JP2000144274A - Method and apparatus for electrolytic treatment of zirconium waste - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide an electrolytic treatment method for converting zirconium waste into an oxide suitable for a disposal environment, without decreasing the treatment speed. Kind Code: A1 Abstract: In electrolysis using a nitric acid solution as an electrolytic solution, regarding the oxidation treatment of zirconium waste, electric conduction generated on the surface of the zirconium waste while heating the electrolytic solution to accelerate the electrolysis speed, and performing ultrasonic irradiation. Continuous peeling of a very low degree zirconium oxide thin film layer,
Apply pressure from above to the entire zirconium or zirconium alloy to accelerate the peeling of the zirconium oxide thin film layer formed on the surface.Continuously impact the entire zirconium or zirconium alloy to separate the zirconium oxide thin film layer formed on the surface. Accelerate. When the zirconium waste is relatively small and the surface is covered with oxide, the electrolyte is stirred to remove the zirconium oxide flakes from the electrolysis cell. Is sent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for treating zirconium waste, and more particularly to a method for treating zirconium waste such as spent fuel cladding tubes and plutonium concentrators. The present invention relates to a processing method and a processing apparatus.

[0002]

2. Description of the Related Art Spent fuel used in a nuclear power plant is transported to a reprocessing plant, where a fuel cladding tube made of zirconium is cut and dissolved in nitric acid. Uranium and plutonium dissolved in the nitric acid solution are separated, purified, and reused.

[0003] On the other hand, the cut fuel cladding tubes are stored in a water tank without any treatment. Storage of fuel cladding in a water tank
It is provisional and requires enormous storage space for storage. In addition, a device for maintaining water quality in the water tank is required. For this reason, there is a demand for the development of volume reduction and solidification treatment of the cut fuel cladding tubes.

[0004] In a reprocessing plant, equipment such as a plutonium concentrator, a dissolution tank, and an iodine ejection tank that handle nitric acid at a high temperature are made of zirconium metal. These devices will be disposed of after a period of use. Development of a method for reducing the volume of these devices as solid zirconium waste and solidifying it is required. As methods for treating zirconium metal, methods such as cutting, compression, and melting have been reported.

[0005] However, in these methods, it is necessary to control the atmosphere and treat the radioactive gas generated during the treatment in order to handle relatively active metals. For the final disposal of zirconium-containing metal waste, a method of burying it in the stratum can be considered.

[0006] In groundwater in the currently assumed formation environment, zirconium is most stable in the form of IV valence. In the treatment method of compressing, cutting, melting, and then filling in a container, water infiltration is considered for a long time, and in this case, zirconium is oxidized by the reaction with the infiltrated water and hydrogen gas is generated. Can be In this case, there is a concern that the soundness of the disposal facility may be impaired due to a chemical change of the metal waste into an oxide, a change in volume, an accumulation of generated gas, and the like.

[0007] A method for suppressing the spontaneous ignition of zirnium metal and an electrolytic treatment method for considering compatibility with final disposal, that is, ensuring the integrity of the disposal facility, are known.
However, in this electrolytic treatment method, as the electrolytic reaction proceeds, a zirconium oxide layer having a very low electric conductivity is generated on the surface of the zirconium waste, and the current during electrolysis is reduced, and the treatment speed is reduced.

[0008] Further, it is considered that waste having a tank structure is contaminated with radioactive material only in the contents for the purpose of use. In order to dispose of waste efficiently, removing only radioactive materials can be applied to waste disposal at lower cost. However, the above-mentioned electrolysis method only mentions a method of processing everything into an oxide.

[0009]

The problem of the conventional treatment (compression, cutting, and melting) of zirconium metal is the control of the gas system for suppressing ignition and the chemical change under the environmental conditions at the time of final disposal. Inevitable. In the above-described electrolysis technique for avoiding this, there is a problem that the processing speed during electrolysis is reduced.

