WO2015037630A1

WO2015037630A1 - Technique and treatment method for converting one element to another element and technique and method for detoxifying radioactive substances such as radioactive cesiums-137 and -134 by using both energy produced by high-frequency vibration stirring and energy produced by rupture of nano/microbubbles generated by electrolysis of water with vibrating blades of stirrer as both electrodes

Info

Publication number: WO2015037630A1
Application number: PCT/JP2014/073960
Authority: WO
Inventors: 大政　龍晋
Original assignee: 日本テクノ株式会社
Priority date: 2013-09-11
Filing date: 2014-09-10
Publication date: 2015-03-19
Also published as: JP2015055527A

Abstract

A technique and treatment method for converting one element to another element, and a system for detoxifying cesium-134, cesium-137, and the like are provided with a treatment tank (1), a high-frequency vibrating motor (3), two vibrating rods (4) extending toward the bottom of the treatment tank (1) coupled to the motor (3), and a high-frequency vibration stirring device configured to include multistage vibrating blades (5) mounted to the lower parts of the vibrating rods (4). By controlling the motor (3) by an inverter (6) and vibrating the multistage vibrating blades (5) at a frequency of 100-200 Hz in a solution containing radioactive substances in the treatment tank (1), the detoxification of the radioactive substances progresses. Further, by performing electrolysis using the multistage vibrating blades (5) also as electrodes, the conversion of an element and the effect of detoxification are greatly improved by intense energy produced by rupture of nano/microbubbles generated at that time. Furthermore, this element conversion technique enables calcium to be transmuted into precious cobalt or nickel.

Description

Technology and processing method for converting from one element to another, and radioactivity using both the energy of high-frequency vibration agitation and the burst energy of nano / micro bubbles generated by water electrolysis using the vibration blades of the agitator as both electrodes Techniques and methods for detoxifying radioactive materials such as cesium 137 and 134

The present invention shares the energy of high-frequency vibration agitation and the burst energy of nano / micro bubbles generated by electrolysis of water using the vibration blades of the high-frequency vibration agitator as both poles. For example, radioactive cesium 137 and 134 are constant. The present invention relates to an element conversion from barium to platinum or the like by time treatment, that is, a technique and a processing method for converting from one element to another element, and a system and a processing method for detoxifying radioactive materials such as radioactive cesium 137 and 134.

Becquerel discovered in 1896 that radiation that was extremely harmful to the human body emerged from uranium ore, and atomic bombs and nuclear power generation that emit such radioactive elements were developed around the time of World War II, Although more than a century has passed since discovery, human beings are unable to find an effective way to detoxify radioactive elements. However, due to the accident at the Fukushima Daiichi Nuclear Power Station following the Great East Japan Earthquake on March 11, 2011, the demand for detoxification of radioactive elements is increasing.

There are radioactive elements cesium 134 and cesium 137 released in the atmosphere from the Fukushima Daiichi Nuclear Power Station, and their half-lives are about 2 years and about 30 years, respectively. Means that it takes a long time. In principle, detoxification is possible, but it is necessary to input a large amount of energy, and so far no technically effective means has been obtained. The URL (for example, Non-Patent Document 1) has information that the radioactive cesium is detoxified by photosynthetic bacteria and bacteria, but based on this, there is no report that the detoxification of the radioactive substance has been put into practical use. . At present, no method for industrial detoxification has been found. When detoxifying, it is considered necessary to put a large amount of energy locally into the radioactive element.

Also, regarding element conversion, since it is necessary to input a large amount of energy as in the case of detoxification, it has not been put into practical use at present.

The inventor previously generated water by electrolyzing water with special vibration agitation to generate nano / micro bubbles (which are fine bubbles of oxygen and hydrogen gas), which generate energy. I have confirmed that. In view of the above, the present invention has an object to render a radioactive substance harmless by generating strong energy generated when the nano / micro bubbles burst.

