JP2010259496A - Decomposition treatment method for organic halogen compound and decomposition treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decomposition treatment method for organic halogen compounds and a decomposition treatment device for easily detoxifying an oil in which an organic halogen compound such as an insulating oil used in a pole-mounted transformer is mixed in a short time and for showing a low possibility of generating side reaction products. <P>SOLUTION: In the decomposition treatment method for decomposing the organic halogen compounds contained in the oil filled or kept in a container 1, the organic halogen compound is decomposed by repeating the operation of preparing a mixture liquid 2 by adding a hydrogen donor and an alkali compound to the oil containing the organic halogen compound, of cooling the mixture liquid 2, heated by microwaves applied in circulating in a catalyst filled device 4, in a liquid accumulation in a lower part of the catalyst tank 7 after the mixture liquid 2 is circulated in the catalyst filled device 4 disposed in an upper part of a catalyst tank 7, and of circulating the mixture liquid in the catalyst filled device 4 again. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic halogen compound decomposition treatment method and a decomposition treatment apparatus for decomposing an organic halogen compound contained in oil filled or stored in a container and detoxifying the oil. The present invention relates to an organic halogen compound decomposition treatment method and a decomposition treatment apparatus for decomposing polychlorinated biphenyl contained in an insulating oil filled or stored in a container such as a vessel to render the insulating oil harmless.

  Among various organic halogen compounds, polychlorinated biphenyl (hereinafter sometimes abbreviated as PCB) is extremely harmful to living organisms including the human body. Therefore, it was designated as a specified chemical substance in 1973, and its manufacture, importation, Use is prohibited. However, tens of thousands of tons of PCB are left untreated without finding an appropriate disposal method. Since PCB is a by-product of highly toxic dioxins by high-temperature decomposition, it is difficult to safely decompose PCB, and various safe and efficient decomposition methods for PCB have been studied for many years.

  As a treatment of oil containing organic halogen compounds filled or stored in a container such as a pole transformer, a method of treating the oil together with the container and a method of treating the container and the oil separately after extracting the oil from the container There is. The latter is desirable because oil can be reused.

  As the former, for example, a pole transformer is housed in an autoclave containing water and an oxidant while containing oil containing PCB, and the autoclave is heated to oxidize PCB by bringing water into a supercritical state. There is a method of detoxifying the entire pole transformer containing the oil containing PCB by decomposing, but this method requires a large-scale device.

  As the latter, for example, after removing the insulating oil from the pole transformer, the pole transformer is washed with a solvent to make it harmless, while the drained oil is heated by adding alkali metal tertiary butoxide, etc. Stir and detoxify the PCB by decomposing the PCB. However, since this system is a batch process, the equipment becomes very large for large-scale processing, and the catalyst is separated from the oil after the PCB decomposition process because the powdered catalyst is put into the oil as it is. However, when a fixed bed type catalyst is used instead of the powder catalyst, there are problems such as the reaction does not proceed satisfactorily because the contact opportunity with the PCB is reduced.

  Furthermore, since assessment is required for the construction of PCB processing equipment, it is possible to detoxify PCBs in the field, such as transformer storage, and to disassemble PCBs safely, in large quantities, and at low cost. Development of a method is desired.

  Therefore, as a method for detoxifying an oil containing PCB filled or stored in a container such as a pole transformer, a liquid to be treated is obtained by adding a hydrogen donor (isopropyl alcohol) and an alkali compound to the oil. A method for decomposing an organic halogen compound by extracting the product from a container and circulating it in a container filled with a catalyst such as a metal-supported carbon compound was proposed (for example, see Patent Documents 1 to 4). ).

  According to the method described in Patent Document 1, the PCB concentration can be reduced to 0.23 ppm in 8 days by treating the insulating oil containing 10 ppm of PCB at room temperature (without microwave irradiation). According to the above, by irradiating the liquid to be circulated through the catalyst filling device with microwaves and decomposing at 60 ° C., the deteriorated insulating oil (containing 36 ppm of PCB) can be reduced to 0.5 ppm or less in 4 to 5 days. From these results, it can be said that it is effective to irradiate the liquid to be processed with microwaves in order to increase the PCB processing speed.

  The method described in Patent Document 3 is a combination of the methods described in Patent Documents 1 and 2, and by installing the catalyst filling device inside the container and inside the microwave irradiation device (outside the container), It is proposed that the decomposition processing time can be shortened. The catalyst is more active when heated by microwaves than by simple heating. Therefore, it is effective to increase the microwave irradiation time in order to shorten the processing time. However, the method described in Patent Document 3 has a problem that when the microwave irradiation amount is increased, the temperature of the treatment liquid is excessively increased and dioxins and the like are easily generated as a by-product.

  Therefore, it was also considered to install a cooling device in the middle of a line (pipe) connecting the container and the catalyst filling device. However, since the temperature of the liquid returned to the container from the catalyst filling device does not fall completely in summer, the cooling effect may be insufficient, and the liquid temperature at the inlet of the catalyst filling device that irradiates microwaves becomes high. There was a problem that the amount of microwave irradiation had to be reduced.

  On the other hand, other treatment methods for organic halogen compounds using microwave energy are also known (see, for example, Patent Documents 5 to 7). In Patent Document 5, microwave plasma is irradiated to gaseous chlorofluorocarbon to generate thermal plasma, and chlorofluorocarbon is reacted with water vapor in thermal plasma to be decomposed. In Patent Document 6, moisture and an alkaline substance are added to the inside of a housing to which dioxins are attached, and the treatment is performed by irradiation with microwaves. However, since these methods are not liquid treatment methods, there is no problem with adjusting the liquid temperature during microwave irradiation.

  Patent Document 7 discloses an aromatic chlorine compound by irradiating a reaction system including a platinum group catalyst supported on a carbon-based support and an aromatic chlorine compound with microwaves in the presence of a reducing substance such as hydrogen. A method of dechlorinating is described. However, this method needs to supply hydrogen gas from the outside to the reaction system containing the aromatic chlorine compound, which is not preferable as a practical method and difficult to decompose difficult-to-decompose PCB. .