[0010] Further, regarding waste having a tank structure, since the radioactive material is contaminated only on the inner surface, by removing this, the waste can be treated as non-radioactive waste. By performing such treatment, a reasonable and inexpensive treatment method can be examined, but the conventional method is a method of treating the entire amount into oxide, and a method of treating only the inner surface of the tank which is a contaminated portion. There are issues that are not considered.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is an electrolytic treatment method for converting zirconium waste into an oxide suitable for a disposal environment. An object of the present invention is to provide an electrolytic treatment method and an apparatus therefor.

Another object of the present invention is to provide a method and an apparatus for electrolytically treating zirconium waste, which can promote the separation of oxides generated on the surface of zirconium waste.

[0013]

According to a first aspect of the present invention, in a method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis, when a nitric acid solution is used as an electrolytic solution, the electrolysis speed is improved. Therefore, the electrolyte is heated.

According to a second aspect of the present invention, there is provided a method for oxidizing a solid waste composed of zirconium or a zirconium alloy by electrolysis, in order to maintain the processing speed during electrolysis, while performing ultrasonic irradiation while applying zirconium or zirconium alloy surface. Is characterized in that the zirconium oxide thin film layer having very low electric conductivity is continuously peeled off.

According to a third aspect of the present invention, when the zirconium waste is relatively small and the surface is covered with an oxide,
In order to increase the current efficiency, only the waste is placed in the electrolytic solution, and in order to maintain the processing speed during the electrolysis, pressure is applied to the entire zirconium and zirconium alloy from above, and zirconium oxide generated on the surface of the waste It is characterized in that the peeling of the thin film layer is accelerated.

According to a fourth aspect of the present invention, when the zirconium waste is relatively small and the surface is covered with an oxide,
In order to increase the current efficiency, only the waste is placed in the electrolytic solution, and in order to maintain the processing speed during the electrolysis, the whole zirconium and the zirconium alloy are continuously impacted, and the zirconium oxide thin film layer generated on the surface is It is characterized in that peeling is accelerated.

According to a fifth aspect of the present invention, when the zirconium waste is relatively small and the surface is covered with an oxide,
The method is characterized in that the electrolyte is agitated in order to keep the electrolyte normal in the electrolytic bath even so that the oxide generated by the electrolysis treatment can be recovered without inhibiting the electrolysis.

According to a sixth aspect of the present invention, when the zirconium waste is relatively small and the surface is covered with an oxide,
In order to continuously drop the oxide generated by the electrolytic treatment from the waste storage cell, a large number of pores are provided on the bottom surface of the waste storage cell, and the electrolyte is circulated in the waste storage cell. And

According to a seventh aspect of the present invention, when the zirconium waste is relatively small and the surface is covered with an oxide,
In order to increase the current efficiency, only the waste is placed in the electrolytic solution in the electrolytic cell, heated to accelerate the peeling of the zirconium oxide thin film layer on the surface of the waste, and the heating section and the entire electrolytic cell are heated. Is irradiated with ultrasonic waves, and further, pressure and impact are applied to the entire waste.

According to the invention of claim 8, when the zirconium waste has a structure like a tank, an electrolytic solution is injected into the tank to remove only radioactive substances adhering to the inner surface of the tank, and a cathode is inserted therein. And decontamination of radioactive substances by using only waste as an anode and electrolyzing only the inner surface of the tank.

According to a ninth aspect of the present invention, there is provided an electrolytic cell containing an electrolytic solution, an electrolytic cell provided in the electrolytic cell, having a flow path hole for the electrolytic solution and containing zirconium waste, and an electrolytic cell containing the zirconium waste. An anode in contact with an object, a cathode in contact with the electrolytic solution in the electrolytic cell, a DC power supply for applying a DC voltage to the cathode and the anode, and a heating medium attached to the electrolytic cell for heating the electrolytic solution. A stirrer or an ultrasonic vibrator for stirring the electrolytic solution.

