JP5863480B2 - Method for storing contaminants caused by radioactive cesium, and container for storing contaminants caused by radioactive cesium - Google Patents

Description

  The present invention relates to a method for storing contaminants by radioactive cesium and a container for storing contaminants by radioactive cesium.

Until now, solidified containers for the treatment and disposal of so-called low-level radioactive waste such as concentrated waste liquid, spent ion exchange resin, radioactive solids, etc. generated from radioactive material handling facilities such as nuclear power plants and nuclear fuel reprocessing facilities , Cement, concrete, and hydraulic inorganic solidification materials such as water glass (sodium silicate) are used for solidification materials, backfill materials, and disposal site structures.

Moreover, as a thing which delays leaking out of a radionuclide, there exists a thing which provides the protective layer in the solidification container of a radioactive waste, and embeds the filler which has ion exchange property and adsorption property in this protective layer. (Patent Document 2).

Furthermore, in order to provide a radioactive waste filling container capable of increasing the bending strength and improving impact resistance and reducing the radioactive leach rate, and a radioactive waste solidifying material capable of increasing the filling amount of the radioactive waste. A concrete radioactive waste filling container characterized by including a nuclide adsorption reinforcing material such as fibrous activated carbon that adsorbs radionuclides has been developed (Patent Document 1).

These hydraulic inorganic solidification materials and solidification containers are considered to be easy to solidify, relatively inexpensive and excellent in radiation resistance for a relatively small amount of low-level radioactive waste.

However, for example, in order to solidify and store in a solidified container for a large amount of rubble and contaminated soil containing low-level radioactivity of cesium due to a nuclear accident, a large amount of processing must be performed safely and quickly. It has been demanded.

For this reason, if possible, it is desirable to have a method that can be stored without performing a solidification process with a large number of steps. However, if the solidification process is omitted, the object to be stored contains water, so that cesium-contaminated water is generated in the storage container. Further, it is difficult to completely seal water with a storage container with ordinary concrete. Also, it is assumed that a large amount of storage containers are stored for a long time not in the building but in a place affected by rainwater, and there is a concern that water may permeate from the outside of the storage container. Therefore, when ordinary concrete containers are used for processing and disposal of large amounts of low-level radioactive waste, and when the storage location is outdoors, radionuclides may leak out of the storage containers via water. Is assumed.

JP-A-10-153690 JP-A-58-0400000

Patent Document 1 provides a radioactive waste filling container that can increase bending strength, improve impact resistance, and reduce the rate of radioactive leaching using fiber reinforced concrete, and the amount of radioactive waste filled. It is possible to provide a solidified material for radioactive waste that can increase the amount of waste. However, there are many man-hours for container production, and it is difficult to say that a large amount of these can be prepared and a large amount of contaminants can be processed more quickly. Also, no radioactive containment measures were taken according to the nuclide. In addition, these large amounts of contaminated waste are usually accompanied by moisture, but it is difficult to say that measures against water-soluble radionuclides are sufficient.

Therefore, if a large amount of soil, rice straw, rubble, sewage sludge or incinerated ash contaminated with radioactive cesium, which is water soluble, can be stored in a normal thick concrete container without solidification, Done quickly.

However, concrete itself has excellent radiation shielding performance, but it cannot be said to have perfect watertightness. In addition, radioactive cesium has a relatively low adherence to cementitious materials and exists as a cation even in a highly alkaline environment in cement and concrete. Therefore, it diffuses in the pore water of concrete for many years. There is concern about leakage outside the container.

In other words, cesium ions are more soluble in cement and less adsorbed from water (liquid phase) to cement (solid phase) than nuclides that have low solubility in high alkaline environments such as cobalt ions. Since it is small and the partition coefficient between the solid and liquid is small, special consideration is necessary for the containment of radioactive cesium itself in the container in the presence of water. In the case of a concrete container, since the water permeability coefficient of concrete is not zero, there is a risk of leakage of cesium-containing water.

  Therefore, the present invention provides a storage method for pollutants for quickly processing a large amount of waste containing a relatively low level of radioactive cesium, and a container for storing the contaminants. The purpose is to reduce the radioactive cesium leaking from the storage container as much as possible even if it is an environment that may come into contact with groundwater or if the container is cracked. .

