JP5902996B2 - Detoxification treatment apparatus for organic halogen compounds and detoxification treatment method - Google Patents

Description

  The present invention relates to an organic halogen compound detoxification treatment apparatus and a detoxification treatment method for detoxifying an organic 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. A typical treatment process for dechlorinating PCB by reacting metallic sodium with PCB-containing insulating oil is a dehydration step for removing moisture contained in the oil to be treated, and a reaction for dechlorination by reacting PCB with metallic sodium. It consists of a process, a quenching process for quenching excess metal sodium, and a purification process for removing impurities in the treated oil (see, for example, Patent Documents 1 and 2).

JP 2011-217982 A JP 2002-212109 A

  In the conventional treatment process in which PCB and metal sodium are reacted to dechlorinate PCB, the chemicals used in each step and the operating conditions are different, so the number of steps in the whole treatment process is large and the operation is complicated. Yes. Furthermore, an independent apparatus is required for each process, and the facilities are large.

  An object of the present invention is to provide a detoxification treatment apparatus and detoxification of an organic halogen compound that can simplify the treatment process and detoxify an organic halogen compound in oil such as PCB mixed insulating oil by a simple apparatus configuration and simple operation. It is to provide a processing method.

The present invention relates to an organic halogen compound detoxifying apparatus for reacting an organic halogen compound in oil with metallic sodium and a hydrogen donor to dehalogenate the organic halogen compound. A first reactor for reacting with sodium, a solid hydrogen donor having a hydroxyl group on the solid surface, and a second oil that is reacted in the first reactor and the solid hydrogen donor are brought into contact with each other and reacted. A reactor, and a circulation line that circulates the oil to be treated between the first reactor and the second reactor so that the oil to be treated can be circulated , wherein the solid hydrogen donor is made of cellulose or cellulose-based material becomes the second reactor, quenching apparatus in which an organic halogen compound is quenching the excess metallic sodium remaining in the treated oil dehalogenated, the organic halogen compound is removed A detoxification device organohalogen compound, characterized in that also functions as an oil purification device for separating the solid impurities contained in the halogenated been processed oil.

The present invention is also characterized in that, in the organic halogen compound detoxifying apparatus, the solid hydrogen donor is cotton .

  The present invention is also characterized in that in the organic halogen compound detoxifying apparatus, the solid hydrogen donor is in the form of a filter, and the second reactor is a filter type reactor.

  According to the present invention, in the organic halogen compound detoxification treatment apparatus, oil to be treated that has reacted in the first reactor breaks through the solid hydrogen donor from pressure loss when passing through the second reactor. It is characterized by detecting a state.

  The present invention is also a method for detoxifying an organic halogen compound using the organohalogen compound detoxifying apparatus, wherein the first reactor reacts an organic halogen compound in oil with metallic sodium. 1 reaction step, a second reaction step in which the oil to be treated after the first reaction step and the solid hydrogen donor are contacted and reacted in the second reactor, and a treatment after the second reaction step A confirmation step for confirming the concentration of the organic halogen compound in the oil, and after the confirmation step, while cooling the treated oil, the second reactor is used to quench excess metal sodium remaining in the treated oil and to treat the oil. And a quenching / oil refining step for separating solid impurities contained in the finished oil.

  The organohalogen compound detoxification treatment apparatus and detoxification treatment method of the present invention use a solid hydrogen donor having a hydroxyl group on the solid surface as a hydrogen donor, and further quench the excess metal sodium with the solid hydrogen donor. Because it is also used as a quenching means and an oil refining means for separating solid impurities contained in the treated oil, the treatment process is simplified, and a simple apparatus configuration and a simple operation can be used in the oil such as PCB mixed insulating oil. Organic halogen compounds can be rendered harmless.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows schematic structure of the organic halogen compound detoxification processing equipment 1 containing the detoxification processing apparatus of the organic halogen compound which is one Embodiment of this invention. It is a flowchart which shows the process sequence of the organic halogen compound detoxification processing equipment 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 2nd reactor 18 used with the organic halogen compound detoxification processing equipment 1 of FIG. It is the photograph which image | photographed the external appearance of the processed oil of Example 1 and Comparative Example 1 of this invention.