According to a tenth aspect of the present invention, the electrolytic cell is provided with an off-gas processing device having a function of recovering hydrogen gas, carbon dioxide gas, nitrogen oxide, or the like generated during the oxidation process.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of an apparatus for electrolytically treating zirconium waste according to the present invention will be described with reference to FIG. In FIG. 1, reference numeral 1 denotes an electrolytic cell, and an upper lid 2 is detachably attached to an upper end opening of the electrolytic cell 1. An electrolytic cell 3 is installed in the electrolytic cell 1 via a support 4, and a perforated plate 5 having a large number of pores serving as electrolyte flow holes is attached to the bottom of the electrolytic cell 3. ing.

In the electrolysis cell 3, zirconium waste 6 as an object to be electrolyzed is stored on a perforated plate 5, and a plate-shaped anode 7 is placed on the zirconium waste 6. The zirconium waste 6 is, for example, zirconium metal or an alloy thereof such as a small fragment of a spent fuel cladding tube, a small fragment of a plutonium concentrating can 4, or the like.

An electrolytic solution 8 such as a nitric acid solution is stored in the electrolytic bath 1, and a cathode 9 is immersed and immersed in the electrolytic solution 8 between the inner surface of the electrolytic bath 1 and the outer surface of the electrolytic cell 3. . An anode 7 and a cathode 9 are respectively connected to a lead wire 10 penetrating the upper lid 2,
11 connects to a DC power supply 12. The lead wires 10 and 11 penetrate the insulator 13 attached to the upper lid 2 to maintain electrical insulation between the lead wires 10 and 11 and the electrolytic cell 1.

The electrolytic cell 1 is set on a base 14,
The base 14 is provided with a magnetic stirrer 15. A stirrer 16 is arranged on the bottom surface in the electrolytic cell 1 facing the magnetic stirrer 15. Magnetic stirrer
The starter 15 rotates the stirrer 16 and moves around to move the electrolyte 8
Is stirred.

A jacket 17 for heating the electrolytic solution 8 is attached to the outer surface of the electrolytic cell 1 from substantially the center to the lower part, and a heating medium line 18 is connected from the upper right to the lower left of the jacket 17. The line 18 is provided with a temperature controller 19 and a circulation pump 20.

The heating medium is maintained at a predetermined temperature by the temperature controller 19 and the circulation pump 20 is driven to supply the heating medium to the jacket 17 and circulate the heating medium line 18. When the nitric acid solution is used as the electrolytic solution 8 by heating the electrolytic solution 8 in the electrolytic cell 1 with a heating medium, the electrolysis speed can be improved.

In this embodiment, the electrolytic cell 3 in the electrolytic cell 1 is filled with the electrolytic solution 8 flowing through the perforated plate 5, and the zirconium waste 6 is subjected to an electrochemical reaction when a voltage is applied to the cathode 9. Occurs, and the metal (Zr) base material of the zirconium waste 6 dissolves in the electrolytic solution 8. By dissolving the metal, the radioactive substance attached to the metal surface can be removed.

Further, an ultrasonic vibrator can be used instead of the stirrer 16. When an ultrasonic vibrator is used, the ultrasonic vibrator is connected to an ultrasonic generator, and the ultrasonic vibrator irradiates ultrasonic waves into the electrolytic solution 8. This allows
The processing speed during the electrolysis can be maintained, and the zirconium oxide thin film layer having extremely low electric conductivity generated on the surface of the zirconium waste 6 can be continuously peeled off while performing ultrasonic irradiation.

Next, embodiments of the electrolytic treatment method for zirconium waste according to the present invention will be described with reference to Examples 1 to 6. (Embodiment 1) Embodiment 1 of the method of the present invention will be described with reference to FIGS.

This embodiment corresponds to the invention of claim 1 and relates to a method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis. In the case of using a nitric acid solution as an electrolytic solution, the electrolytic reaction speed is improved. In this case, the electrolytic solution is heated.

FIG. 2 schematically shows an electrolytic treatment test apparatus, in which reference numeral 21 denotes an electrolytic cell, 22 denotes simulated waste, 23 denotes zirconium oxide, 24 denotes an anode, 25 denotes a cathode, and 26 denotes an electrolyte. It is shown schematically.

Simulated waste 22 called hulls such as zirconium and zirconium alloy generated at the time of dismantling a radioactive material handling facility such as a nuclear power plant is placed in an electrolytic treatment tank 21 shown in FIG. It was set up to make it. Note that the surface of the simulated waste 22 is oxidized and covered with zirconium dioxide.

The zirconium alloy was electrolytically treated using this electrolytic treatment test apparatus. As the electrolytic solution 26, a 10N nitric acid (HNO ₃ ) solution was used. Cathode with platinum treatment
25 is immersed in an electrolytic solution 26, and the anode 24, which has been subjected to a platinum treatment, is brought into contact with zirconium and a zirconium alloy outside the liquid,
The electrolytic treatment was performed by applying a DC voltage of 15 V for 1 hour from the power supply unit.

Although electrolysis did not occur in the electrolysis at room temperature, electrolysis occurred at a temperature of 40 ° C. or higher (see FIG. 3). In addition, the time at which the electrolysis was started tended to become shorter as the temperature increased.

(Embodiment 2) Embodiment 2 corresponds to the first aspect of the present invention. As in Example 1, electrolysis was performed using the electrolytic processing test apparatus shown in FIG. Using the nitric acid concentration of the electrolytic solution 26 as a parameter, electrolysis was performed at room temperature and in a case where the electrolytic solution 26 was heated to 80 ° C. respectively. The electrolytic treatment was performed by applying a constant DC voltage of 14 V for one hour. The electrolysis start time for each case is shown in FIG. At room temperature, electrolysis was started after a certain period of time in all cases, whereas at 80 ° C., electrolysis was started immediately after energization, and oxides were constantly generated.

(Embodiment 3) This embodiment 3 is characterized by claims 2 and 4.
Corresponding to the invention of the above. That is, regarding the oxidation treatment of zirconium waste by electrolysis, in order to maintain the processing speed during electrolysis, a zirconium oxide thin film layer with extremely low electrical conductivity generated on the surface of zirconium waste is continuously formed while performing ultrasonic irradiation. To peel off.

When the zirconium waste is relatively small and the surface is covered with an oxide, an oxidizing method having a structure in which only the waste is disposed in a liquid and oxidized to improve the current efficiency. In order to maintain the processing speed during electrolysis, the impact is continuously applied to the entire zirconium and zirconium alloy to accelerate the peeling of the zirconium oxide thin film layer formed on the surface.

Electrolysis was performed using the electrolytic processing apparatus shown in FIG. The electrolyte solution 8 contains 10 N nitric acid (H
Using a NO ₃ ) solution, a DC voltage of 14 V was applied from a DC power supply 12 for 1 hour to perform an electrolytic treatment. FIG. 5 shows the change with time of the current when the ultrasonic wave of 400 W was irradiated, and FIG. 6 shows the change with time of the current without irradiation.

The current value immediately after the start of electrolysis is high, but in any case, the current value decreases with time. However,
In the case where the ultrasonic irradiation was performed, the minimum value of the current was 10 A, whereas in the case where the irradiation was not performed, almost no current flowed after 45 minutes, and the electrolytic treatment was stopped.

In the case where ultrasonic irradiation was not performed, immediately after the current stopped flowing (after 45 minutes), the electrolytic cell was applied 0.98 kg · m ² / sec ² from the cell top to the electrolytic cell 10 times for 30 seconds.
Made a shock. As a result, current flows after 50 minutes,
Electrolysis was started again.

(Embodiment 4) This embodiment 4 is a third embodiment of the present invention.
This corresponds to the inventions of 5, 6, and 7. That is, when the zirconium waste is relatively small and the surface is covered with an oxide, in order to increase the current efficiency, only the waste is disposed in a liquid and an oxidation treatment apparatus having a structure for performing oxidation treatment is used. In order to maintain the processing speed at the time, pressure is applied to zirconium and the zirconium alloy as a whole from the top to accelerate the peeling of the zirconium oxide thin film layer formed on the surface.

When the zirconium waste is relatively small and the surface is covered with an oxide, the oxide has a pore structure that does not hinder the electrolysis and allows the oxide generated by the electrolytic treatment to be recovered. Regarding the recovery container, the electrolytic solution is stirred to keep the properties of the electrolytic solution in the electrolytic cell uniform.

When the zirconium waste is relatively small and the surface is covered with an oxide, the oxide generated by the electrolytic treatment is continuously dropped from the lower part from the waste storage cell, so that the bottom is thin. For a waste storage cell having a hole structure, an electrolyte is circulated in the waste storage cell.

Furthermore, when the zirconium waste is relatively small and the surface is covered with an oxide, an oxidation treatment method having a structure in which only the waste is placed in a liquid and oxidized in order to increase current efficiency. , A heating section for accelerating the peeling of the zirconium oxide thin film layer on the surface, a structure capable of irradiating the entire electrolytic cell with ultrasonic waves, and further applying pressure and applying an impact to the entire zirconium waste. As in Example 3, electrolysis was performed using the electrolytic processing apparatus shown in FIG. A DC voltage of 350 W is applied to the electrolyte for 1 hour.
The electrolytic treatment was performed while irradiating the ultrasonic waves. In addition, a stirrer was put into the electrolytic cell 1, and the electrolytic solution 8 was stirred from outside the electrolytic cell 1 with a magnetic stirrer 15 so as to be uniform in the electrolytic cell 1 and the electrolytic cell 3. At this time, a load of 5 kg was applied to the simulated waste inside the electrolysis cell 3.

FIG. 7 shows the change over time of the current. Start of electrolysis 15
After one minute, the current value showed a remarkable decrease. Sixteen minutes after the start of electrolysis, an impact of 0.98 kg · m ² / sec ² was applied to the electrolysis cell 3 from the top of the electrolysis cell 3 for 15 seconds five times. Immediately after that, the current value was almost constant at 20 A, and the electrolysis occurred steadily without reducing the processing speed.

(Embodiment 5) Embodiment 5 corresponds to the eighth aspect of the present invention. In other words, if the zirconium waste has a tank-like structure, an electrolyte is injected into the tank to remove only radioactive substances adhering to the tank inner surface, a cathode is placed inside, and the waste is treated as an anode. To electrolyze only the inner surface of the tank to enable decontamination of radioactive materials.

In the case where the zirconium waste has a tank-like structure, a heating section for accelerating the peeling of the zirconium oxide thin film layer on the inner surface of the tank in order to enhance the current efficiency in the treatment method, and an electrolytic cell A structure capable of irradiating the whole with ultrasonic waves is provided so that only the inner surface of the tank of the electrolytic treatment device can be subjected to electro-release dyeing.

A 10 N nitric acid solution was added as an electrolytic solution to a simulated waste in which a pipe made of Zircaloy was cut and a lower part was closed with a silicon stopper cured with a seal made of tetrafluoroethylene resin. A platinum wire was placed inside, a DC power supply was connected so that the simulated waste became an anode, and the platinum wire became a cathode, and a DC voltage of 14 V was applied from the power supply for 10 minutes to perform electrolysis.

During electrolysis, it was confirmed that black flakes were continuously peeled from the entire surface in contact with the electrolytic solution. The black flaky substance accumulated inside after completion of the electrolysis was recovered and analyzed for composition by X-ray diffraction. As a result, it was found that the substance was zirconium dioxide.

(Embodiment 6) Embodiment 6 corresponds to the tenth aspect of the present invention. That is, with respect to an off-gas system in which the zirconium waste has a tank-like structure, an off-gas processing device having a function of collecting hydrogen gas, carbon dioxide gas, nitrogen oxide, and the like generated during the oxidation treatment is provided.

In the upper part of the simulated waste described in Example 5, 10
An offgas line equipped with an air-washing bottle containing 250 ml of a specified sodium hydroxide aqueous solution was installed, a 10N nitric acid solution was used as an electrolyte, a platinum wire was placed inside, a simulated waste was used as the anode, and the platinum wire was used as the cathode. A DC power supply was connected so that a DC voltage of 14 V was applied from the power supply for one hour.

Incidentally, a nitrogen carrier gas was introduced into the inside at a flow rate of 1 l / min. At the time of electrolytic NO _x gas it was confirmed that has occurred. However, the NO _x gas concentration at the off-gas line outlet was below the detection limit.

[0055]

According to the present invention, there is provided a method for electrolytically oxidizing zirconium waste composed of zirconium or a zirconium alloy. The present invention relates to a method for heating an electrolytic solution, irradiating ultrasonic waves, and applying pressure to the entire zirconium and zirconium alloy from above. , Zirconium and the entire zirconium alloy can be continuously impacted to avoid a reduction in the electrolytic reaction rate.

In particular, when the solid waste is relatively small and the surface is covered with an oxide, the electrolytic solution is stirred and the electrolytic solution is fed into the waste storage cell, so that the electrolytic solution is discharged. It is possible to ensure uniformity of solution properties in the vicinity of the reaction portion, and to remove flakes of zirconium oxide having extremely low electric conductivity from the inside of the electrolytic cell. Further, for waste having a tank structure, only radioactive substances adhering to the tank inner surface can be removed.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view schematically showing a part of an embodiment of an apparatus for electrolytically treating zirconium waste according to the present invention.

FIG. 2 is a longitudinal sectional view schematically showing an electrolytic treatment test apparatus used in the embodiment of the electrolytic treatment method for zirconium waste according to the present invention.

FIG. 3 is a characteristic diagram showing the dependence of the temperature of the electrolyte on the oxidation reaction start time in Example 1 of the electrolytic treatment and preservation of zirconium waste according to the present invention.

FIG. 4 is a comparative diagram showing the effect of heating on electrolysis start time in Example 2 at room temperature.

FIG. 5 is a characteristic diagram showing a change in current value during ultrasonic irradiation (400 W) in Example 3.

FIG. 6 is a characteristic diagram showing a change in a current value when ultrasonic waves are not irradiated in Example 3.

FIG. 7 is a characteristic diagram showing a change in current value during ultrasonic irradiation (350 W) in Example 4.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Electrolysis tank, 2 ... Top lid, 3 ... Electrolysis cell, 4 ... Support,
5 ... plate, 6 ... zirconium waste, 7 ... anode, 8 ...
Electrolyte, 9 ... Cathode, 10, 11 ... Lead wire, 12 ... DC power supply,
13 ... insulator, 14 ... base, 15 ... magnetic stirrer,
16… Stirrer or ultrasonic vibrator, 17… Jacket, 18…
Heating medium line, 19 ... temperature controller, 20 ... circulation pump, 21 ...
Electrolytic treatment tank, 22: simulated waste, 23: zirconium oxide (ZrO2), 24: anode, 25: cathode, 26: electrolytic solution.