It is also an object to easily convert an element into an arbitrary element with a simple device.

The above problem is solved by any one of the following configurations (1) to (10).

(1) A treatment tank, a high-frequency vibration motor fixed to the upper stage of the treatment tank, two vibration bars extending downward from the treatment tank connected to the stage, and a lower part of the vibration bar A high-frequency vibration agitating device configured to include the multi-stage vibration blade, wherein the high-frequency vibration motor is controlled by an inverter, and the multi-stage vibration blade is placed in a liquid containing a radioactive substance in the treatment tank. And a detoxification system such as cesium 134 and cesium 137, which is characterized in that the radioactive substance in the liquid is detoxified by vibrating at a frequency of 100 to 200 Hz.

(2) In the multistage vibrating blades attached to the two vibrating bars, the first vibrating blade is physically and electrically connected to the right vibrating bar and physically connected to the left vibrating bar. However, the second vibrating blade is physically connected to the first right vibrating bar, but is electrically insulated from the left vibrating bar. Is physically and electrically connected, and as described above, a plurality of vibrating blades are electrically connected, and the left and right vibrating bars are electrically insulated by alternately repeating insulation on the left and right vibrating bars. (1), wherein a DC power source is connected to the left and right vibrating rods via a rectifier, and an electrolysis circuit is formed in which the plurality of vibrating blades alternately serve as anodes and cathodes. To convert from the elements described in 1 to other elements, and cesium 1 Detoxification systems, such as 4 and cesium-137.

(3) A pipe is provided at the top of the treatment tank, and the pipe is connected to the top of the bubbling tank so that radioactive cesium is not released into the atmosphere, and electrolysis in the treatment tank is performed in the liquid of the bubbling tank. The oxyhydrogen gas (OHMASA-GAS) generated in step (2) is blown into the element, the technology for converting from one element to another element described in (2) above, and cesium 134 and cesium 137 Detoxification system.

(4) A step of pouring radioactive contaminated water into the treatment tank of the electrode combined high frequency stirrer, a step of energizing by setting the frequency of the high frequency stirrer with an inverter, a step of detoxifying for a predetermined time, and the electrode combined use A treatment method for converting from one element to another element, and a detoxification method for cesium 134, cesium 137, and the like, including a step of turning off the power of the high-frequency stirring device.

(5) The step of pouring radioactive contaminated water into the treatment tank of the electrode combined type high-frequency agitator, the step of pouring into the treatment tank so that the potassium hydroxide concentration becomes 3%, and the frequency of the high-frequency agitator is set by an inverter. Energizing, turning on the rectifier for electrolysis, setting the electrolysis current value to DC7V, 11A, performing detoxification for a predetermined time, and turning off the power of the electrode combined high-frequency agitator And a detoxification method such as cesium 134 and cesium 137.

(6) The processing method for converting from one element to another, and cesium 134 and cesium according to (4) or (5), wherein the frequency of the high-frequency stirrer is set to 140 to 180 Hz Detoxification method such as 137.

(7) The detoxification treatment temperature is set to 20 to 40 ° C., the treatment method for converting from one element to another element according to (4) or (5), and cesium 134 and cesium 137 Detoxification method.

(8) The treatment method for converting from one element to another as described in (4) or (5) above, wherein the detoxification treatment period is 30 to 60 days, cesium 134, cesium 137, etc. Detoxification method.

(9) A step of introducing 0.5% concentration of calcium chloride into the treatment tank of the electrode combined type high-frequency agitator, a step of energizing by setting the frequency of the high-frequency agitator with an inverter, a power supply of the rectifier for electrolysis, and electrolysis Including a step of setting the current value to DC7V, 11A, a step of performing a predetermined element conversion treatment, and a step of turning off the power of the electrode combined type high-frequency stirrer, from calcium to cobalt, nickel, iron, copper, etc. Processing method to convert to element.