  FIG. 1 is a diagram showing a schematic configuration of an organic halogen compound detoxification treatment facility 1 including an organic halogen compound detoxification treatment apparatus according to an embodiment of the present invention. FIG. 2 is a flowchart showing the processing procedure of the organic halogen compound detoxification processing facility 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 organic halogen compound detoxification treatment facility 1 (hereinafter referred to as detoxification treatment facility 1) will be described.

  The detoxification treatment facility 1 uses the first reactor 15 and the second reactor 17 for the step of dechlorinating (decomposing) PCB by reacting PCB, metal sodium, and hydrogen donor contained in the oil to be treated. The solid hydrogen donor (solid hydrogen donor) is used as the hydrogen donor, and surplus metallic sodium contained in the dechlorinated insulating oil (treated oil) is removed from the solid hydrogen donor. It has a great feature in that it is used as a quenching agent (quenching means) for quenching and an adsorbent (oil refining means) for adsorbing and separating solid impurities contained in the treated oil.

  The detoxification treatment facility 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, a first reactor 15 for dechlorination by reacting PCB with metallic sodium, The second reactor 17 for obtaining the treated oil by reacting the to-be-treated oil containing PCB reacted with the metallic sodium in the reactor 15 and the solid hydrogen donor 41, the unreacted metallic sodium remaining in the treated oil, and A treated oil tank 19 is provided for storing refined oil obtained by removing solid impurities.

  The oil to be treated is a distillate that is recovered by crushing the PCB trace insulating oil extracted from the pole transformer and the pole transformer after extracting the PCB trace insulating oil, and vacuum-heating it. These are stored in the storage tank 11 (accepting step: step S1) and then sent to the vacuum distillation tank 13. The oil to be treated is not limited to this. Only the trace amount of insulating oil mixed with PCB 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 treated oil. It can be.

  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 first reactor 15.

  The first reactor 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 first reactor 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 the sodium metal are heated to about 90 ° C. by the heated heating medium supplied to the jacket while being stirred, and the PCB reacts with the sodium metal and dechlorinates (first reaction step: step S3).

  The type of the first reactor 15 is not particularly limited as long as the PCB in the oil to be treated and the metal sodium can be sufficiently brought into contact with each other. Since the viscosity of the mixture of the oil to be treated and the metal sodium dispersion is not high, a general-purpose stirring blade or stirring means can be used. Also, the heating method is not particularly limited.

  The second reactor 17 incorporates a solid hydrogen donor 41 and sufficiently dechlorinates PCB by contacting and reacting the oil to be treated sent from the first reactor 15 and the solid hydrogen donor 41. The second reactor 17 is a filter-type device, and has a filter-shaped solid hydrogen donor 41 in which a cotton nonwoven fabric is formed in a cylindrical shape with a bottom. The oil to be treated containing metallic sodium can pass through the solid hydrogen donor 41.

  The non-woven fabric made of cotton that forms the solid hydrogen donor 41 has a hydroxyl group (OH group) on the surface. Therefore, when the metal sodium reacted with PCB and the remaining unreacted metal sodium come into contact with the solid hydrogen donor 41, the metal Sodium reacts with the hydroxyl group to produce hydrogen. This hydrogen acts on the dechlorination reaction of PCB. The oil to be treated is a paraffinic oil and does not react with the solid hydrogen donor 41.

  In the detoxification treatment facility 1 shown in the present embodiment, hydrogen is generated by reacting the hydroxyl group on the surface of the solid hydrogen donor 41 with metallic sodium. Therefore, the solid hydrogen donor 41 may be a solid material that does not dissolve in the oil to be treated and has a hydroxyl group (OH group) on the surface, and has many hydroxyl groups on the material surface in terms of reactivity with metallic sodium. And a thing with a large specific surface area is preferable.

