

  Such solid quenching agents 43 include those derived from plants and animals, and those derived from synthetic resins. Specific examples include cellulose, cellulose based wood, cotton, hemp, starch, chitin, chitosan, hyaluronic acid, animal protein, acetate rayon, cellulose acetate, cellulose acetate propionate, carboxymethylcellulose, and other cellulose plastics. Examples thereof include polyvinyl alcohol, biodegradable plastics, raw materials based on these, and fibers, cloths, and papers containing these as main components.

  As a simple judgment index as to whether or not the solid quenching agent 43 can be used, a small amount of SD is dropped on the solid quenching agent 43, and the heat generation at that time can be used. For example, when SD spilled on the floor is wiped off with a cellulosic cloth, it generates heat violently, but it does not generate heat even if it is wiped off with a cloth made of polypropylene having no hydroxyl group.

  If the size of the opening of the solid quenching agent 43 is increased too much, the treated oil will easily pass through, and unreacted metallic sodium will also pass through the solid quenching agent 43 without coming into contact with the solid quenching agent 43. Resulting in. On the other hand, when the size of the opening of the solid quenching agent 43 is reduced, unreacted metallic sodium is trapped on the surface of the solid quenching agent 43. It is preferable that unreacted metallic sodium is trapped on the surface of the solid quenching agent 43 from the viewpoint of the reaction between the unreacted metallic sodium and the hydroxyl group on the surface of the solid quenching agent 43, but the treated oil is solid. Since the resistance when passing through the quenching agent 43 increases and the processing speed decreases, the size of the opening of the solid quenching agent 43 should not be extremely reduced.

  The sodium hydroxide produced by the reaction between the unreacted metallic sodium and the hydroxyl group on the surface of the solid quenching agent 43 remains adsorbed on the surface of the solid quenching agent 43, so that the solid quencher progresses as quenching proceeds. The opening of the ching agent 43 is reduced and the eyes are clogged. From the above points, the size of the opening of the solid quenching agent 43 is preferably a size obtained by adding 1 to 5 μm to the average particle diameter of unreacted metallic sodium remaining in the treated oil, and remains in the treated oil. A size obtained by adding 2 to 3 μm to the average particle diameter of unreacted metallic sodium is more preferable. In this PCB-mixed insulating oil detoxification processing apparatus 1, the processed oil from which the solid impurities are substantially separated by the electrostatic adsorption machine 21 is sent to the quenching device 33, so that it is quenched by the quenching device 33. The amount of unreacted metallic sodium to be used is very small.

  An example of how to use the quenching device 31 is shown. The treated oil from which solid impurities are substantially separated by the electrostatic adsorber 21 is sent to the quenching device 33 via the oil feed pump 35. The treated oil sent to the quencher 33 passes through the solid quenching agent 43 and is discharged from the outlet. When the treated oil passes through the solid quenching agent 43, the unreacted metallic sodium contained in the treated oil comes into contact with the solid quenching agent 43, and the unreacted metallic sodium is on the surface of the solid quenching agent 43. It reacts with the hydroxyl group of the product to become sodium hydroxide and remains on the surface of the solid quenching agent 43 as it is.

  If it is not possible to quench all unreacted sodium metal once it has passed through the quencher 33, it may be returned to the quencher 33 through the circulation line 39. It is desirable to conduct preliminary experiments in advance to obtain the necessity of circulation, the number of circulations, the circulation amount, and the like.

  As the treated oil passing through the quenching device 33 increases or the processing time increases, the number of hydroxyl groups on the surface of the solid quenching agent 43 decreases, and conversely, the amount of sodium hydroxide attached increases, The pressure loss when passing through the chucking device 33 increases. Therefore, a breakthrough curve of the so-called solid quenching agent 43 can be obtained by acquiring the relationship between the pressure at the inlet of the quenching device 33 and the amount or ratio of the remaining hydroxyl groups in the solid quenching agent 43. If the breakthrough curve of the solid quenching agent 43 is obtained, the breakthrough state of the solid quenching agent 43, more specifically, the remaining hydroxyl group of the solid quenching agent 43 is determined from the pressure at the inlet of the quenching device 33. The amount or ratio can be grasped.

  As described above, in the present embodiment, solid impurities contained in the treated oil are separated by the electrostatic adsorber 21, and then the unreacted metallic sodium remaining in the treated oil is further removed using the solid quenching agent 43. Therefore, the operation is very simple as compared with the conventional quenching using water. In addition, since unreacted metallic sodium remaining in the treated oil is removed through two apparatuses having different characteristics, unreacted metallic sodium can be efficiently removed. Further, when the treated oil is sent from the decomposition confirmation tank 17 to the electrostatic adsorber 21 and further from the electrostatic adsorber 21 to the quenching device 33, a temperature operation such as cooling is unnecessary, so that the PCB is rendered harmless in a short time. It can be carried out. In addition, post-treatment of the treated oil after quenching is not required as in the quenching method using water, and energy consumption is low. Furthermore, the structure of the detoxification processing apparatus is simple and the entire apparatus can be made compact. Usually, in the case of a quenching method using water, a neutralizing agent is added to neutralize the water after quenching. Since the added neutralizing agent becomes a part of waste, the amount of waste increases. However, in this embodiment, the amount of waste does not increase because neutralization operation is unnecessary. In addition, when the solid quenching agent 43 of this embodiment breaks through, it can also be disposed of as it is or washed with water, dried and regenerated.