Continuing from the front page (72) Inventor Masaaki Kaneko 1st Toshiba R & D Center, Komukai-ku, Kawasaki City, Kanagawa Prefecture (72) Inventor Shinya Miyamoto 1st Toshiba-cho, Komukai Toshiba-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Toshiba Research and Development Center Co., Ltd. (72) Inventor Jun Nakajima 66-2 Horikawacho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture Toshiba Engineering Corporation (72) Inventor Nobuyuki Ikenaga 66-2, Horikawacho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture F-term in Toshiba Engineering Corporation (reference) 4K001 AA31 DB05 DB15

Claims (10)

[Claims] 1. A method for oxidizing zirconium waste composed of zirconium or zirconium alloy by electrolysis, wherein a nitric acid solution is used as an electrolytic solution, wherein the electrolytic solution is heated in order to improve the electrolysis speed. Of electrolytic treatment of waste zirconium waste. 2. In the method for oxidizing zirconium waste composed of zirconium or zirconium alloy by electrolysis, in order to maintain the processing speed during electrolysis, electricity generated on the surface of the zirconium waste while performing ultrasonic irradiation. A method for electrolytically treating zirconium waste, comprising continuously peeling a zirconium oxide thin film layer having a very low conductivity. 3. The method for oxidizing zirconium waste composed of zirconium or zirconium alloy by electrolysis, wherein the zirconium waste is relatively small,
When the surface is covered with an oxide, only the zirconium waste is placed in an electrolytic solution in order to increase current efficiency, and a pressure is applied to the entire zirconium waste from above in order to maintain a processing speed during electrolysis. And accelerating the separation of the zirconium oxide thin film layer formed on the surface of the zirconium waste. 4. A method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis, wherein the zirconium waste is relatively small,
When the surface is covered with an oxide, only the zirconium waste is disposed in an electrolytic solution in order to increase current efficiency, and in order to maintain a processing speed during electrolysis, the zirconium waste is continuously dispersed throughout the zirconium waste. A method for electrolytically treating zirconium waste, comprising applying an impact to accelerate the separation of a zirconium oxide thin film layer formed on a surface. 5. The method for oxidizing zirconium waste composed of zirconium or zirconium alloy by electrolysis, wherein the zirconium waste is relatively small,
When the surface is covered with oxide, the electrolyte is agitated to keep the normality of the electrolyte in the electrolytic cell uniform so that the oxide generated by the electrolytic treatment is not hindered and the oxide generated by the electrolytic treatment is recovered. Method for electrolytic treatment of zirconium waste. 6. A method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis, wherein the zirconium waste is relatively small,
When the surface is covered with oxide, the oxide generated by the electrolytic treatment is continuously dropped from the waste storage cell. A method for electrolytically treating zirconium waste, wherein the method is circulated in the waste storage cell. 7. A method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis, wherein the zirconium waste is relatively small,
When the surface is covered with an oxide, only the zirconium waste is placed in the electrolytic solution in the electrolytic cell to increase the current efficiency, and the peeling of the zirconium oxide thin film layer on the zirconium waste surface is accelerated. And heating the heating section and the entire electrolytic cell with ultrasonic waves, and further applying pressure and impact to the entire zirconium waste. 8. A method for oxidizing zirconium waste composed of zirconium or a zirconium alloy by electrolysis, wherein when the zirconium waste has a tank-like structure, only radioactive substances adhering to the tank inner surface are removed. In order to remove the zirconium waste, the electrolyte is injected into the tank and a cathode is arranged, the zirconium waste is used as an anode, and only the inner surface of the tank is electrolyzed to decontaminate the radioactive material. Electrolytic treatment method. 9. An electrolytic cell containing an electrolytic solution, an electrolytic cell installed in the electrolytic cell, having a flow path hole for the electrolytic solution, and containing zirconium waste, and an anode in contact with the zirconium waste. A cathode for contacting the electrolytic solution in the electrolytic cell, a DC power supply for applying a DC voltage to the cathode and the anode, a heating medium line attached to the electrolytic cell for heating the electrolytic solution, An electrolyzer for zirconium waste, comprising a stirrer or an ultrasonic vibrator for stirring a liquid. 10. The apparatus according to claim 9, wherein the electrolytic cell is provided with an off-gas processing device having a function of recovering hydrogen gas, carbon dioxide gas, nitrogen oxide, or the like generated during the oxidation treatment. Electrolytic treatment equipment for zirconium waste.