  The form of the solid hydrogen donor 41 may not be in the form of a filter, but a filter form is preferable because the solid hydrogen donor 41 and the metal sodium can be efficiently contacted. As the solid hydrogen donor 41, a woven fabric, paper, a porous material, or the like can be used in addition to the non-woven fabric. In addition, the reinforcing material for maintaining the shape of the solid hydrogen donor 41 may be provided, and the shape of the filter is not limited to a specific shape.

  When the filter-shaped solid hydrogen donor 41 is used, if the opening is made too large, the oil to be treated will easily pass through, and the metal sodium that has reacted with the PCB, the unreacted metal sodium, and the solid hydrogen donor 41 Contact opportunities are reduced. On the other hand, when the mesh is made small, metallic sodium reacted with PCB and unreacted metallic sodium are easily captured on the surface of the solid hydrogen donor 41. It is preferable from the viewpoint of the reaction between the metal sodium and the hydroxyl group on the surface of the solid hydrogen donor 41 that the metal sodium reacted with the PCB and the unreacted metal sodium are trapped on the surface of the solid hydrogen donor 41. Since the resistance when the processing oil passes through the solid hydrogen donor 41 increases and the processing speed decreases, the size of the opening of the solid hydrogen donor 41 should not be extremely small.

  When metal sodium reacted with PCB, unreacted metal sodium and the hydroxyl group on the surface of solid hydrogen donor 41 react, sodium hydroxide is generated. Since the produced sodium hydroxide remains adsorbed on the surface of the solid hydrogen donor 41, as the reaction proceeds, the opening of the solid hydrogen donor 41 becomes smaller and the eyes are clogged. From the above points, the size of the opening of the solid hydrogen donor 41 is preferably a size obtained by adding 1 to 5 μm to the average particle size of the metal sodium to be added, and 2 to 3 μm added to the average particle size of the metal sodium. A size is more preferable.

  The solid hydrogen donor 41 includes 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 hydrogen donor 41 can be used, a small amount of SD can be dropped on the solid hydrogen donor 41, 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.

  The first reactor 15 and the second reactor 17 are connected via a first circulation line 21 so that the oil to be treated can be circulated. The first circulation line 21 is connected to the bottom of the first reactor 15 and the second reactor 17, the oil feeding line 25 interposing the circulation pump 23, and the outlet provided at the outlet of the second reactor 17. Line 27, and a return line 29 connecting the outlet line 27 and the top of the first reactor 15.

  The oil to be treated containing PCB that has been stirred and mixed in the first reactor 15 for a predetermined time and reacted with metallic sodium is sent to the second reactor 17 via the first circulation line 21. The oil to be treated sent to the second reactor 17 passes through the solid hydrogen donor 41 from the outside to the inside. In this process, the PCB contacts and reacts with the hydroxyl group of the solid hydrogen donor 41, hydrogen is added to the PCB, and it is sufficiently dechlorinated (second reaction step: step S4). The oil to be treated discharged from the second reactor 17 is returned to the first reactor 15 via the first circulation line 21.

  As described above, PCB is sufficiently dechlorinated in the second reactor 17 while the oil to be treated is circulated between the first reactor 15 and the second reactor 17. At this time, a heating medium heated in the jacket is supplied to the first reactor 15, and the oil to be treated is maintained between the first reactor 15 and the second reactor 17 while being maintained at a temperature of about 90 ° C. Circulate. By using the heating means of the first reactor 15 in this way, it is possible to omit providing the heating means in the second reactor 17. Needless to say, like the first reactor 15, the second reactor 17 may be provided with heating means such as a jacket.

  The treated oil from which PCB has been sufficiently dechlorinated while circulating between the first reactor 15 and the second reactor 17 is sampled through the second circulation line 31 and the PCB concentration in the treated oil is increased. It is confirmed whether the concentration is lower than the predetermined concentration (confirmation step: step S5).

  The second circulation line 31 is provided so as to bypass the second reactor 17. The first circulation line 21 is provided with a bypass line 33 that bypasses the second reactor 17 and connects the oil feed line 25 and the return line 29. The oil feed line 25, the bypass line 33, and the return line 29 Two circulation lines 31 are formed. A sampling valve 35 is provided in the middle of the second circulation line 31, and at the time of sampling, a part is sampled while circulating the oil to be treated through the second circulation line 31.