  In the said embodiment, although the example which uses one quenching machine 33 was shown, you may operate | move, arranging two quenching machines 33 in parallel and switching alternately. Further, the quenching device 33 may be arranged in series so that completely unreacted sodium metal can be quenched by one pass. The return of the circulation line 39 may be used as the decomposition confirmation tank 17.

  FIG. 4 is a diagram showing a schematic configuration of another quenching device 32. The same components as those in the quenching device 31 shown in FIG. The quenching device 32 quenches unreacted metallic sodium remaining in the treated oil that has passed through the electrostatic adsorber 21, using the solid quenching agent, similarly to the quenching device 31 described above. Although the quenching mechanism is the same as that of the quenching apparatus 31, the forms of the quencher 51 and the solid quenching agent 53 are different.

  The quenching device 51 used in the quenching device 32 is a fluidized bed type. The quenching device 51 has a treated oil inlet 55 at the bottom and an outlet 57 at the top, and a granular solid quencher inside. A ching agent 53 is filled. The treated oil is supplied from the bottom of the quencher 51, and while the solid quenching agent 53 is fluidized, it is brought into contact with unreacted metallic sodium remaining in the treated oil to quench the unreacted metallic sodium.

  The solid quenching agent 53 reacts with unreacted metallic sodium to reduce the number of hydroxyl groups. However, the sodium hydroxide produced by the reaction simultaneously stops on the surface of the solid quenching agent 53, so the weight gradually increases. Become. For this reason, the solid quenching agent 53 sufficiently reacted with unreacted metallic sodium and the unreacted solid quenching agent 53 or the solid quenching agent 53 that has hardly reacted can be separated by a specific gravity difference. By utilizing this, the unreacted solid quenching agent 53 is supplied from the upper part, and the reacted solid quenching agent 53, that is, the so-called breakthrough solid quenching agent 53, is taken out from the lower part, thereby enabling continuous operation. The form of the solid quenching agent 53 to be filled therein is not particularly limited, and in addition to the granular form, a pellet form, a cylindrical form, or a ball form may be used. Basically, the smaller the particle size is, the smaller the specific surface area increases. However, the particle size is preferably determined in consideration of the separability. If it is extremely small, separation from the treated oil becomes difficult.

  In the said embodiment, although the solid quenching apparatus 31 and 32 which used the quencher 33 and 51 of a filter type and a fluidized bed type was shown, the model of a quencher is not specifically limited, A fixed bed , Packed bed, moving bed type. The specifications of the solid quenching apparatus are preferably determined according to the separation performance of the electrostatic adsorption machine that separates the solid impurities located on the upstream side.

  In the above embodiment, the PCB-mixed insulating oil detoxification treatment apparatus 1 is shown. However, the present invention removes solid impurities in the dehalogenated oil by electrostatic adsorption, and further removes them by electrostatic adsorption. A process characterized by quenching unreacted metallic sodium remaining in a halogen oil with a solid quenching agent, and a process for dehalogenating an oil containing a halogen compound in addition to PCB mixed insulating oil with metallic sodium The present invention can be preferably used. 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 11 Storage tank 13 Vacuum distillation tank 15 Reaction tank 17 Decomposition | disassembly confirmation tank 21 Electrostatic adsorption machine 31 Quenching apparatus 32 Quenching apparatus 33 Quenching apparatus 41 Pressure detector 43 Solid quenching agent 45 Processed oil tank 51 Quenching device 53 Solid quenching agent

Claims (3)

A reaction tank for dehalogenating a halogen compound in oil to be treated with metallic sodium to obtain a dehalogenated oil;
An electrostatic adsorption machine that electrostatically adsorbs and separates solid impurities contained in the dehalogenated oil;
Built-in solid quenching agent consisting of a solid having a hydroxyl group on the surface and insoluble in oil, bringing the solid quenching agent into contact with the dehalogenated oil from which solid impurities have been separated by the electrostatic adsorption machine, A quenching device for reacting unreacted metallic sodium remaining in the dehalogenated oil with a hydroxyl group of the solid quenching agent to quench the metallic sodium;
Only including,
The solid quenching agent is in the form of granules, pellets, or balls,
The quencher is a fluidized bed;
The dehalogenated oil in which unreacted metallic sodium remains in the fluidized bed is supplied, the metallic sodium is quenched while fluidizing the solid quenching agent, and the solid quenching agent that has passed through is separated by a specific gravity difference. the separated detoxification device characteristics and to Ruha androgenic compound-containing oil be withdrawn from the fluidized bed. The said solid quenching agent consists of a solid derived from a plant and / or an animal, and a synthetic resin, The detoxification processing apparatus of the halogen compound containing oil of Claim 1 characterized by the above-mentioned. 3. The treated oil includes an oxidized modified oil, and the solid impurities include a reaction product generated by a reaction between the oxidized modified oil and metallic sodium. Detoxification processing equipment for halogen compound-containing oils as described in 1.

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