JP 2005-253484 A Japanese Patent No. 3970286 JP 2007-105061 A JP 2007-105062 A JP 2002-177735 A JP 2005-169291 A JP 2001-019466 A

  The present invention has been made in view of the above-described conventional problems, and can be easily detoxified in a short time with oil mixed with an organic halogen compound such as insulating oil used in a pole transformer. In addition, an object of the present invention is to provide an organic halogen compound decomposition treatment method and decomposition treatment apparatus that are less likely to produce a side reaction product.

  As a result of intensive studies to solve the above problems, the present inventors have added a hydrogen donor and an alkali compound to oil in a pole transformer mixed with a trace amount of an organic halogen compound to form a mixed solution, The mixed solution is taken out, and the taken out mixed solution is circulated through the catalyst filling device arranged in the catalyst tank, and then circulated to the pole transformer, and the microwave is irradiated when the mixed solution circulates through the catalyst filling device. In the decomposition method for decomposing the organic halogen compounds contained in the oil, the mixed liquid that has been circulated through the catalyst filling device is stored in a liquid reservoir at the bottom of the catalyst tank and cooled, so that the processing time is about ½ of the conventional processing time. And found that the organic halogen compound contained in the oil can be detoxified, thereby completing the present invention.

  That is, the present invention is as follows.

(1) A decomposition treatment method for decomposing an organic halogen compound contained in oil filled or stored in a container,
After adding a hydrogen donor and an alkali compound to the oil containing the organic halogen compound to obtain a mixed solution, a part of the mixed solution was taken out and circulated through a catalyst filling device disposed in the upper part of the catalyst tank. In the decomposition method for decomposing the organic halogen compound contained in the oil by irradiating the mixed liquid flowing through the catalyst filling device with microwaves while circulating in the rear container,
A decomposition treatment method characterized in that the mixed liquid circulated through the catalyst filling device is cooled in a liquid reservoir at the bottom of the catalyst tank and then circulated in a container.
(2) A decomposition treatment method for decomposing an organic halogen compound contained in oil filled or stored in a container,
After adding a hydrogen donor and an alkali compound to the oil containing the organic halogen compound to obtain a mixed solution, the mixed solution is taken out, and after passing through a catalyst filling device disposed in the upper part of the catalyst tank, the catalyst In the decomposition method for decomposing the organic halogen compound contained in the oil by irradiating the mixed liquid flowing through the catalyst filling device with microwaves while circulating in the filling device,
A decomposition treatment method characterized in that the mixed liquid circulated through the catalyst filling device is cooled in a liquid reservoir at the bottom of the catalyst tank and then circulated through the catalyst filling device.
(3) The mixed liquid that has been circulated through the catalyst filling device is cooled at a temperature of 5 ° C. or more than the temperature of the mixed liquid in the catalyst filling device in a liquid reservoir at the bottom of the catalyst tank. Decomposition method.
(4) The temperature (T) of the liquid mixture in the catalyst filling device is in the range of 40 to 80 ° C., and the difference between the temperature of the liquid mixture and T in the liquid reservoir at the bottom of the catalyst tank is in the range of 10 to 30 ° C. The decomposition treatment method according to any one of (1) to (3).
(5) The decomposition treatment method according to any one of (1) to (4), wherein the addition amount of the hydrogen donor is in the range of 50 to 200% by volume with respect to the oil containing the organic halogen compound.
(6) The decomposition processing method according to any one of (1) to (5), wherein the microwave output is controlled by PID control of a temperature controller.
(7) A rod-like, tubular, or fiber-like structure formed of a heat-resistant material that transmits microwaves is disposed so that a part thereof protrudes from the catalyst layer in the catalyst filling device. The decomposition treatment method according to any one of (6) to (6).
(8) The decomposition treatment method according to any one of (1) to (7), wherein the hydrogen donor is isopropyl alcohol.
(9) The decomposition treatment according to any one of (1) to (8), wherein the alkali compound is at least one compound selected from the group consisting of caustic soda, caustic potash, sodium alkoxide, potassium alkoxide, and calcium hydroxide. Method.
(10) The decomposition treatment method according to any one of (1) to (9), wherein the addition amount of the alkali compound is 0.1 to 10% (w / v) as a ratio to the hydrogen donor.
(11) The decomposition method according to any one of (1) to (10), wherein the hydrogen donor and the alkali compound are added after the alkali compound is dissolved in the hydrogen donor in advance.
(12) The decomposition treatment method according to any one of (1) to (11), wherein the catalyst used in the catalyst filling device is a metal-supported carbon compound.
(13) The decomposition treatment method according to any one of (1) to (12), wherein the oil is a hydrocarbon oil and the organic halogen compound is polychlorinated biphenyl.
(14) The decomposition processing method according to any one of (1) to (13), wherein the container is a pole transformer.

(15) A decomposition treatment apparatus for decomposing an organic halogen compound contained in oil filled or stored in a container,
(A) a catalyst filling device;
(B) a catalyst tank containing the catalyst filling device;
(C) a supply means for taking out a liquid mixture of oil, hydrogen donor and alkali compound in the container and supplying the mixture to the catalyst filling device;
(D) a microwave device for irradiating the catalyst filling device with microwaves;
(E) a cooling coil for cooling the mixed liquid stored in the liquid reservoir at the bottom of the catalyst tank;
The decomposition processing apparatus characterized by including at least.
(16) The decomposition processing apparatus according to (15), wherein the catalyst tank includes a discharge port for returning the mixed liquid discharged from the catalyst tank into the container.
(17) The decomposition processing apparatus according to (15) or (16), wherein the microwave device includes a temperature controller that measures and controls the temperature of the mixed liquid.
(18) A rod-like, tubular, or fiber-like structure formed of a heat-resistant material that transmits microwaves is dispersed and arranged so that a part thereof protrudes from the catalyst layer in the catalyst filling device. (15) The decomposition processing apparatus according to any one of (17).
(19) The decomposition processing apparatus according to any one of (15) to (18), wherein the catalyst filling apparatus includes a replaceable catalyst cartridge.
(20) The decomposition processing apparatus according to any one of (15) to (19), wherein the container is a pole transformer.

  In the organic halogen compound decomposition treatment method of the present invention, the circulating liquid is cooled in the liquid reservoir at the bottom of the catalyst tank, so that it is possible to increase the amount of microwave irradiation as compared with the prior art, and in a container such as a pole transformer. The organic halogen compound contained in the oil can be decomposed in about half of the conventional time. In addition, since cooling is performed using a liquid reservoir in the catalyst tank, the space of the apparatus can be saved, and problems that may occur when the line (pipe) is cooled from the outside, for example, precipitation of by-product inorganic salts There is no risk of clogging of the line (pipe) due to.

In addition, if the amount of hydrogen donor added to the oil is increased, the handling of the liquid and the temperature controllability of the liquid to be circulated become better, so the microwave output can be controlled by the PID control of the temperature controller. Thereby, the increase and leveling of the microwave irradiation amount can be achieved.
By disposing the microwave permeable structure in the catalyst filling device, the microwave is transmitted to the catalyst layer all over and the utilization efficiency of the catalyst is increased, so that the decomposition processing speed is improved.

By selecting the hydrogen donor and / or alkali compound to be used for the decomposition treatment, the organic halogen compound can be decomposed with high efficiency, and further, by defining the amount of use thereof, the decomposition of the organic halogen compound can be performed. Processing can be performed with higher efficiency. Moreover, the initial decomposition rate of the organic halogen compound can be increased by adding a solution in which an alkali compound is previously dissolved in a hydrogen donor to the oil.
By using a metal-supported carbon compound as the catalyst used in the decomposition treatment, the organic halogen compound can be decomposed with high efficiency, and the processing cost can be reduced.

  The organic halogen compound decomposition treatment apparatus of the present invention is an apparatus capable of decomposing an organic halogen compound contained in oil filled or stored in a container without substantially extracting the oil from the container, Since no special equipment is required for liquid cooling and temperature control, it is simple and does not require an installation location.

It is a figure explaining the outline of the usage example of the decomposition processing apparatus which concerns on this invention. It is a front perspective view which shows one Embodiment of the decomposition processing apparatus and decomposition processing method concerning Claim 1 of this invention, and match | combines the circulation path of the to-be-processed liquid when the liquid quantity of a container is larger than the volume of a catalyst tank. It is shown. It is a front perspective view which shows one Embodiment of the decomposition processing apparatus and decomposition processing method which concern on Claim 2 of this invention, and match | combines the circulation path of the to-be-processed liquid when the liquid quantity of a container is smaller than the volume of a catalyst tank. It is shown.

  The organic halogen compound decomposition treatment method and decomposition treatment apparatus according to the present invention will be described below in detail with reference to the drawings.

The decomposition treatment method of the present invention is not limited to a container such as a pole transformer filled or stored with an oil containing an organic halogen compound (content: 1 ppm to 10,000 ppm, preferably 1 ppm to 500 ppm). The decomposition treatment apparatus is installed, and the apparatus is used for the implementation.
The embodiment is not particularly limited. For example, as shown in FIG. 1, a pole transformer (container) is placed on the oil pan 27, and the decomposition treatment apparatus of the present invention is placed on the oil pan 28 above the pole transformer. After connecting the transformer and the decomposition treatment apparatus with a line, the organic halogen compound contained in the oil filled or stored in the pole transformer can be decomposed by performing a predetermined treatment.

  In the decomposition treatment method of the present invention, a hydrogen donor and an alkali compound are added to the oil in the container to form a mixed solution, and the mixed solution is circulated through the catalyst filling device provided in the decomposition treatment device. A known method is employed in which the organic halogen compound contained in the oil is decomposed by irradiating with microwaves while contacting the catalyst. Therefore, the decomposition treatment method of the present invention is characterized in that the mixed liquid circulated through the catalyst filling device is cooled in a liquid reservoir at the lower part of the catalyst tank and then circulated.

  Examples of the container include a pole transformer, a large transformer, an OF cable oil tank, and the like, and a pole transformer is preferable.

  Examples of the organic halogen compound that is the subject of the decomposition treatment of the present invention include polychlorinated biphenyls (PCBs) and dioxins, and the type is not particularly limited, but is preferably PCBs. It is. PCBs include PCBs containing dioxins. Examples of commercially available PCBs include KC-200 (main component: biphenyl dichloride), KC-300 (main component: biphenyl trichloride), KC-400 (main component: tetrachloride) manufactured by Kaneka Chemical Co., Ltd. Biphenyl), KC-500 (main component: biphenyl pentachloride), KC-600 (main component: biphenyl bichloride), Arocrol 1254 (54% Chlorine) manufactured by Mitsubishi Monsite Corporation, and the like.

  The decomposition treatment method of the present invention is suitable for decomposition treatment of oil containing a small amount or a small amount of PCBs, which are generally difficult to dehalogenate, among organic halogen compounds. The oil is mainly hydrocarbon oil. Specific examples include electrical insulating oil, heat medium oil, lubricating oil, or mineral oil obtained by extracting an organic halogen compound contained in a solid.

  2 and 3 are schematic views showing an embodiment of the decomposition treatment method and the decomposition treatment apparatus of the present invention, and an example of the decomposition treatment of the organic halogen compound-containing oil filled in the pole transformer (container). It is shown.

  The decomposition processing apparatus of the present invention is a decomposition processing apparatus capable of decomposing an organic halogen compound contained in oil filled or stored in a container in a state of being contained in the container. In carrying out the decomposition treatment, first, a hydrogen donor and an alkali compound are added to the oil containing the organic halogen compound in the container to prepare a mixed solution (hereinafter referred to as “liquid to be treated”). It is necessary.

  When preparing the liquid to be processed, the volume of the liquid to be processed is set so as not to overflow from the container. 2 and 3, reference numeral 29 denotes the liquid level of the liquid to be treated 2 filled in the pole transformer (container) 1. The liquid to be treated is a pillar installed in the pole transformer. This is the amount by which the upper transformer internal winding (coil) 3 is immersed.

  Although not shown, the container 1 may include a supply line for a hydrogen donor and an alkali compound. Alternatively, a device (pre-tank) (not shown) for storing a hydrogen donor and an alkali compound previously mixed and dissolving the alkali compound in the hydrogen donor is installed, and the hydrogen donor and the alkali compound are transferred from the device to the container 1. You may provide the supply line (illustration omitted) to supply.

  The decomposition treatment apparatus of the present invention comprises: (a) a catalyst filling device 4, (b) a catalyst tank 7 containing the catalyst filling device, and (c) a mixed liquid obtained by adding a hydrogen donor and an alkali compound to the oil in the container. Supply means (pump) 9 for supplying to the catalyst filling device, (d) a microwave device 12 for irradiating the catalyst filling device with microwaves, and (e) a liquid mixture stored in a liquid reservoir at the bottom of the catalyst tank. A cooling coil 18 for cooling is configured as an essential component. Hereinafter, the configuration of the apparatus will be described in order.