  When it is confirmed in the confirmation step that the PCB concentration in the oil to be treated is equal to or lower than the predetermined concentration (step S6), the PCB dechlorination reaction is completed, and then the PCB is dechlorinated. Shift to quenching and oil refining process for oil to be treated (treated oil).

  Since unreacted metallic sodium is highly active, the treated oil containing it is subject to various difficulties in storage, storage, and reuse. For this reason, in the quenching / oil refining step, unreacted metallic sodium contained in the treated oil is quenched, and further, reaction products that are solid impurities contained in the treated oil are removed to obtain a refined oil. .

  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 of PCB, metallic sodium, and solid hydrogen donor, the oxidized modified oil reacts with metallic sodium and further the solid hydrogen donor.

  The treated oil from which PCB has been dechlorinated includes the reaction product of PCB, metal sodium and solid hydrogen donor 41, as well as the product of oxidized modified oil and metal sodium, and solid hydrogen donor 41. Is included. In addition, surplus unreacted sodium metal remains. The reaction product and unreacted sodium metal are solid and dispersed in the treated oil.

  In the quenching / oil refining process, unreacted metallic sodium contained in the treated oil is quenched using the second reactor 17, and further, reaction products that are solid impurities contained in the treated oil are removed. To do. When it is confirmed in the confirmation step that the PCB concentration in the oil to be treated is below a predetermined concentration, the treated oil is passed through the first circulation line 21 between the first reactor 15 and the second reactor 17. Cycle between them. At this time, in order to lower the temperature of the treated oil, a low-temperature heat medium is supplied to the jacket of the first reactor 15, and the first reactor 15 is used as a cooler.

  The treated oil is brought into contact with the solid hydrogen donor 41 in the second reactor 17 while gradually decreasing the temperature. At this time, the unreacted metallic sodium contained in the treated oil reacts with the hydroxyl group on the surface of the solid hydrogen donor 41 to become sodium hydroxide. At the same time, when the solid reaction product contained in the treated oil passes through the solid hydrogen donor 41, it is adsorbed and captured by the solid hydrogen donor 41 (quenching / oil refining step: step S7). The solid hydrogen donor 41 having a hydroxyl group on the surface easily adsorbs metallic sodium and a solid reaction product.

  It has been found that the reaction product immediately after the formation has a strong cohesiveness and thus gradually adheres to the wall surfaces of the first reactor 15 and / or the second reactor 17 if left as it is. When a seed crystal is added, the reaction product adheres to the seed crystal and grows into a nucleus. When the reaction product having such properties comes into contact with the solid hydrogen donor 41, it adheres to the solid hydrogen donor 41. The reason for lowering the temperature of the treated oil in the quenching / oil refining step is to increase the adsorptivity of unreacted metallic sodium and reaction products to the solid hydrogen donor 41.

  As the treated oil passing through the second reactor 17 increases or the processing time increases, the number of hydroxyl groups on the surface of the solid hydrogen donor 41 decreases, and the amount of sodium hydroxide attached increases, The pressure loss when passing through the second reactor 17 increases. Therefore, a breakthrough curve of the so-called solid hydrogen donor 41 can be obtained by obtaining the relationship between the pressure at the inlet of the second reactor 17 and the amount or ratio of the hydroxyl group remaining in the solid hydrogen donor 41. . If the breakthrough curve of the solid hydrogen donor 41 is obtained, the breakthrough state of the solid hydrogen donor 41, more specifically, the hydroxyl group remaining in the solid hydrogen donor 41 is determined from the pressure at the inlet of the second reactor 17. The amount or percentage of

  When the solid hydrogen donor 41 breaks through, it can be disposed of as it is or washed with water, dried and regenerated. In the present embodiment, an example in which one second reactor 17 is used has been described. However, two second reactors 17 may be arranged in parallel and operated while being switched alternately.