A sepiolite powder and / or bentonite powder layer, which is an aggregate of fibrous sepiolite, and one or more adsorbent layers selected from zeolite, ferrocyanide salt, manganese compound, and silicotitanate are brought into close contact with each other, and made of concrete. Provided is a storage method characterized in that the storage container is spread over at least the bottom of the storage container and disposed so as to cover the bottom surface, and cesium contaminants are stored in the concrete storage container on the storage container.

The sepiolite powder and / or bentonite powder and one or more adsorbents selected from zeolite, ferrocyanide salt, manganese compound, and silicotitanate are mixed to cover at least the bottom of the concrete container so that the bottom is covered. And a storage method for storing cesium contaminants in the concrete storage container.

Measure the solid-liquid distribution coefficient for cesium of one or more adsorbents selected from zeolite, ferrocyanide salt, manganese compound and silicotitanate, and determine the adsorbent amount in consideration of the volume in the storage container. Then, after the sepiolite and / or bentonite and the adsorbent are installed so as to cover the bottom surface, a cesium contaminant storage method is provided, wherein the cesium contaminant is stored in a storage container.

One or more adsorbents selected from zeolites, ferrocyanide salts, manganese compounds, and silicotitanates are measured for the solid-liquid distribution coefficient Kd for cesium using Equation (1), and the volume in the storage container is taken into account. Then, the minimum required amount m of the adsorbent is determined from the formula (2), and the sepiolite and / or bentonite and the adsorbent are installed so as to cover the bottom surface, and then cesium contaminants are stored in a storage container. A concrete cesium contaminant storage method is provided. Expressions (1) and (2) will be described later.

A water-stopping material (said sepiolite, bentonite) or adsorbent (zeolite, ferrocyanide salt, manganese compound, silicotitanate) is placed in the bottom of the flexible container in advance, and these flexible containers are stored in a concrete container. Thus, there is provided a radioactive cesium contaminant storage method characterized in that a water-stopping material or an adsorbent is disposed on a water-stopping material or an adsorbent-installing portion at the bottom of a concrete storage container.

A concrete container for cesium contaminants, characterized in that the sepiolite powder and / or bentonite powder and the adsorbent are disposed so as to cover the bottom as described above, and cesium contaminants are stored in a storage container. provide.

(Storage container)
The radiation shielding performance can be reduced to 1/10 by sealing with 15 cm thick concrete having a density of 2.3 cm ³ / g. In heavy concrete using heavy aggregate, the shielding performance can be enhanced due to its high density. On the other hand, in rural areas and mountainous areas where road maintenance is not good, it may be difficult to carry heavy machinery that can handle thick concrete containers, so at the expense of radiation shielding performance. It is also effective to apply concrete containers using lightweight aggregates. In the present application, a container having a density of 1.7 cm ³ / g or more is used. Preferably, a container having a density of 2.3 cm ³ / g or more is used. When the density is less than 1.7 cm ³ / g, radiation shielding performance is not sufficient. Volume of the container is not limited, the movement, in consideration of the handling such as transportation, about 2m ³ of 1 m ³ is preferred.

Although the present invention has a radiation shielding effect equivalent to that of the conventional one, it is possible to dramatically prevent external leakage of cesium ions by using concrete having a density of 1.7 cm ³ / g or more.

Specifically, for example, a concrete rectangular container having a thickness of about 15 cm, a side of 1 to 1.5 m, an internal volume of 1 to 2 m ³ , and a weight of 2 t to 6 t can be used. The one with a weight of 2t is one that has improved transportability using a lightweight aggregate, and the one with a weight of 6t uses a heavy aggregate to increase the density and enhance the shielding performance.

The contaminated material is adjusted to a size that can be accommodated in the storage container, and the cesium radiation dose is measured. Soil, rice straw, and small debris (concrete waste generated from the removal of concrete and pavement repair work such as buildings and buildings such as houses and buildings) are collected in container bags. Measure the cesium radiation dose at a size that fits into the storage container. The total amount of cesium is calculated from the cesium radiation dose in consideration of the half-life.