(A) Catalyst filling device The catalyst filling device 4 is filled with a catalyst capable of decomposing an organic halogen compound (particularly PCB). The catalyst filling device 4 is provided with a replaceable catalyst cartridge 5 in that it can be easily and quickly replaced when the decomposition rate is lowered during the process, and the post-treatment of the catalyst after the process is easy. Is preferred.

  The catalyst filling device 4 is installed in the upper part of the catalyst tank 7. Then, by installing the catalyst filling device 4 above the container 1, it is possible to save space during processing. In addition, by installing the catalyst filling device above the container, the liquid after circulation of the device can be returned to the container by its own weight, so that the discharging means can be provided simply by providing a liquid supply means from the container to the catalyst filling device. Has the advantage of becoming unnecessary. In addition, by installing it above the container, the liquid flow cross-sectional area of the catalyst layer can be designed to be large according to the inner diameter of the container, and the liquid flow rate can be increased even when the space velocity (SV) is constant. , Leading to shortening of the time required for disassembly. On the other hand, if the catalyst filling device is installed separately or below, a pump is required to return the liquid after passing into the container, and it is necessary to balance the supply and discharge of the liquid to the catalyst filling device, When the balance is lost, there is a risk of overflow or liquid leakage, and when the liquid runs out, there is a risk of sparks or abnormal heating of the catalyst.

  The shape and size of the catalyst filling device are not particularly limited, and may be in various forms. For example, a cylindrical shape, a rectangular tube shape, or the like. However, the catalyst filling device needs to have an inlet and an outlet for the liquid to be processed.

  The catalyst filling device 4 shown in FIGS. 2 and 3 is formed with a catalyst layer 6 filled with a catalyst, which will be described later, capable of decomposing organic halogen compounds. The liquid 2 to be treated is introduced into the upper portion of the catalyst filling device through an inlet provided in the upper portion of the catalyst filling device 4 via the supply line 15 and the pump 9 as indicated by an arrow in the figure. The introduced liquid to be treated flows continuously through the catalyst layer 6, and the liquid to be treated 2 after flowing through the catalyst layer flows down from the bottom of the catalyst filling device 4. Since the liquid level of the liquid to be treated introduced into the catalyst filling device is always kept high, the liquid to be treated flowing down from the bottom of the catalyst filling device flows into the catalyst tank 7 containing the catalyst filling device. Then, it is stored at the bottom of the catalyst tank 7 and cooled by the cooling coil 18 before being circulated. The arrows in FIG. 2 and FIG. 3 indicate the general flow direction of the liquid to be treated that has flowed through the catalyst filling device.

  2 and 3, in the catalyst layer 6, rod-like structures 8 formed of a heat-resistant material that transmits microwaves are dispersed and arranged so that a part thereof protrudes from the catalyst layer. ing. The existence of this structure is not essential, but by installing the structure, the microwave is transmitted to the depth of the catalyst layer. The shape of the structure is not particularly limited, and may be a rod shape, a tubular shape, a fiber shape, or a combination thereof. The inside of the structure may be hollow. The size, arrangement, and number of arrangements are arbitrary, but in order to ensure that microwaves reach the catalyst evenly, multiple structures are arranged as evenly as possible, and the microwave arrival circle of each structure It is preferable to arrange so as to approach close packing.

  The material of the structure is not particularly limited, and may be ceramic; Teflon (registered trademark), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), polyarylate (if it is a material that transmits microwaves) PAR), polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), polyamideimide (PAI), polyetheretherketone (PEEK), liquid crystal polyester (LCP), liquid crystal polymer (LCP), polyacetal (POM), polyamide (PA), polybutylene terephthalate (PBT), polycarbonate (PC), modified polyphenylene ether, or other heat-resistant resin; glass or other material without a dipole or a material with a small dipole moment; Can That.

(B) Catalyst tank The catalyst tank 7 is configured to accommodate the catalyst filling device 4, store the liquid to be treated in the catalyst filling device 4 at the bottom of the catalyst tank, and return it to the container. . A liquid discharge port 30 for returning the liquid to be treated to the container is provided on the bottom surface of the catalyst tank. As will be described later, the catalyst tank 7 is configured such that the processing method (that is, the liquid circulation path) can be changed depending on the amount of liquid in the container.

  When the amount of liquid in the container 1 is larger than the volume of the catalyst tank 7, as shown in FIG. 2, the liquid to be treated is first sucked from the container 1 through the pump 9 into the catalyst tank 7 and sucked up. Flows down in the catalyst filling device 4, is stored and cooled in a liquid reservoir at the bottom of the catalyst tank, and then returned to the container 1 through the discharge port 30. At this time, the extraction valve 22 and the pump outlet valve 23 are opened, the pump inlet valve 24 and the processing oil sampling valve 26 are closed, and the liquid to be processed is circulated. The return valve 25 adjusts opening and closing so that the liquid is always stored in the liquid reservoir in the lower part of the catalyst tank.

  When the amount of liquid in the container 1 is smaller than the volume of the catalyst tank 7, the liquid to be treated is first sucked from the container 1 to the catalyst tank 7 via the pump 9 as shown in FIG. 3. At this time, most of the liquid to be treated in the container 1 is sucked up to the catalyst tank. The sucked liquid to be treated flows down in the catalyst filling device 4 and is stored and cooled in a liquid reservoir in the lower part of the catalyst tank, and then circulated through lines 21 and 16 connecting the catalyst tank 7 and the pump 9. At this time, the pump inlet valve 24 and the outlet valve 23 are opened, the extraction valve 22, the return valve 25 and the sampling valve 26 are closed, and the liquid to be treated is circulated. The discharge port 30 is kept closed.

(C) Liquid supply means The liquid supply means (pump) 9 is used as means for transferring the liquid to be processed in the container to the catalyst filling device and means for circulating the liquid to be processed in the catalyst tank. The mounting position of the pump 9 is not particularly limited, and may be provided at an arbitrary location outside the container 1. In particular, when the pump 9 is provided adjacent to the catalyst tank 7, the bottom of the catalyst tank is provided. The operation (see FIG. 3) for circulating the liquid to be treated stored in the liquid reservoir to the catalyst filling device is facilitated. The pump 9 is provided with lines 15, 16 and 21 for supplying and circulating the liquid 1 to be processed through the pump 9. As a result, the liquid to be treated can be continuously supplied to the catalyst filling device, and the organic halogen compound can be brought into contact with the catalyst.

(D) Microwave device The microwave device 12 includes a temperature controller (with a PID control function) for temperature measurement and temperature control of the liquid to be treated in the catalyst filling device in order to level the microwave irradiation amount. It is good to have. Based on the temperature detected by the temperature sensor 10 and the set temperature of the temperature controller 11, the output of the microwave device 12 is PID controlled to keep the liquid temperature of the liquid to be processed at a substantially constant temperature while continuously irradiating the microwave. can do.

  In the decomposition processing apparatus of the present invention, the installation location of the microwave device 12 is not particularly limited, but space saving can be achieved if it is provided above the catalyst filling device 4. The liquid to be treated that flows through the catalyst layer 6 comes into contact with the catalyst heated by the microwave irradiated from the microwave oscillator, so that the organic halogen compound in the liquid is rapidly decomposed.

  The frequency of the microwave applied to the catalyst filling device is preferably 1 to 300 GHz, and in the frequency range of less than 1 GHz or more than 300 GHz, the catalyst and the hydrogen donor are not sufficiently heated. As the microwave oscillator, a microwave oscillator such as a magnetron, a microwave oscillator using a solid element, or the like can be used as appropriate.

  The microwave irradiation method with respect to the catalyst filling apparatus is not limited, and can be carried out continuously or intermittently. From the viewpoint of rapid processing, microwave irradiation is desired to be as continuous as possible or as long as possible. However, it is also possible to carry out only during the day taking into consideration the safety and cost of driving, securing personnel, etc. For example, intermittent irradiation such as irradiating microwaves during the day and stopping microwave irradiation at night You can also

(E) Cooling coil The cooling coil 18 is provided at an appropriate location inside the catalyst tank 7 so as to cool the liquid to be treated stored in the liquid reservoir below the catalyst tank 7. The illustrated cooling coil 18 uses a cooling water circulation device 13 such as a general heat exchanger to which a cooling medium is supplied from a cold heat source, and the cold water supplied from the device 13 to the cooling coil inlet via a line 19 is supplied. After the contact with the liquid to be treated, it is designed to return to the apparatus 13 through the line 20 from the outlet of the cooling coil. If the temperature of the liquid reservoir becomes too low, the liquid returned to the container will be too cold, and it will be difficult for the organic halogen compound that has permeated the member to elute into the liquid. The flow rate of the cooling water may be adjusted by the adjuster 14.

  The installation location and the installation form of the cooling coil are not particularly limited. For example, as shown in the drawing, the catalyst filling device 4 circulates in the liquid stored in the catalyst tank 7 containing the catalyst filling device. If arranged in this way, the cooling efficiency is good. Since the microwave is blocked by the catalyst filling device and does not reach the liquid reservoir, the liquid reservoir has no fear of being heated by the microwave.

  As described above, when the liquid amount in the container is larger than the volume of the catalyst tank, the decomposition treatment apparatus of the present invention contacts the catalyst while circulating the liquid to be processed between the container and the catalyst tank, When the amount of liquid is smaller than the volume of the catalyst tank, it is preferable to contact the catalyst while circulating the liquid to be treated only in the catalyst tank. In either case, the treatment liquid flowing through the catalyst filling device is irradiated with microwaves to accelerate the decomposition of the organic halogen compounds, and the liquid reservoir at the bottom of the catalyst tank is cooled so that the microwave irradiation time can be as long as possible. It is comprised so that it can cool with a coil.

  As a means for cooling the liquid to be treated heated by the microwave irradiation, a cooling means may be provided in the middle of the line 17 for returning the catalyst tank 7 to the container. However, this means cannot cope with the case of circulating only in the catalyst tank. In addition, when such means is adopted, there is no problem when circulating both the catalyst tank and the container, but the liquid returned to the container becomes too cold, and the organic halogen compound that has permeated the member is difficult to elute into the liquid. There is inconvenience such as becoming.

  Further, as another cooling means, it is conceivable to provide a cooling means immediately before the entrance of the catalyst tank 7 (in the middle of the line 16). However, this means is not preferable from the viewpoint of space saving because it is necessary to newly install a liquid reservoir for providing a cooling coil. Therefore, when cooling the middle of the line, a method of cooling the line from the outside (for example, introducing the liquid to be treated into the chiller tube) is suitable, but the decomposition processing apparatus of the present invention is necessary for cooling. It is difficult to secure a sufficiently long line, and there is a risk that clogging occurs due to precipitation of by-products (KCl, etc.) at the cooling line location.

  Thus, when the cooled liquid to be treated comes into contact with the catalyst heated by the microwave, the organic halogen compound in the liquid to be treated is rapidly decomposed. That is, since the liquid to be treated that circulates through the catalyst filling device is circulated after being cooled, the liquid temperature at the inlet of the catalyst filling device is lowered, thereby increasing the microwave irradiation amount. The decomposition efficiency of the organic halogen compound is remarkably improved as compared with the case where the liquid to be treated is circulated without cooling.

  The treatment liquid may be circulated until the organohalogen compound in the treatment liquid reaches a predetermined concentration or less. When appropriate, the treatment liquid is sampled from the sampling valve 26 provided in the decomposition treatment apparatus and analyzed. By doing so, the organic halogen compound concentration can be measured.

  Next, an embodiment of the organic halogen compound decomposition treatment method according to the present invention using the decomposition treatment apparatus will be described with reference to FIG.

  First, to-be-processed liquid 2 is prepared by adding a hydrogen donor and an alkali compound, which will be described later, to a container 1 containing oil mixed with a trace amount or a small amount of PCB shown in FIG. Stir and mix inside the container as necessary. The addition amount is preferably such that the amount of hydrogen donor is in the range of 50 to 200% by volume with respect to the oil. More preferably, it is the range of 100-200 volume%. When the amount of the hydrogen donor is less than 50% by volume, even if the liquid to be treated is introduced into the decomposition treatment apparatus of the present invention, it is difficult to obtain the cooling effect of the liquid to be treated because the thermal conductivity of the liquid to be treated is low. In addition, since it becomes difficult to control the PID of the liquid to be treated, the decomposition reaction is difficult to proceed due to a decrease in the microwave irradiation amount. On the other hand, if the amount of the hydrogen donor exceeds 200% by volume, it exceeds the allowable amount of the container, which is a practical limit. What is necessary is just to add the amount which an alkali compound mentions later with respect to a hydrogen donor.

  Next, the liquid to be treated 2 is continuously circulated through the catalyst filling device 4 filled with the catalyst to dehalogenate the organic halogen compound. When the liquid to be treated circulates through the catalyst filling device, microwaves are used. Irradiate. The temperature (T) of the liquid to be treated when flowing through the catalyst filling device is detected by a temperature sensor 10 installed in the liquid above the catalyst layer. The reaction temperature (that is, the temperature T of the liquid to be treated) is preferably as low as possible in order to make it difficult for byproducts such as dioxins to be generated, but is preferably from room temperature to 200 ° C. in view of the decomposition rate. More preferably, the reaction temperature is 100 ° C. or lower, and when the reaction temperature exceeds 200 ° C., the dehalogenation reaction proceeds sufficiently, but by-products are easily generated and the economy is inferior. Especially the temperature which can fully exhibit a cooling effect is the range of 40 to 80 degreeC. The time for circulating the liquid to be treated through the catalyst filling device is not particularly limited, and the treatment is carried out until the organohalogen compound in the liquid falls below a predetermined treatment reference value. The cooling in the liquid pool is preferably performed so that the temperature of the liquid to be treated is at least 5 ° C., preferably 10 ° C. or more lower than the reaction temperature. Especially preferably, it is 10-30 degreeC. If the liquid to be treated is cooled too much, the fluidity of the liquid to be treated may be reduced, making it difficult to return to the container 1 or causing clogging. Or there exists a possibility that the reaction temperature cannot be maintained by microwave irradiation.

  By performing the above decomposition treatment, the insulating oil 10-15L having a PCB concentration of about 20 ppm can be reduced to 0.5 ppm or less in about 10-30 hours. After completion of the decomposition, the mixed liquid in the container is extracted from the container via an extraction pump or a drain valve.

  The atmosphere of the decomposition reaction is more preferably performed in an inert gas because undesirable side reactions do not occur. However, since it may be difficult to procure an inert gas depending on the processing environment of the contaminated oil, the reaction can be performed in a natural atmosphere.

  In the detoxification treatment method of the present invention, examples of the “hydrogen donor” added to the oil include organic hydrogen such as heterocyclic compounds, amine compounds, alcohol compounds, ketone compounds, and alicyclic compounds. And donors. Among these compounds, alcohol compounds, ketone compounds, and alicyclic compounds are preferable from the viewpoint of safety. In particular, they are highly safe, can be obtained at low cost, and reaction control is easy. From the viewpoint of high decomposition efficiency, alcohol compounds are preferred. These hydrogen donors can be used alone or in any combination of two or more.

  Here, the alcohol compound may be either an aliphatic alcohol or an aromatic alcohol, and a monohydric alcohol or polyhydric alcohol having a linear or branched chain can be used. The carbon number of the alcohol compound is preferably in the range of 1 to 12, more preferably in the range of 2 to 9, and still more preferably in the range of 3 to 6. Specific examples of the alcohol compound include, for example, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, s-butanol, t-butanol, 1-pentanol, 2-pentanol, and 3-pentanol. 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol and other aliphatic alcohols, cyclopropyl alcohol, cyclobutyl alcohol, cyclopentyl alcohol, cyclohexyl Examples thereof include alicyclic alcohols such as alcohol, cycloheptyl alcohol and cyclooctyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol and decalin diol. Among these, 2-propanol and cyclohexanol are preferable from the viewpoint of decomposition efficiency, and 2-propanol (isopropyl alcohol) is particularly preferable.

  The alkali compound can be used without limitation as long as it can accelerate the dehalogenation reaction of the organic halogen compound, but from the viewpoint of increasing the dehalogenation efficiency, caustic soda, caustic potash, sodium alkoxide, potassium alkoxide. , Calcium hydroxide and the like are preferably used. Among these, caustic soda and caustic potash are particularly preferable from the viewpoint of cost and handling properties. An alkali compound can be used individually or in combination of 2 or more types.

  In the detoxification treatment method of the present invention, it is preferable to prepare a liquid mixture in which the hydrogen donor and the alkali compound are pre-stirred in advance to dissolve the alkali compound in the hydrogen donor.

  Moreover, it is preferable that an alkali compound shall be 0.1-10% (w / v) as a ratio with respect to a hydrogen donor, More preferably, it is 0.2-5% (w / v). If the ratio is less than 0.1%, the decomposition reaction does not proceed, and if it exceeds 10%, the alkali compound is difficult to dissolve.

  In the detoxification method of the present invention, when the organic halogen compound in the container is dissolved in the mixed solution, stirring from the outside by shaking, stirring from the inside by a stirrer, microscopic stirring by ultrasonic waves, etc. Any method may be used. As agitation from the outside by shaking, for example, a method in which a container is vibrated using a vibration stirrer, a shaking table, a shaker, etc. Etc.) and the like. Examples of the stirring from the inside by the stirrer include a method of stirring the liquid mixture using a stirrer such as a stirring blade or a magnetic stirrer. In the case of stirring, either continuous stirring or intermittent stirring may be employed.

  As the catalyst filled in the catalyst filling apparatus of the present invention, any catalyst can be used without limitation as long as it can accelerate the dehalogenation reaction of PCB, and the kind thereof is not particularly limited. An inorganic catalyst is preferable to an organic catalyst because it has a long catalyst life and is stable even in the presence of an alkali compound. Preferred specific examples of the inorganic catalyst include composite metal oxides, carbon crystal compounds, metal-supported carbon compounds, metal-supported oxides, metal-supported composite metal oxides and metal oxides from the viewpoint of increasing the dehalogenation efficiency. Preferably used. Among them, a carbon crystal compound, a metal-supported carbon compound, a metal-supported oxide, and a metal-supported composite oxide are preferable from the viewpoint of high safety in an alkaline atmosphere, and a metal-supported carbon compound having high microwave absorption is particularly preferable. These catalysts can be used individually or in combination of 2 or more types. In addition, a regenerated catalyst regenerated by the following method may be used.

  The catalyst used for the decomposition treatment of the present invention may be reused for the treatment of other containers after the regeneration treatment. The regeneration process of the catalyst may be performed by a known method. For example, the catalyst can be regenerated by washing the catalyst with an organic solvent such as acetone or a lower alcohol. There is no limitation on the washing time, and it may be determined appropriately according to the desorption status of the adsorbed organic halogen compound.

  The metal-supported carbon compound may be a carbon compound supporting a metal, but the metal-supported amount is 0.1 to 20 wt%, more preferably 0.1 to 10 wt% with respect to the total amount of the catalyst. preferable. Examples of the supported metal include iron, silver, platinum, ruthenium, palladium, and rhodium, and palladium, ruthenium, or platinum is preferable from the viewpoint of increasing the dehalogenation efficiency. Specific examples of the metal-supported carbon compound include Pd / C (palladium-supported carbon compound), Ru / C (ruthenium-supported carbon compound), and Pt / C (platinum-supported carbon compound).

  The catalyst such as a metal-supported carbon compound may be granular or honeycomb. In the case of a granular shape, it is necessary to fix the upper and lower sides of the catalyst layer with a mesh or the like. When it exceeds 10 mm, the specific surface area is insufficient, and when it is less than 75 μm, the mesh is clogged and the differential pressure becomes high. More preferably, it is 150 micrometers-5 mm. The catalyst particles are preferably as uniform as possible.

  According to the cracking treatment method of the present invention, the concentration of the organic halogen compound mixed in the oil becomes 0.5 ppm or less in a short time, so that the oil after the cracking treatment can be recovered and reused as fuel or the like. .

  In addition, according to the method for decomposing an organic halogen compound of the present invention, the organic halogen compound is decomposed and dehalogenated by heating with microwaves without applying hydrogen gas or heat from the outside. Although the mechanism is not clear, it is considered that the alkali compound promotes the dehalogenation reaction of the organic halogen compound, and the hydrogen radical from the hydrogen donor enters therein. Even at a site such as a transformer store, it is possible to safely treat difficult-to-decompose organic halogen compounds such as PCB simply by carrying out a circulation operation without preparing a new heating source.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited only to a following example. In the following examples and the like, “mass%” is abbreviated as “%” unless otherwise specified.

Example 1
10 L of Type 1 No. 2 actual deteriorated insulating oil was added to the pole transformer container, and 210 μL of KC-400 (biphenyl tetrachloride, manufactured by Kaneka Chemical Co., Ltd.) was added as PCB to prepare a test oil containing 21 ppm of PCB. To this was added 10 L of isopropyl alcohol (IPA) as a hydrogen donor (100% by volume of the test oil) and 100 g of KOH (1% of the test oil) as an alkali, followed by stirring to obtain an oil to be treated.

On the other hand, a catalyst (average particle diameter of about 1 mm) in which 5% palladium (Pd) was supported on granular activated carbon (trade name: Diahop 008) was prepared and dried at 70 ° C. for 8 hours. 2 kg of this catalyst was put into a catalyst filling apparatus, and the upper and lower sides were sandwiched between 100 mesh nets, and the catalyst was filled to form a catalyst layer (cross-sectional area: 330 cm ² ). A gear pump manufactured by EFNIC (ModelGPE-031, 12V DC) is attached to the outside of the container, a Teflon (registered trademark) tube having an inner diameter of 6 mm is attached to each pump, and one end is immersed in the bottom of the liquid to be treated. Was connected to an inlet provided at the top of the catalyst filling device (see FIG. 2).

The oil to be treated was extracted from the container with a pump and circulated through the container while continuously passing through the catalyst filling device at a rate of 1 L / min. In the meantime, the temperature of the liquid to be treated was continuously maintained at 60 ° C. by setting the temperature controller to 60 ° C. and continuously irradiating microwaves having a frequency of 2.45 GHz and a maximum output of 1.5 kW while controlling PID.
On the other hand, the liquid to be treated that circulated through the catalyst layer was allowed to flow out from a liquid reservoir provided at the bottom of the catalyst filling device, and the flowed out liquid was cooled by a cooling coil. The temperature of the effluent was 40 ° C.

  The treated oil treated with the catalyst filling device was returned to the container by opening the valve of the pipe, and the treated liquid in the container was periodically sampled. The PCB concentration in the sampled oil to be treated was analyzed using a gas chromatography mass spectrometer QP5050AW (hereinafter, “GC-MS”) manufactured by Shimadzu Corporation using DB1 (manufactured by J & W Scientific) as a capillary column. did.

  When the PCB concentration in the oil to be treated did not fall below the target of 0.5 ppm, the operation of returning the oil to be treated to the catalyst filling device was circulated and circulated again and then returned to the container.

(Example 2)
As in Example 1, except that 15 liters of isopropyl alcohol (IPA) as a hydrogen donor (150 vol% to test oil) and 100 g of KOH (1% to test oil) as alkali were added and stirred to obtain an oil to be treated. A decomposition treatment was performed.

(Comparative Example 1)
45 L of a Type 1 No. 2 actual deteriorated insulating oil was added to a 45 L column transformer, and 720 μL of KC-400 (biphenyl tetrachloride, manufactured by Kaneka Chemical Co., Ltd.) was added as a PCB to prepare a test oil containing 16 ppm of PCB. To this was added 9 L of isopropyl alcohol (IPA) as a hydrogen donor (20 vol% with respect to the test oil) and 474 g of KOH (1% with respect to the test oil) as an alkali, followed by stirring to obtain an oil to be treated.
On the other hand, a catalyst (average particle diameter of about 1 mm) in which 5% palladium (Pd) was supported on granular activated carbon (trade name: Diahop 008) was prepared and dried at 70 ° C. for 48 hours. 2 kg of this catalyst was put into a catalyst filling apparatus, and the upper and lower sides were sandwiched between 100 mesh nets, and the catalyst was filled to form a catalyst layer (cross-sectional area: 330 cm ² ).
Thereafter, the decomposition treatment was performed in the same manner as in Example 1. During this time, the microwave to be processed was irradiated while turning on / off the microwave with the maximum output of 1.5 kW without performing the cooling operation of the liquid to be processed. The temperature was maintained at 60 ° C. The catalyst was exchanged a total of 4 times until the PCB concentration in the oil to be treated fell below the target of 0.5 ppm. (Total amount of catalyst used is 10 kg)

  The above experimental results are summarized in Table 1.

As is clear from the above results, the example and the comparative example have the same amount of catalyst per amount of treated oil. Since the microwave irradiation efficiency is increased by PID control, the time required for decomposition until the target of 0.5 ppm is achieved can be halved compared to the case where cooling is not performed (comparative example). Since the IPA addition rate is high, it is considered that the effect by the microwave PID control and the cooling operation is easy.
On the other hand, when the cooling operation of the liquid to be processed was not performed (Comparative Example 1), the output control of the microwave was difficult because the IPA addition rate was low, and the time required for decomposition was long.

  The present invention provides a method that can be easily decomposed under normal pressure conditions without collecting contaminated oil. If the decomposition apparatus of the present invention is installed at a site such as a transformer storage, The dehalogenation treatment can be performed as it is on site. Therefore, according to the present invention, since a large amount of PCB can be rendered harmless on a practical scale, the practical value of the present invention is extremely great.

1 Pillar transformer 2 Liquid to be treated (mixed liquid)
3 Pillar transformer internal winding (coil)
DESCRIPTION OF SYMBOLS 4 Catalyst filling apparatus 5 Catalyst cartridge 6 Catalyst layer 7 Catalyst tank 8 Structure 9 Pump 10 Temperature sensor 11 Temperature controller 12 Microwave apparatus 13 Cooling water circulation apparatus 14 Cooling water flow regulator 15, 16, 17, 21 Line 18 Cooling coil 30 Vent

Claims (20)

A decomposition treatment method for decomposing an organic halogen compound contained in oil filled or stored in a container,
After adding a hydrogen donor and an alkali compound to the oil containing the organic halogen compound to obtain a mixed solution, a part of the mixed solution was taken out and circulated through a catalyst filling device disposed in the upper part of the catalyst tank. In the decomposition method for decomposing the organic halogen compound contained in the oil by irradiating the mixed liquid flowing through the catalyst filling device with microwaves while circulating in the rear container,
A decomposition treatment method characterized in that the mixed liquid circulated through the catalyst filling device is cooled in a liquid reservoir at the bottom of the catalyst tank and then circulated in a container. A decomposition treatment method for decomposing an organic halogen compound contained in oil filled or stored in a container,
After adding a hydrogen donor and an alkali compound to the oil containing the organic halogen compound to obtain a mixed solution, the mixed solution is taken out, and after passing through a catalyst filling device disposed in the upper part of the catalyst tank, the catalyst In the decomposition method for decomposing the organic halogen compound contained in the oil by irradiating the mixed liquid flowing through the catalyst filling device with microwaves while circulating in the filling device,
A decomposition treatment method characterized in that the mixed liquid circulated through the catalyst filling device is cooled in a liquid reservoir at the bottom of the catalyst tank and then circulated through the catalyst filling device.   The decomposition treatment method according to claim 1 or 2, wherein the mixed solution that has been circulated through the catalyst filling device is cooled at a temperature of 5 ° C or more than the temperature of the mixed solution in the catalyst filling device in a liquid reservoir at the bottom of the catalyst tank.   The temperature (T) of the liquid mixture in the catalyst filling device is in the range of 40 to 80 ° C., and the difference between the temperature of the liquid mixture and T in the liquid reservoir at the bottom of the catalyst tank is in the range of 10 to 30 ° C., The decomposition | disassembly processing method in any one of Claims 1-3.   The decomposition treatment method according to any one of claims 1 to 4, wherein the addition amount of the hydrogen donor is in the range of 50 to 200 vol% with respect to the oil containing the organic halogen compound.   The decomposition processing method according to claim 1, wherein the microwave output is controlled by PID control of a temperature controller.   A rod-like, tubular, or fiber-like structure formed of a heat-resistant material that transmits microwaves is disposed so that a part thereof protrudes from a catalyst layer in the catalyst filling device. The decomposition method according to any one of the above.   The decomposition | disassembly processing method in any one of Claims 1-7 whose said hydrogen donor is isopropyl alcohol.   The decomposition treatment method according to any one of claims 1 to 8, wherein the alkali compound is at least one compound selected from the group consisting of caustic soda, caustic potash, sodium alkoxide, potassium alkoxide, and calcium hydroxide.   The decomposition treatment method according to any one of claims 1 to 9, wherein an addition amount of the alkali compound is 0.1 to 10% (w / v) as a ratio to a hydrogen donor.   The decomposition treatment method according to claim 1, wherein the hydrogen donor and the alkali compound are added after the alkali compound is dissolved in advance in the hydrogen donor.   The decomposition treatment method according to claim 1, wherein the catalyst used in the catalyst filling device is a metal-supported carbon compound.   The decomposition treatment method according to any one of claims 1 to 12, wherein the oil is a hydrocarbon oil and the organic halogen compound is polychlorinated biphenyl.   The decomposition processing method according to claim 1, wherein the container is a pole transformer. A decomposition treatment apparatus for decomposing an organic halogen compound contained in oil filled or stored in a container,
(A) a catalyst filling device;
(B) a catalyst tank containing the catalyst filling device;
(C) a supply means for taking out a liquid mixture of oil, hydrogen donor and alkali compound in the container and supplying the mixture to the catalyst filling device;
(D) a microwave device for irradiating the catalyst filling device with microwaves;
(E) a cooling coil for cooling the mixed liquid stored in the liquid reservoir at the bottom of the catalyst tank;
The decomposition processing apparatus characterized by including at least.   The decomposition processing apparatus according to claim 15, wherein the catalyst tank further includes a discharge port for returning the mixed liquid discharged from the catalyst tank into the container.   The decomposition processing apparatus of Claim 15 or 16 with which the said microwave apparatus is provided with the temperature controller which measures and controls the temperature of a liquid mixture.   16. A rod-like, tubular, or fiber-like structure formed of a heat-resistant material that transmits microwaves is arranged in a dispersed manner so that a part thereof protrudes from a catalyst layer in a catalyst filling device. The decomposition processing apparatus in any one of -17.   The decomposition processing apparatus according to any one of claims 15 to 18, wherein the catalyst filling device includes a replaceable catalyst cartridge. The decomposition processing apparatus according to any one of claims 15 to 19, wherein the container is a pole transformer.

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