  The refined oil obtained by quenching the unreacted metallic sodium contained in the treated oil in the second reactor 17 and removing the reaction product, which is a solid impurity contained in the treated oil, is the second reaction. It is sent to the treated oil tank 19 and stored through a storage line 37 connecting the container 17 and the treated oil tank 19 (storage process: step S8).

  As described in the Examples section below, basic experiments (1) Even when absorbent cotton is used as the hydrogen donor, PCB can be sufficiently decomposed in the same manner as when water is used as the hydrogen donor. (2) When absorbent cotton is used for the hydrogen donor, the pH after PCB decomposition is 4.8 lower than when water is used for the hydrogen donor, and 99% or more of sodium in the oil is adsorbed to the absorbent cotton. be able to. (3) Since the insulating oil after decomposition was transparent as shown in FIG. 5, it was confirmed that the solid reaction product (decomposition product suspension) was also adsorbed to the absorbent cotton. From the above, it was found that the method of using absorbent cotton as a hydrogen donor can sufficiently decompose PCB, and the insulating oil after decomposition is clean and can be used as fuel oil / insulating oil as it is.

  FIG. 4 is a diagram showing a schematic configuration of another second reactor 18. The same components as those of the second reactor 17 shown in FIG. Similarly to the second reactor 17 shown above, the second reactor 18 has a solid hydrogen donor 41, an oil to be treated containing PCB reacted with metallic sodium in the first reactor 15, and solid hydrogen donation. The body 41 is reacted to sufficiently dechlorinate PCB. Further, similarly to the second reactor 17, it is used as a quenching device and an oil refining device (impurity removing device). The function and usage of the second reactor 18 are basically the same as those of the second reactor 17.

  The second reactor 18 is a fluidized bed type reactor. An oil feed line 25 is connected to the bottom, an outlet line 27 is connected to the top, and a granular solid hydrogen donor 41 is filled inside. The oil to be treated is supplied from the bottom of the second reactor 18 and the solid hydrogen donor 41 is fluidized while the oil to be treated and the solid hydrogen donor 41 are contacted and reacted to sufficiently dechlorinate the PCB.

  When the solid hydrogen donor 41 reacts with metallic sodium, the number of hydroxyl groups gradually decreases, and the sodium hydroxide produced by reaction simultaneously stops on the surface, so that the weight gradually increases. For this reason, the solid hydrogen donor 41 sufficiently reacted with metallic sodium and the solid hydrogen donor 41 that has not reacted or hardly reacted can be separated by a specific gravity difference. Utilizing this, the unreacted solid hydrogen donor 41 is supplied from the upper part and the reacted solid hydrogen donor 41, that is, the so-called broken solid hydrogen donor 41 is taken out from the lower part, so that continuous operation is possible.

  The operation of supplying the unreacted solid hydrogen donor 41 and taking out the reacted solid hydrogen donor 41 from the lower part, that is, the so-called broken solid hydrogen donor 41, includes the quenching device and the impurity removing device of the second reactor 18. It can also be carried out in the quenching / oil refining process used as

  The form of the solid hydrogen donor 41 filled in the interior is not particularly limited, and a pellet, column, or ball may be used in addition to the granular form. Basically, the smaller the particle size is, the smaller the specific surface area increases. If it is extremely small, separation from the oil to be treated becomes difficult.

  As described above with reference to the embodiments, the organic halogen compound detoxification apparatus and detoxification process method of the present invention uses a solid hydrogen donor as the hydrogen donor, and performs the dehalogenation reaction of PCB 2. Using the base reactor, the PCB in the oil to be treated is reacted with sodium metal in the former reactor, and the oil to be treated and the solid hydrogen donor reacted in the former reactor in the latter reactor. It is characterized in that the hydroxyl group on the surface of the solid hydrogen donor is reacted with metallic sodium.