(10) It is characterized in that, in place of the step of adding calcium chloride, a step of adding a 10-30% slurry solution obtained by mixing hen egg shells pulverized to a particle size of several μm to several tens of μm with pure water is provided. The processing method of converting from calcium as described in said (9) to elements, such as cobalt, nickel, iron, copper.

The fact that the present invention has made it possible to detoxify radioactive elements at a low cost by simple technology, and to be able to convert calcium into valuable cobalt and nickel, it is a great thing that remains in human history. It can be said that it is an invention.

In addition, this innovative technology that makes it possible to select the processing conditions using this element conversion technology and obtain the necessary elements when needed is a highly conducive tool for creating new technological fields in the future. is there.

It is sectional drawing of an electrode combined type high frequency vibration stirring apparatus, A is front sectional drawing, B is side sectional drawing Cross section of bubbling tank Enlarged view of the multistage vibrating blade part of the electrode combined type high frequency vibration stirring apparatus shown in FIG.

The system used for detoxifying the radioactive cesiums 134 and 137 includes the electrode combined high-frequency vibration agitator shown in FIG. 1 and the bubbling tank (cushion tank) shown in FIG. The electrode combined high-frequency vibration stirrer is made of transparent heat-resistant resin and is equipped with a treatment tank 1 with a width of 200 mm, a depth of 300 mm, and a height of 250 mm. The tank capacity is about 12L. A high-frequency vibration motor 3 (200 V × 150 W) is fixed to the upper stage of the processing tank 1, and two vibrating bars 4 are connected to this stage, and the vibrating bar 4 extends downward into the processing tank 1. Yes. A multistage vibrating blade 5 is attached to the lower part of the vibrating bar 4. The high-frequency vibration motor 3 can be set so that the multistage vibration blade 5 vibrates at a frequency of 100 to 200 Hz in the liquid of the processing tank 1 by controlling using the inverter 6.

As shown in the enlarged view of the multistage vibrating blade portion in FIG. 3, two multistage vibrating blades 5 are attached to the vibrating rod 4, but the first vibrating blade is physically and electrically connected to the right vibrating rod. The left vibrating bar is physically connected, but is electrically insulated by the insulator 7. The second vibrating blade is physically connected to the first right vibrating bar, but is electrically insulated by the insulator 7 and physically and electrically connected to the left vibrating bar. Yes. In this way, the left and right vibrating bars are electrically insulated by electrically connecting the vibrating blades and alternately repeating the insulation between the left and right vibrating bars. Therefore, it is possible to form a DC voltage application circuit, that is, an electrolysis circuit, in which a DC power source is connected to the left and right vibrating bars via the rectifier 8 and the plurality of vibrating blades 5 are alternately anodes and cathodes.

With the above-described configuration, the processing tank 1 can be operated to perform only high-frequency vibration or electrolysis simultaneously with high-frequency vibration. When electrolysis is performed, a DC voltage (DC 12 V × 20 A) is applied to the two vibrating bars 4 via the rectifier 8.

FIG. 2 is a cross-sectional view showing a bubbling tank, that is, a cushion tank made of a transparent resin and having a diameter of 100 mm and a height of 230 m. When the liquid level is set to 190 mm, the liquid volume is about 1.6 L. The bubbling tank is provided so that radioactive cesium accompanies the oxyhydrogen gas (OHMASA-GAS) generated by electrolysis in the vibration stirrer and is not released into the atmosphere. From the top of the bubbling tank, potassium hydroxide 3 It is connected with the top part of the processing tank 1 with piping so that the gas produced | generated in the processing tank 1 of the high frequency vibration stirrer may be blown into% aqueous solution.

Using this system, radioactive cesium was detoxified by the following operation procedure. The contaminated water used for detoxification was collected on October 17, 2012 at a certain place in Fukushima Prefecture. The procedure for detoxification with only high-frequency stirring is as follows.
1) Charge 12 L of radioactively contaminated water 2 to the treatment tank 1 of the high-frequency stirrer that also serves as an electrode.
2) The inverter 6 sets the frequency of the high-frequency vibration motor 3 and energizes it.
3) A detoxification process is performed for a predetermined time.
4) Turn off the high-frequency vibration motor 3.
5) After stirring and homogenizing the contaminated liquid 2 in the treatment tank 1 for 3 minutes, 1 L of the treatment liquid is sampled and the amount of radioactive element is measured.

The amount of radioactive element in the final process was measured by operating a germanium semiconductor detector (manufacturer: PGY, model: NIGC 16190 SD) for 3600 seconds (1 hour).

The procedure for detoxification using high-frequency agitation and electrolysis in combination with the expectation of the powerful burst energy effect of nano / micro bubbles generated during water electrolysis is as follows.
1) Charge 12 L of radioactively contaminated water 2 to the treatment tank 1 of the high-frequency stirrer that also serves as an electrode.
2) The treatment tank 1 is charged so that the potassium hydroxide concentration is 3%.
3) The inverter 6 sets the frequency of the high-frequency vibration motor 3 and energizes it.
4) Turn on the rectifier 8 for electrolysis.
5) Set the electrolysis current value to DC7V, 11A (this starts the detoxification process). 6) A detoxification process is performed for a predetermined time.
7) Turn off the rectifier 8 for electrolysis.
8) Turn off the high frequency vibration motor 3.
9) After stirring and homogenizing the contaminated liquid 2 in the treatment tank 1 for 3 minutes, 1 L of the treatment liquid is sampled and the amount of radioactive element is measured.

For the measurement of the amount of radioactive element, the same apparatus as in the case of only the high frequency stirring apparatus was used.

As described above, an example of the vibration agitation method has been described. Patent No. 1941498, Patent No. 2707530, Patent No. 262388, Patent No. 2767777, Patent No. 2852878, Patent No. 2911359, obtained by the inventor, Japanese Patent No. 2911393, Japanese Patent No. 29898624, Japanese Patent No. 29898440, Japanese Patent No. 299217, Japanese Patent No. 3035114, Japanese Patent No. 3244334, Japanese Patent No. 3142417, Japanese Patent No. 3209984, Japanese Patent No. 10-369453, Japanese Patent No. 3196890. Patent Nos. 2,298,440, JP-A-10-309453, JP-A-3196890, JP-A-2000-317295, JP-A-2002-210341, JP-A-2009-028667, and published patents As described in the application It goes without saying that the dynamic stirrer can be used.

As for the method of performing electrolysis simultaneously with high-frequency vibration, it is needless to say that the “vibrating plate of a vibration stirrer can be used as both an anode and a cathode” as disclosed in Japanese Patent No. 4269318 can be used. Yes.

An example of detoxification performed by changing the conditions using the above system will be described.

Table 1 shows the results of a detoxification experiment for 22 days at a frequency of 160 Hz using a high-frequency agitator for contaminated water containing radioactive cesium 137 and 134.

As a result, the detoxification rate after about 3 weeks of treatment was about 20%.

Table 2 shows the results of a detoxification experiment in which electrolysis is used in combination with Example 1 (the frequency is also 160 Hz).

As a result, the detoxification rate in the treatment for about 2 weeks was about 50%, and further about 50% in the treatment for about 2 weeks (about 75% of the amount before the treatment). As compared with Example 1 (detoxification rate 20%), it was found that the detoxification rate was significantly improved when electrolysis was used in combination. This confirmed the effect of the powerful burst energy of the nano / micro bubbles generated during electrolysis.

As shown in Table 3, cesium 137 in the bubbling tank is 21 to 23 Bq, cesium 134 is 10 to 12 Bq, and each has a concentration of about 1/1000 of the original contaminated water. It can be seen that the amount of radioactive elements associated with (OHMASA-GAS) is small.

Tables 4 to 7 show the results of the detoxification experiment using electrolysis in the same manner as in Example 2 and setting the frequency of the high-frequency stirrer to 120 Hz, 140 Hz, 160 Hz (Example 2), 180 Hz, and 190 Hz.

As a result, a large difference was observed in the detoxification rate depending on the frequency, and the detoxification rate in the case of 160 Hz (Example 2) was the highest.

Next, a detoxification test was performed by using both high-frequency stirring and electrolysis in the same manner as in Example 2 and setting the temperatures to 40 ° C. and 80 ° C. The results are shown in Tables 8 and 9.

As a result, as shown in Tables 8 and 9, the cesium 137 detoxification rates were 74% and 72%, and cesium 134 was 73%, and no influence by temperature was observed.

When cesium 133 (reagent) was used and elemental conversion experiment of cesium 133 was performed with high-frequency stirring and electrolysis combined, as shown in Table 10, cesium 133 was converted into barium and platinum after approximately 2 weeks of treatment. I was able to confirm. In addition, it is estimated that the intermediate value is larger than the final value as a result of conversion to another element.

The measuring instrument used for elemental analysis was an ICP mass spectrometer (HP-4500, model: NIGC16190 SD) manufactured by Yokogawa Analytical System Co., Ltd., so that the concentration of cesium 133 was 350 mg / L. A sample of 0.5 L was taken and measured.

Further, in order to confirm the element conversion, an element conversion experiment was performed using 0.5% calcium chloride aqueous solution with high-frequency stirring and electrolysis using the same apparatus as in Example 5. The element conversion was confirmed as described in.

Elemental analysis was performed under the same conditions using the same measuring instrument as in Example 5. The results are shown in Table 11. From this table, after 20 days, the calcium concentration decreased significantly (2800 → 1800 mg / L), instead of iron (<10 → 7700 μg / L), copper (3 → 370 μg / L), cobalt (1 → 270 μg / L). ) And nickel (12 → 14000 μg / L). In particular, the increase in iron and nickel concentrations is significant. From this, it is considered that calcium was mainly converted into nickel and iron by high-frequency stirring and electrolysis combined use.

In Example 6, it was demonstrated that “calcium” can be elementally converted to “nickel” and “cobalt” that are extremely valuable. Therefore, as a calcium source, egg shells whose daily discharge is several tens to several hundreds of tons and whose processing costs are enormous are problematic, are pulverized by a pulverizer to a particle size of several to several tens of μm. Then, an experiment was conducted in which the slurry was poured into pure water to form a slurry having a concentration of 10 to 30%, which was treated in the same manner as in Example 6 and converted into valuable cobalt and nickel. As shown in Table 12, as a result of the treatment for 20 days, the concentration of calcium was reduced (3200 → 2500 mg / L), instead of cobalt (<1 → 1800 μg / L) and nickel (<1 → 11000 μg / L). The concentration increased and elemental conversion was confirmed in this example.

If the contaminated water is treated using the method according to the present invention, the radioactive element is converted into another element and the concentration can be significantly reduced. Therefore, it can be applied to detoxify the radioactive element and is currently becoming a big problem. , I think it will help to prevent contaminated water leaking from the Fukushima Daiichi Nuclear Power Station.

In addition, if this element conversion technology is put to practical use, not only the huge waste disposal cost of egg shells will be greatly reduced, but also elemental conversion can be recovered as valuable cobalt and nickel, which is extremely profitable Will not only be produced, but it will be an invention that contributes more than imagined to Japan, which has few resources.

As for other elements, any element can be converted at any time, and its contribution is extremely high.

DESCRIPTION OF SYMBOLS 1 Treatment tank 2 Contaminated water 3 High frequency vibration motor 4 Vibration bar 5 Multistage vibration blade 6 Inverter 7 Insulator 8 Rectifier

Claims

Treatment tank,
A high-frequency vibration motor fixed to the upper stage of the treatment tank,
A high-frequency vibration agitation device configured to include two vibrating bars extending downward from the processing tank connected to the table, and a multistage vibrating blade attached to the lower part of the vibrating bar;
The high-frequency vibration motor is controlled by an inverter to make the radioactive substance in the liquid harmless by vibrating the multistage vibrating blade at a frequency of 100 to 200 Hz in the liquid containing the radioactive substance in the treatment tank. And a detoxification system such as cesium 134 and cesium 137, and a technology for converting from one element to another.
In the multistage vibrating blades attached to the two vibrating bars, the first vibrating blade is physically and electrically connected to the right vibrating bar, and physically connected to the left vibrating bar. , Electrically insulated by an insulator,
The second vibrating blade is physically connected to the first right vibrating bar, but is electrically insulated, and physically and electrically connected to the left vibrating bar,
As described above, the plurality of vibrating blades are electrically connected, and by alternately repeating the insulation in the left and right vibrating bars, the left and right vibrating bars are in an electrically insulated state,
The element according to claim 1, wherein a DC power source is connected to the left and right vibrating bars via a rectifier to form an electrolysis circuit in which the plurality of vibrating blades alternately serve as anodes and cathodes. Technology to convert to other elements, and detoxification systems such as cesium 134 and cesium 137.
A pipe is provided at the top of the treatment tank,
The piping is connected to the top of the bubbling tank so that radioactive cesium is not released into the atmosphere accompanied by radioactive cesium,
3. An element according to claim 2, wherein oxyhydrogen gas (OHMASA-GAS) generated by electrolysis in the treatment tank is blown into the liquid in the bubbling tank. And detoxification systems such as cesium 134 and cesium 137.
A process of introducing radioactively contaminated water into the treatment tank of the electrode combined high-frequency agitator,
Setting the frequency of the high frequency agitator with an inverter and energizing it;
A treatment method for converting from one element to another element, comprising a step of detoxifying for a predetermined time, and a step of turning off the power of the high-frequency stirrer also serving as an electrode, and cesium 134 and Detoxification method such as cesium 137.
A process of introducing radioactively contaminated water into the treatment tank of the electrode combined high-frequency agitator,
Introducing the treatment tank so that the potassium hydroxide concentration is 3%;
Setting the frequency of the high frequency agitator with an inverter and energizing it;
Turning on the electrolysis rectifier and setting the electrolysis current value to DC7V, 11A;
A process of detoxifying for a predetermined time,
A treatment method for converting from one element to another, and a detoxification method for cesium 134, cesium 137, and the like, characterized by including a step of turning off the power of the electrode combined high-frequency stirring device.
6. The method for converting from one element to another element and harmless such as cesium 134 and cesium 137 according to claim 4, wherein the frequency of the high-frequency stirrer is set to 140 to 180 Hz. Method.
6. The treatment method for converting from one element to another element and the detoxification method for cesium 134, cesium 137, etc. according to claim 4 or 5, wherein the detoxification treatment temperature is 20 to 40 ° C.
6. A treatment method for converting one element into another element, and a detoxification method for cesium 134, cesium 137, etc. according to claim 4 or 5, wherein the detoxification treatment period is 30 to 60 days .
A step of introducing 0.5% concentration of calcium chloride into the treatment tank of the electrode combined high-frequency stirrer;
Setting the frequency of the high frequency agitator with an inverter and energizing it;
Turning on the electrolysis rectifier and setting the electrolysis current value to DC7V, 11A;
Performing a predetermined element conversion process,
A processing method for converting calcium into an element such as cobalt, nickel, iron, copper, and the like, comprising a step of turning off the power of the electrode combined type high-frequency stirring device.
The method according to claim 1, further comprising a step of adding a 10 to 30% slurry solution in which a shell of egg eggs pulverized to a particle size of several μm to several tens of μm is mixed with pure water instead of the step of adding calcium chloride. A processing method for converting calcium as described in 9 into an element such as cobalt, nickel, iron, or copper.