(Adsorbent)
Next, a cesium adsorbent is prepared. In order to improve handling properties, it is also possible to use powdered granules. For example, clinoptilolite and mordenite are used as natural zeolite. Synthetic zeolite, silica gel, aluminosilicate compounds, activated alumina, activated carbon, and silicotitanate are also preferable. Further, as the ferrocyanide salt, cobalt ferrocyanide, ferrocyanide, and manganese-based adsorbent, manganese oxide and manganese sand are preferably used. If necessary, a flocculant, silica sand as a carrier, or the like can be used.

(Weighing and placement)

Formula (1) shows the formula for calculating the partition coefficient of the adsorbent. The distribution coefficient Kd can be calculated by an experiment in which cesium ions are adsorbed and transferred from the aqueous layer to the solid layer. In the experiment method, a predetermined amount (V) of a cesium ion aqueous solution having a predetermined concentration Co and a predetermined amount (m) of an adsorbent are mixed and shaken, and the cesium ion concentration C after adsorption is measured to calculate Kd. That is, Co is the cesium ion concentration of simulated water and is diluted with distilled water. Seawater, simulated seawater, simulated groundwater, etc. are appropriately selected according to the installation environment of the storage container. C is a cesium concentration in the simulated water measured after adsorption with an adsorbent. m is the amount of adsorbent used in the experiment. From the calculated Kd, the amount of adsorbent used in the present invention can be determined. At this time, cesium is the total amount including radioactive cesium.

Expression (2) is an expression for calculating the amount of adsorbent disposed in the container from the measured distribution coefficient. V is the storage container volume, Co is the ion concentration when it is assumed that cesium is uniformly dissolved in the water of the container volume, and C is filled with water after adsorption to the adsorbent. It is the cesium ion concentration when it is assumed. When the distribution coefficient Kd is large, the amount of adsorbent used is small. This is the minimum required amount of adsorbent. It is preferable to set the adsorbent amount obtained by multiplying this by one or more safety factors, for example, 1.5, as the minimum amount.

Furthermore, the adsorbent is laid so that the installation thickness is 5 mm or more, preferably 20 mm or more so as to spread over the entire surface of the container bottom, and the container bottom and the stored item or the container covering the container directly It is preferable to be installed so as not to contact. Therefore, when the minimum required amount calculated from (2) cannot cover the entire bottom surface of the container, the installation thickness is set to 5 mm or more. If it is less than 5 mm, the probability that water containing cesium ions will come into contact with the concrete storage wall increases.

FIG. 1 shows a schematic diagram of a method for storing an object contaminated with cesium in this container. The container was a cubic concrete container 10 made of a cube having a thickness of 15 cm and a storage area of 1 m square. A water blocking material or adsorbent installation portion 20 was provided at the bottom of the container. Here, a powder or granular adsorbent was installed. This is because, depending on the type of powder, the fluidity is poor and it is preferable to form granules in order to improve handling. A powder having a large specific surface area is preferable because it quickly reaches the adsorption equilibrium.

As the adsorbent, a plurality of adsorbents can be mixed and used. Adsorption reactions to different adsorbents occur competitively, but depending on the nature of the contaminated material, the performance of certain adsorbents may not be as effective as experimental values, such as zeolite and ferrocyanide. Is also preferred. The fine powder adsorbent may be used in combination with a flocculant or silica sand as a carrier.

Further, sepiolite and bentonite can be preliminarily spread on the bottom of the container as a waterstop material. Moreover, it is also preferable to mix these. Since these water-stopping materials do not interfere with the action of the adsorbent, they can be mixed and used at any use ratio as long as they do not interfere with the contact between the adsorbent and the cesium ion-containing water. In particular, short fiber type sepiolite (Turkish sepiolite) can absorb about 300% of its dry weight, and this performance is less affected by pH of water and coexisting ions, and water that is a leaking medium for radioactive cesium. Is particularly preferable. Sepiolite powder (for example, aggregate of fibrous sepiolite obtained by crushing and crushing Turkish sepiolite ore to a fiber length of 200 to 1 μm) is mixed with the adsorbent in the same amount or less, or adsorbed. It is preferable to lay in layers between the agent and the bottom surface of the storage container. When laid in layers, the amount of sepiolite powder used is a layer thickness of 5 mm or more that can cover the bottom surface. At this time, the water-stopping material may absorb water after the cesium ions are adsorbed, or adsorb cesium ions in water once trapped by sepiolite.

For example, the bentonite is preferably mixed with the trade name Super Clay (manufactured by Hojun Co., Ltd.) in the same amount or less as the adsorbent, or laid in layers between the adsorbent and the bottom surface of the storage container. The amount of bentonite used is also the same as that of sepiolite. The reason why the adsorbent installation portion is provided at the bottom of the container is that water in the contaminated material in the container stays at the bottom due to gravity. The water stop material keeps the water in the container and secures the time to reach the adsorption equilibrium of the adsorbent, and prevents water leakage due to concrete cracks and the like.

If the water-stopping material and the adsorbent are in the form of close coexistence, the effect of confining cesium ions is ensured. It is preferable to directly mix the two or to arrange the two separately in close contact with each other. Both have different roles, and the water-stopping material stops contaminated water and prevents fluidization, but does not selectively retain cesium ions. On the other hand, the adsorbent selects and adsorbs cesium ions in water to produce a concentration gradient of cesium ions in water, but the absorption capacity of water itself is not as good as that of the water-stopping material.

When the cesium ions in the water trapped by the water-stopping material are adsorbed by the adsorbent that is in close contact with the water-stopping material, the concentration of cesium ions becomes smaller and the concentration gradient is generated near the adsorbent powder surface. Then, cesium ions move sequentially from the surrounding water toward the adsorbent surface, and the fixation of cesium ions proceeds efficiently. When the partition coefficient Kd is large and the adsorbent is small and the cesium ions are fixed, the water stopping power does not decrease even if both are mixed, but the Kd is relatively small and the adsorbent is a relatively large amount. When the water stop is insufficient, it is preferable to divide the two into separate layers and arrange them closely or to distribute a relatively large amount of the water stop material. It is also preferable to dispose both layers alternately in two or more layers. The time required for the cesium ions to reach adsorption equilibrium is related to the distribution ratio of both and the close form of both.

Thus, after the waterstop material powder and the adsorbent powder are installed, the contaminated object 30 is stored in the container. At this time, the contaminated object can be stored in a flexible container and stored together with the container. At this time, when the water-stopping material or adsorbent is set in advance in the bottom of the container and the container is stored, the water-stopping material or adsorbent is set in the water-stopping material or adsorbent installation portion 20 at the bottom of the container. It can also be done. The arrangement of the water blocking material and the adsorbent in the container can be performed in accordance with the above-described method of directly arranging in the concrete container.

Thereafter, the lid 12 of the storage container is placed on the storage container main body 11 to seal the contaminants in the storage container.

Provided are a storage container and a storage method for greatly improving the confinement performance of radioactive cesium ions of radioactive contaminants that are not solidified. The radiation shielding performance does not change, but when there is water penetration into a container that satisfies the shielding performance, or when water is brought into the container together with the contaminated material, cesium ions in the water Stops adsorbent, lowers the concentration of water containing cesium ions, delays leakage of cesium ions to the outside, and absorbs water that does not contain cesium by a water-stopping material that does not depend on the pH of the water-stopping effect. Thus, it is possible to prevent cesium ions from penetrating into the container and to prevent cesium ions from desorbing from the adsorbent.

[Embodiment]
Using the rectangular concrete container shown in FIG. 1 (normal concrete cube internal volume 1 m ³ , heavy concrete cube internal volume 1 m ³ ), the solution containing radioactive cesium leaked from the storage contaminated with radioactive cesium. The penetration test was conducted assuming that Assuming that 1000 kg of surface soil contaminated with 400,000 Bq / kg of cesium 137 is packed in a flexible container, the amount of cesium is calculated to be 0.124 mg from the half-life of cesium. Assuming that the total amount of radioactive cesium is dissolved in 1 liter of water and leached to the bottom of the container, the concentration of cesium in the solution is 0.124 ppm. Therefore, a cesium solution of this concentration was prepared with a stable isotope cesium chloride reagent to obtain a simulated cesium solution. However, assuming that high-concentration contaminants are to be treated, 100 liters of the simulated cesium solution was sprayed into the storage container 10 to confirm the state of penetration of cesium into the concrete container. That is, the test was conducted with 100 times the amount of cesium equivalent to 400,000 Bq / kg (equivalent to 40 million Bq). After spraying the simulated cesium solution, the adsorbent and the water stop material were collected 7 days later. The state of penetration into the concrete square container was confirmed by scraping the surface of the bottom surface of the concrete container in contact with the simulated cesium solution by 1 mm and measuring the amount of cesium present in the recovered concrete powder. The collected concrete powder was dissolved in hydrochloric acid, and the concentration of cesium in the concrete square container was evaluated by measuring the concentration of cesium in the hydrochloric acid solution using ICP-MAS. Evaluation of cesium adsorption performance to adsorbent and water-stopping material was conducted by separating 100 g of representative sample from the collected adsorbent and / or water-stopping material and immersing it in 1 liter of water for 24 hours. Measurement was performed using ICP-MAS.

The simulated cesium solution was put into a square concrete container as it was, and a penetration experiment (A) of cesium into concrete was performed.

On the other hand, the penetration experiment (B) was performed using clinoptilolite (natural zeolite in Itaya, Yamagata Prefecture) and bentonite (trade name Super Clay, manufactured by Hojun Co., Ltd.) as the adsorbent.
A concrete cube having the same specifications as in the penetration experiment (A) was used. A 2 cm thick bentonite was spread on the bottom of the concrete cube, and 17.9 kg of clinoptilolite was layered on it. And the simulated cesium solution was thrown into the container of the present invention. When Kd of clinoptilolite was calculated from the formula (1), it was 5.6 × 10 ³ . Using this value, in order to reduce the ion concentration assumed to have dissolved cesium in water equivalent to the volume of the storage container to 1/100, the necessary amount to be adsorbed is calculated from the equation (2). kg is obtained.

(Penetration experiment (C))
Sepiolite was spread 2 cm thick on the bottom of the storage container. On top of that, 1 kg of ferrocyanide powder was placed, and the simulated cesium solution was put into the container of the present invention. The Kd of ferrocyanide was calculated from the formula (1) and found to be 1.0 × 10 ⁶ . Using this value, in order to reduce the ion concentration assumed to be cesium dissolved in water equivalent to the volume of the storage container to 1/1000, the amount necessary to adsorb on solid iron ferrocyanide (1 kg) Was calculated from equation (2).

(Penetration experiment (D))
It was 1.6 * 10 < ⁵ > when Kd of crystalline silicotitanate CST-2 (made by UOP USA) was computed from Formula (1). Using this value, the necessary amount of crystalline silicotitanate CST-2 from formula (2) to make the ion concentration 1/1000 assuming that cesium was dissolved in water comparable to the volume of the storage container (6.25 kg) was calculated.
Crystalline silicotitanate CST-2 (manufactured by UOP, USA), 6.25 kg and 5 kg of sepiolite powder were mixed and installed at the bottom of the storage container, and the simulated cesium solution was charged into the container of the present invention.

(Penetration experiment (E))
At the bottom of the storage container, 2 cm of sepiolite powder was installed without using an adsorbent, and the simulated cesium solution was charged into the container of the present invention.

(Penetration experiment (F))
It was 1.6 * 10 < ⁵ > when Kd of crystalline silicotitanate CST-2 (made by UOP USA) was computed from Formula (1). Using this value, the necessary amount of crystalline silicotitanate CST-2 from formula (2) to make the ion concentration 1/1000 assuming that cesium was dissolved in water comparable to the volume of the storage container (6.25 kg) was calculated.
At the bottom of the storage container, 3 kg of crystalline silicotitanate CST-2 (manufactured by UOP, USA) is layered so as to cover it in layers, and 3 kg of sepiolite powder is spread on top of it, and 3.25 kg of CST- 2 and 2 kg of sepiolite powder were placed closely in a layered manner, and the simulated cesium solution was charged into the container of the present invention.

In the above penetration examples A to F, the amount of penetration into the concrete container and the amount of adsorption were measured. 100 liters of a simulated cesium solution was sprayed into a concrete cube provided with the adsorbent and water-stopping material. After being left for 7 days, the adsorbent and / or water-stopping material was collected, and 1 mm concrete was scraped from the bottom surface of the concrete container to evaluate the cesium penetration state. Further, a representative sample was taken from the adsorbent and / or water-stopping material and immersed in 1 liter of water for cesium ion extraction measurement to evaluate the amount of cesium ion adsorbed. After immersing the adsorbent and / or water-stopping material, it was allowed to stand for 24 hours, water for measuring the amount of cesium adsorbed was collected, and unadsorbed cesium ion concentration was measured by ICP-MAS. These results are shown in Table 1.

As Table 1 shows, the shielding effect can be expected to be a normal effect evaluated from the density and thickness of the concrete material, and the excellent water stopping effect against cesium ion adsorption and penetration is shown in Experimental Examples B to D. Met. In addition to the above experiments using simulated cesium water, tests were conducted by mixing actual soil and simulated cesium water. In both cases, simulated cesium was used to promote adsorption of cesium ions and inhibit penetration into concrete walls. Preferred results were obtained from experiments with water alone. Therefore, the experiment of single spraying of simulated cesium water was a test that assumed the most severe conditions, and by clearing this, it was confirmed that it was possible to handle storage of contaminants such as actual soil. .

In Experimental Example F, the adsorption ability of cesium comparable to that of Experimental Example D was obtained, and the penetration of cesium into the container was reduced to the same extent as in Experimental Example D.

It is a schematic diagram of the method of accommodating the to-be-contaminated thing contaminated with cesium in this container.

DESCRIPTION OF SYMBOLS 10 Storage container 11 Storage container main-body part 12 Cover part 20 of a storage container Water-stopping material or adsorbent installation part 30

Claims (7)

A sepiolite powder and / or bentonite powder layer, which is an aggregate of fibrous sepiolite, and one or more adsorbent layers selected from zeolite, ferrocyanide salt, manganese compound, and silicotitanate are brought into close contact with each other, and made of concrete. A storage method comprising: laying at least a bottom portion of a storage container so as to cover a bottom surface, and storing a cesium contaminant in the concrete storage container thereon. Fibrous sepiolite powder and / or bentonite powder and one or more adsorbents selected from zeolite, ferrocyanide salt, manganese compound, and silicotitanate are mixed to cover at least the bottom of the concrete container. Thus, the storage method is characterized in that the cesium contamination is stored in the concrete storage container. Measure the solid-liquid distribution coefficient for cesium of one or more adsorbents selected from zeolite, ferrocyanide salt, manganese compound and silicotitanate, and determine the adsorbent amount in consideration of the volume in the storage container. The cesium contaminant according to claim 1 or 2, wherein the cesium contaminant is stored in a storage container after being placed in close contact with the fibrous sepiolite powder and / or bentonite powder and covering the bottom surface. Storage method. One or more adsorbents selected from zeolites, ferrocyanide salts, manganese compounds, and silicotitanates are measured for the solid-liquid distribution coefficient Kd for cesium using Equation (1), and the volume in the storage container is taken into account. Then, the minimum required amount m of the adsorbent is determined from the formula (2) and is placed in close contact with the fibrous sepiolite and / or bentonite so as to cover the bottom surface, and then the cesium contaminant is stored in the storage container. The cesium contaminant storing method according to any one of claims 1 to 3, wherein:
By placing water-stopping material or adsorbent in the bottom of the flexible container in advance and storing these flexible containers in the concrete storage container, the water-stopping material or adsorbent is installed at the bottom of the concrete storage container. 5. The radioactive cesium contaminant storage method according to claim 1, wherein a material or an adsorbent is disposed. In the container, a layer of sepiolite powder and / or bentonite powder, which is an aggregate of fibrous sepiolite, and one or more adsorbent layers selected from zeolite, ferrocyanide, manganese compound, and silicotitanate are in close contact with each other. A concrete storage container characterized by having a storage part for radioactive cesium contaminants at the top thereof, covering the bottom surface in a state of being laid and laid on the bottom of the front container. In the container, a mixed layer of fibrous sepiolite powder and / or bentonite powder and one or more adsorbents selected from zeolite, ferrocyanide salt, manganese compound, and silicotitanate was laid on the bottom of the front container. A concrete storage container characterized by covering the bottom surface in a state and having a storage part for radioactive cesium contaminants in the upper part.