  In the conventional method of dehalogenating (decomposing) an organohalogen compound by reacting an organohalogen compound with metallic sodium and a hydrogen donor, a liquid such as water, alcohols or hydrocarbons has been used as the hydrogen donor. However, when water is used, the reactivity between water and metallic sodium is very high. If water is not added appropriately, the added water will react with metallic sodium and the organic halogen compound will be sufficiently dehalogenated. Can not be converted. For this reason, when water is used as the hydrogen donor, a large amount of metal sodium dispersion is added in consideration of the reaction between water and metal sodium, but the cost increases. On the other hand, when hydrocarbons and alcohols are used for the hydrogen donor, the reaction of the hydrocarbons and alcohols with metallic sodium is slow.

  For this reason, in the conventional method using water, hydrocarbons, and alcohols as the hydrogen donor, if the reaction state between the organic halogen compound and the metal sodium changes, the hydrogen donor becomes insufficient or excessive, and further sufficiently dehalogenated. There are cases where the conversion (decomposition) does not proceed.

  In contrast, the solid hydrogen donor 41 having a hydroxyl group on the surface easily adsorbs metallic sodium, but the reactivity between the hydroxyl group of the solid hydrogen donor 41 and metallic sodium is not as fast as that of water and metallic sodium. The reaction proceeds relatively mildly. For this reason, operation is easier than in the case where water is used as a hydrogen donor, metal sodium is not wasted, and an organic halogen compound can be dehalogenated efficiently and stably.

  The organohalogen compound detoxification treatment apparatus and detoxification treatment method of the present invention uses a solid hydrogen donor as a hydrogen donor, and adsorbs and removes a metal sodium quenching agent and reaction product. It is characterized in that it is used as an agent. Since the second reactors 17 and 18 containing the solid hydrogen donor 41 can be used as a quenching device and an impurity removing device (oil refining device), the number of devices is small and the equipment configuration is very simple. When the solid hydrogen donor 41 is used as a quenching agent, unreacted metallic sodium can be surely quenched because it involves a chemical reaction, and a dehalogenated oil from which unreacted metallic sodium has been sufficiently removed is obtained. Can do. In addition, the operation is very simple as compared with conventional quenching using water.

  By quenching metallic sodium using the solid hydrogen donor 41, post-treatment of the treated oil after quenching is not required as in the quenching method using water, and the energy consumption is small. 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, but in this embodiment, even if neutralization is not necessary or necessary, a simple neutralization operation is sufficient, so the amount of waste Does not increase.

  The organohalogen compound detoxification treatment apparatus and detoxification treatment method of the present invention are not limited to the above-described embodiments, and can be changed and used without departing from the scope of the invention. For example, in the above embodiment, a filter type and fluidized bed type reactor is shown as the second reactor, but the type of the second reactor is not particularly limited, and a fixed bed, a packed bed, and a moving bed are not limited. It may be a layer format. In the above embodiment, when the second reactors 17 and 18 are used as quenching means and oil purification means, the first reactor 15 is used as a cooler. It may be provided and used to cool the treated oil.

  In addition to the insulating oil mixed with PCB, the present invention can be suitably used in a process of dehalogenating an oil containing an organic halogen compound with sodium metal. In the above embodiment, the size of the metallic sodium in the SD is shown as a numerical value. However, this is an example, and the present invention is not limited to this numerical value.

Example 1
The decomposition test of PCB was performed using absorbent cotton as a hydrogen donor.

  1 L of PCB trace amount insulating oil with a PCB concentration of 6.6 mg / kg is collected in a 1 L screw mouth sample bottle, 50 g of anhydrous sodium sulfate is added, the screw mouth bottle is capped, and shaken vigorously by hand for 1-2 minutes. That ’s it. Then, it was left for 24 hours to remove moisture in the insulating oil. 200 ml of the PCB traced insulating oil supernatant from which water has been removed is dispensed into a 200 ml screw mouth sample bottle, and this screw mouth sample bottle is placed in a constant temperature dryer heated to 105 ° C. for 5 hours. Heated to above. Thereafter, 0.5 ml of a 20% metallic sodium slurry was added, shaken vigorously by hand, and heated in a constant temperature dryer for 1 hour.

  After that, shake the screw mouth sample bottle by hand to make the contents uniform, add 0.5 g of absorbent cotton as a hydrogen donor, shake it vigorously by hand, and then heat to 105 ° C. For 1 hour to cause decomposition reaction. The screw mouth sample bottle was taken out from the constant temperature dryer, allowed to cool, and analyzed for PCB and pH of the supernatant oil. PCB analysis was performed by a simple quantitative method using the biochemical method of the Ministry of the Environment “Simple Measurement Manual for Trace PCBs in Insulating Oil”. For the analysis of pH, the same amount of water as oil was added, stirred, allowed to stand and separated, and the pH of the water side was measured. The appearance of the insulating oil was visually observed.

  As a result of analysis, the PCB concentration was 0.2 mg / kg or less. The pH was 8.7. Compared to Comparative Example 1 described later, the PCB concentration was the same and the pH was 4.8 lower. As shown in FIG. 5, the upper part of the insulating oil after the decomposition test was transparent and yellow, and had the same color as the insulating oil before decomposition. Absorbent cotton which became light brown by adsorbing metal sodium and the reaction product was precipitated from the middle part to the bottom part.

Comparative Example 1
PCBs were decomposed using water as the hydrogen donor. A decomposition test was performed in the same manner as in Example 1 except that 0.05 ml of water was added instead of 0.5 g of absorbent cotton.

  As a result of the experiment, the PCB concentration was 0.2 mg / kg or less. The pH was 13.5. As shown in FIG. 5, the insulating oil after the decomposition test had metallic sodium and reaction products suspended as a whole, and was brown and turbid.

1 Organic Halogen Detoxification Treatment Facility 11 Storage Tank 13 Vacuum Distillation Tank 15 First Reactor 17 Second Reactor 18 Second Reactor 19 Treated Oil Tank 21 First Circulation Line 23 Circulation Pump 25 Oil Feed Line 27 Outlet Line 29 Return line 31 Second circulation line 33 Bypass line 35 Sampling valve 37 Storage line 41 Solid hydrogen donor

Claims (5)

An organic halogen compound detoxifying apparatus for reacting an organic halogen compound in oil with metallic sodium and a hydrogen donor to dehalogenate the organic halogen compound,
A first reactor for reacting an organic halogen compound in oil with metallic sodium;
A built-in solid hydrogen donor having a hydroxyl group on the solid surface, contacting the treated oil that has reacted in the first reactor and the solid hydrogen donor, and a second reactor to be reacted,
A circulation line for connecting the oil to be treated between the first reactor and the second reactor so that the oil can be circulated;
With
The solid hydrogen donor is made of cellulose or a cellulose-based material,
The second reactor is a quenching device for quenching excess metal sodium remaining in the treated oil from which the organic halogen compound has been dehalogenated, and a solid contained in the treated oil from which the organic halogen compound has been dehalogenated An organic halogen compound detoxifying treatment device that also functions as an oil refining device for separating impurities. 2. The organic halogen compound detoxifying apparatus according to claim 1, wherein the solid hydrogen donor is cotton .   3. The organohalogen compound detoxifying apparatus according to claim 1, wherein the solid hydrogen donor is in the form of a filter, and the second reactor is a filter type reactor. 4.   The organic material according to claim 3, wherein the treated oil reacted in the first reactor detects a breakthrough state of the solid hydrogen donor from a pressure loss when passing through the second reactor. Detoxification equipment for halogen compounds. An organic halogenated compound detoxifying method using the organic halogenated compound detoxifying apparatus according to any one of claims 1 to 4,
A first reaction step of reacting an organic halogen compound in oil with metallic sodium in the first reactor;
A second reaction step of contacting and reacting the oil to be treated after the first reaction step and the solid hydrogen donor in the second reactor;
A confirmation step for confirming the concentration of the organic halogen compound in the oil to be treated after the second reaction step;
After the confirmation step, while quenching the treated oil, the second reactor quenches excess metal sodium remaining in the treated oil and separates the solid impurities contained in the treated oil. A purification process;
A detoxifying treatment method for an organic halogen compound, comprising: