JP6349166B2 - Operation method of radioactive cesium separation and concentration equipment - Google Patents
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本発明は、放射性セシウム分離濃縮装置の運転方法に関する。 The present invention relates to a method for operating a radioactive cesium separation and concentration apparatus.
原子力発電所等の核分裂反応を利用する機器等から漏洩した放射性物質で汚染された土壌や草木、海や河川等の自然環境を回復するために、放射性物質を含む被処理物から放射性物質を分離して濃縮する様々な方策が研究されている。 In order to recover the natural environment such as soil, vegetation, sea and rivers that were contaminated with radioactive materials leaked from nuclear fission reaction equipment, etc. Various measures for concentrating these are being studied.
放射性物質の中でもセシウム134、セシウム137は沸点、融点が低くて揮散しやすく、水溶性も高い物質であるため、健康への影響が大きく、ヨウ素131と併せて主要三核種と言われている。特にセシウム137は、半減期が30年と長く、土壌に吸着されると容易に除染できない。 Among radioactive materials, cesium 134 and cesium 137 have a low boiling point, a low melting point, are easily volatilized, and are highly water-soluble. Therefore, they have a great impact on health, and are said to be major trinuclear species together with iodine 131. In particular, cesium 137 has a long half-life of 30 years and cannot be easily decontaminated when adsorbed on soil.
特許文献1には、放射性セシウムを含有する土壌に無機カルシウム化合物及び塩化ナトリウムを添加して、ロータリーキルン等の加熱装置を用いて1200℃以下の温度で加熱処理することにより、塩化ナトリウムのみを添加して加熱処理する場合に比べて放射性セシウムの揮散率を上昇させることができる放射性セシウム除去方法が開示されている。 In patent document 1, only sodium chloride is added by adding an inorganic calcium compound and sodium chloride to the soil containing radioactive cesium, and heat-treating at a temperature of 1200 ° C. or less using a heating device such as a rotary kiln. Thus, a method for removing radioactive cesium that can increase the volatilization rate of radioactive cesium as compared with the case of heat treatment is disclosed.
無機カルシウム化合物を土壌に添加することにより放射性セシウムが土壌から脱着され、脱着された放射性セシウムが塩化ナトリウムに由来する塩素原子と結合して、土壌中に含有されていた放射性セシウムが放射性の塩化セシウムとして揮発するためであると推察され、当該放射性セシウム除去方法によれば90%程度の放射性セシウムの除去率が得られる。 By adding inorganic calcium compounds to the soil, radioactive cesium is desorbed from the soil, and the desorbed radioactive cesium is combined with chlorine atoms derived from sodium chloride, so that the radioactive cesium contained in the soil is radioactive cesium chloride. As a result, it is estimated that the removal rate of about 90% of radioactive cesium is obtained.
特許文献2には、放射性セシウムで汚染した可燃物に塩素化合物である塩化ナトリウムまたはポリ塩化ビニールを供給して焼却することにより塩化セシウムを含有する焼却主灰とし、或いは放射性セシウムで汚染した可燃物の焼却により得られた焼却主灰を塩素化合物である塩化ナトリウムまたはポリ塩化ビニールと混合し、何れかの焼却主灰を塩化セシウムの沸点以上で溶融して、塩化セシウムを溶融飛灰中に濃縮させて、溶融固化体中の放射性セシウム濃度を低減させる放射性セシウム汚染物の処理方法が提案されている。当該放射性セシウム汚染物の処理方法によれば放射性セシウムの溶融残存率が5%になり95%の放射性セシウムが除去されるようになる。 In Patent Document 2, combustible material contaminated with radioactive cesium is incinerated main ash containing cesium chloride by supplying sodium chloride or polyvinyl chloride, which is a chlorine compound, to the combustible material and incineration, or combustible material contaminated with radioactive cesium. Incineration main ash obtained by incineration of lime is mixed with sodium chloride or polyvinyl chloride, which is a chlorine compound, and any incineration main ash is melted above the boiling point of cesium chloride, and cesium chloride is concentrated in the molten fly ash Thus, a method for treating radioactive cesium contaminants that reduces the concentration of radioactive cesium in the molten solidified body has been proposed. According to the method for treating radioactive cesium contaminants, the fusion residual rate of radioactive cesium becomes 5%, and 95% of radioactive cesium is removed.
上述した何れの特許文献にも、放射性セシウム汚染物に塩化ナトリウムを添加して加熱または溶融することにより放射性セシウムを放射性の塩化セシウムとして効果的に揮散させることができる旨記載されている。 In any of the above-mentioned patent documents, it is described that radioactive cesium can be effectively volatilized as radioactive cesium chloride by adding sodium chloride to a radioactive cesium contaminant and heating or melting it.
特許文献1には、セシウム除去後の土壌を洗浄して脱塩しなければ、耕作地用には使用できないという課題に対して、酸化カルシウム、炭酸カルシウム、水酸化カルシウム、リン酸カルシウム、ケイ酸カルシウム、カルシウムシアナミド及び硝酸カルシウムからなる群より選択される少なくとも1種類の無機カルシウム化合物を揮散促進剤として用いることにより、塩化ナトリウムの添加量を抑制し、加熱処理後の脱塩を不要にする技術が開示されている。 Patent Document 1 discloses that calcium oxide, calcium carbonate, calcium hydroxide, calcium phosphate, calcium silicate, and the like that cannot be used for cultivated land unless the soil after cesium removal is washed and desalted. Disclosed is a technique that suppresses the amount of sodium chloride added and eliminates the need for desalting after heat treatment by using at least one inorganic calcium compound selected from the group consisting of calcium cyanamide and calcium nitrate as a volatilization accelerator. Has been.
しかし、放射性セシウム汚染物に塩化ナトリウム等の塩素化合物を添加して加熱処理すると、排ガス中に添加物由来の塩化水素ガス等の塩素系ガスが発生して煙道及び排ガス処理設備の腐食を招くため、消石灰等の中和剤を排ガスに投入する中和剤添加機構を設ける必要があり、セシウムの揮散を促進させるために塩化ナトリウム等の塩素化合物の添加量を増量すると、それに伴って中和に必要な設備コスト及び薬剤コストが嵩むという問題があった。 However, when chlorine compounds such as sodium chloride are added to radioactive cesium contaminants and heat-treated, chlorine gas such as hydrogen chloride gas derived from the additive is generated in the exhaust gas, which causes corrosion of flue and exhaust gas treatment equipment. Therefore, it is necessary to provide a neutralizing agent addition mechanism that introduces a neutralizing agent such as slaked lime into the exhaust gas. If the amount of chlorine compound such as sodium chloride is increased in order to promote volatilization of cesium, neutralization is accompanied accordingly. There is a problem that the equipment cost and the drug cost necessary for the process are increased.
そして、放射性セシウムの揮散率をさらに上昇させるためには、塩化ナトリウム等の塩素化合物の添加量を増量せざるを得ず、それだけ塩素化合物を含めた薬剤コストが嵩み、飛灰の発生量が増えるため設備コストの嵩む大型のバグフィルタが必要になるという問題があった。 In order to further increase the volatilization rate of radioactive cesium, it is necessary to increase the amount of chlorine compounds such as sodium chloride, which increases the cost of chemicals including chlorine compounds, and the amount of fly ash generated. There is a problem that a large bug filter with increased equipment cost is required due to the increase.
特許文献2には、放射性セシウムを含む焼却灰を、0.5〜1.3の塩基度に調整することにより好ましい溶融性を得ることが開示されているが、そのために必要な塩基度調整剤のコストも嵩むという問題があり、特に放射性セシウムに汚染された土壌の場合にはその組成が地域により大きく変動し、放射性セシウムを揮散させるための薬剤コストに加えて、溶融時に必要となる塩基度調整剤のコストも処理コストに大きく影響を及ぼすという問題もあった。 Patent Document 2 discloses that incineration ash containing radioactive cesium has a preferable meltability by adjusting the basicity of 0.5 to 1.3, but a basicity adjusting agent necessary for this purpose is disclosed. In particular, in the case of soil contaminated with radioactive cesium, the composition varies greatly depending on the region, and in addition to the chemical cost for volatilizing radioactive cesium, the basicity required for melting There is also a problem that the cost of the adjusting agent greatly affects the processing cost.
本発明の目的は、上述した問題点に鑑み、放射性セシウムの揮散を促進する塩素系助剤の使用量を抑制しながらも、放射性セシウムの揮散率をさらに上昇させることができる放射性セシウム分離濃縮装置の運転方法を提供する点にある。 An object of the present invention is to provide a radioactive cesium separation and concentration apparatus that can further increase the volatilization rate of radioactive cesium while suppressing the amount of use of a chlorine-based auxiliary that promotes volatilization of radioactive cesium in view of the above-described problems. Is to provide a driving method.
上述の目的を達成するため、本発明による放射性セシウム分離濃縮装置の運転方法の第一特徴構成は、特許請求の範囲の請求項1に記載した通り、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤からなる塩基度調整助剤を添加する塩基度調整助剤添加装置と、塩基度調整助剤が添加された被処理物を加熱して放射性セシウムを揮散分離する加熱炉と、前記加熱炉で揮散分離された放射性セシウムを含む飛灰を捕集する集塵機と、を備えて構成される放射性セシウム分離濃縮装置の運転方法であって、被処理物の塩基度が所定値になるように塩基度調整助剤の添加量を決定し、予め求める被処理物の塩基度が前記所定値のもとでの塩素系塩基度調整剤の添加割合とセシウム揮散率との関係に基づいて放射性セシウムの揮散率が最大となる範囲に入るように塩基度調整助剤である塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合を決定する塩基度調整助剤添加量決定工程と、前記塩基度調整助剤添加量決定工程で決定された値に従って、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤を添加する塩基度調整工程と、塩素系塩基度調整助剤と非塩素系塩基度調整助剤が添加された被処理物を前記加熱炉で加熱する加熱処理工程と、前記集塵機で捕集された放射性セシウムを含む飛灰を回収する回収処理工程と、を備えている点にある。 To achieve the above object, a first characterizing feature of the method for operating the radioactive cesium separation and concentration apparatus according to the present invention, as described in claim 1., chlorine basicity adjustment aid to be treated And a basicity adjustment aid addition device for adding a basicity adjustment aid comprising a non-chlorine basicity adjustment aid , and heating a workpiece to which the basicity adjustment aid has been added to volatilize and separate radioactive cesium A method for operating a radioactive cesium separation and concentration device comprising a heating furnace and a dust collector that collects fly ash containing radioactive cesium volatilized and separated in the heating furnace, wherein the basicity of the object to be treated is The amount of the basicity adjusting aid added is determined so as to be a predetermined value, and the basicity of the object to be processed obtained in advance is the addition ratio of the chloric basicity adjusting agent and the cesium volatilization rate under the predetermined value. maximum volatilization rate of radioactive cesium is based on the relationship And basicity adjustment aid amount determination step of determining a Blend ratio of chlorine basicity adjusting aid and chlorine-basicity adjusting aid is a basic adjustment aid to fall range of the basicity A basicity adjustment step of adding a chlorine basicity adjustment aid and a non-chlorine basicity adjustment aid to the object to be treated according to the value determined in the adjustment aid addition amount determination step, and a chlorine basicity adjustment aid And a heat treatment step of heating the object to which the non-chlorine basicity adjusting aid is added in the heating furnace, and a recovery treatment step of collecting fly ash containing radioactive cesium collected by the dust collector, It is in the point to have.
放射性セシウムで汚染された土壌を含む被処理物に塩素系助剤を添加して加熱処理すれば、被処理物が溶融する際に放射性セシウムと塩素が結合して溶融物から塩化セシウムとして揮散分離される。本願発明者らは、その際に被処理物に塩基度調整助剤を添加するとスラグの骨格構造が脆弱化して、スラグからセシウムが遊離し易くなるという知見を得ている。 If a chlorine-based auxiliary agent is added to the object to be treated, including soil contaminated with radioactive cesium, and heat-treated, the radioactive cesium and chlorine combine to separate and volatilize from the melt as cesium chloride. Is done. The inventors of the present application have found that when a basicity adjusting aid is added to the object to be treated at this time, the skeletal structure of the slag becomes weak and cesium is easily liberated from the slag.
そこで、塩基度調整工程で被処理物に添加する塩基度調整助剤として塩素系の塩基度調整助剤を用いれば、好ましい塩基度への調整のみならず、放射性セシウムの揮散促進剤としても機能するのではないかと想到し、鋭意実験を行なったところ、塩基度調整助剤として塩素系塩基度調整助剤及び非塩素系塩基度調整助剤を所定の添加量及び配合割合で被処理物に添加すれば、別途の塩化ナトリウム等の塩素系助剤を添加しなくても、分離工程で高効率に放射性セシウムを揮散させることができ、且つ排ガス中の塩化水素濃度を低減でき、捕集工程で効率的に放射性セシウムを捕集できるという新知見を得たのである。塩素系塩基度調整助剤及び非塩素系塩基度調整助剤の添加量及び配合割合は塩基度調整助剤添加量決定工程で決定される値で、塩基度調整助剤添加量決定工程は、試験等に基づいて被処理物に対して放射性セシウムの揮散率が所定の範囲に入るように塩素系塩基度調整助剤及び非塩素系塩基度調整助剤の添加量及び配合割合を決定する工程である。 Therefore, if a chlorine-based basicity adjusting aid is used as a basicity adjusting aid to be added to the object to be treated in the basicity adjusting step, it functions not only as a preferable basicity but also as a volatilization accelerator for radioactive cesium. As a result of diligent experimentation, a basicity adjustment aid and a non-chlorine basicity adjustment aid were added to the object to be treated at a predetermined addition amount and blending ratio. If added, it is possible to volatilize radioactive cesium with high efficiency in the separation process without adding a separate chlorine-based auxiliary agent such as sodium chloride, and the concentration of hydrogen chloride in the exhaust gas can be reduced. And gained new knowledge that radioactive cesium can be collected efficiently. The addition amount and blending ratio of the chloric basicity adjustment aid and the non-chlorine basicity adjustment aid are values determined in the basicity adjustment aid addition amount determination step, and the basicity adjustment aid addition amount determination step is: A step of determining the addition amount and blending ratio of the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid so that the volatilization rate of the radioactive cesium is within a predetermined range based on the test etc. It is.
つまり、塩素系助剤の添加量を減らしても放射性セシウムの揮散率を最大に上昇させることができ、添加する塩素量を減らすことにより塩素系の腐食ガスの発生量を低減できるようになり、以て、中和剤を含めた薬剤コストを大きく低減することができ、また飛灰の発生量も減少し、大型の排ガス処理設備を構築する必要もなくなるのである。ここに、塩基度とは酸化カルシウムと二酸化珪素の比[CaO(%)/SiO2(%)]のみならず、光学的塩基度等のスラグ骨格の塩基性を表現する指標を意味する。尚、光学的塩基度はDuffyとIngramによって見出された指標であり、紫外光吸収ピークがガラス組成に対して敏感に変化することに注目し、多成分系酸化物ガラスについて、ガラスの組成とそれらを構成するカチオンの電気陰性度とから、所定の数式に基づいて導き出される指標である。 In other words, the volatilization rate of radioactive cesium can be increased to the maximum even if the amount of chlorine-based auxiliary added is reduced, and the amount of chlorine-based corrosive gas generated can be reduced by reducing the amount of chlorine added, Thus, the cost of the chemicals including the neutralizing agent can be greatly reduced, the amount of fly ash generated is reduced, and there is no need to construct a large exhaust gas treatment facility. Here, basicity means not only the ratio of calcium oxide to silicon dioxide [CaO (%) / SiO 2 (%)] but also an index expressing the basicity of the slag skeleton such as optical basicity. The optical basicity is an index found by Duffy and Ingram, and it is noted that the ultraviolet light absorption peak changes sensitively with respect to the glass composition. and an electronegativity of the cation constituting them, Ru indicator der derived based on a predetermined formula.
同第二の特徴構成は、同請求項2に記載した通り、上述した第一の特徴構成に加えて、前記塩基度調整助剤添加量決定工程では、塩基度調整助剤添加後の被処理物の塩基度、光学的塩基度、塩素濃度、被処理物の加熱処理工程後の塩基度、光学的塩基度の何れかから選択される単一または複数の指標が所定の範囲に収まるように、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合が決定される点にある。 In the second characteristic configuration, as described in claim 2 , in addition to the first characteristic configuration described above, in the basicity adjusting auxiliary agent addition amount determining step, the treatment after adding the basicity adjusting auxiliary agent Single or multiple indicators selected from the basicity, optical basicity, chlorine concentration, basicity after heat treatment of the object to be processed, and optical basicity are within a predetermined range. The addition amount and the mixing ratio of the chlorine basicity adjusting aid and the non-chlorine basicity adjusting aid are determined.
塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合を決定するために、塩基度調整助剤添加後の被処理物の塩基度、光学的塩基度、塩素濃度、被処理物の加熱処理ステップ後の塩基度、光学的塩基度の何れかまたは複数の指標の組合せを採用することで、間接的に被処理物に対する放射性セシウムの揮散率を制御することができる。 The basicity, optical basicity, and chlorine concentration of the processed material after the addition of basicity adjusting aid to determine the addition amount and blending ratio of chlorinated basicity adjusting aid and non-chlorine basicity adjusting aid The volatilization rate of radioactive cesium to the object to be treated can be indirectly controlled by adopting any combination of basicity, optical basicity or a plurality of indicators after the heat treatment step of the object to be treated. .
同第三の特徴構成は、同請求項3に記載した通り、上述した第一または第二の何れかの特徴構成に加えて、前記塩基度調整助剤添加量決定工程では、被処理物の組成を自動測定し塩基度調整助剤の添加量が自動決定され、前記塩基度調整工程では、前記塩基度調整助剤添加量決定工程で決定された添加量に従って被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤が自動添加される点にある。 In the third feature configuration, as described in claim 3 , in addition to the first or second feature configuration described above, in the basicity adjustment assistant addition amount determination step, The composition is automatically measured and the addition amount of the basicity adjustment aid is automatically determined. In the basicity adjustment step, the chlorine-based basicity is added to the workpiece according to the addition amount determined in the basicity adjustment aid addition amount determination step. The adjustment assistant and the non-chlorine basicity adjustment assistant are automatically added.
塩基度調整助剤添加量決定工程で、被処理物の組成が自動測定され、その値に基づいて塩基度調整助剤の添加量が自動決定され、自動決定された添加量に従って塩基度調整工程で塩基度調整助剤が自動添加されるので、人手で塩基度調整助剤の添加量を決定し、塩基度調整助剤を添加する場合に比べて、作業負担が大きく低減されるので、被処理物に対する組成の測定回数を増やすことができる。その結果、被処理物の組成の変動に対して細かく塩基度調整助剤の添加量を決定することができ、目標とする放射性セシウムの揮散率に対する実際の揮散率の変動を低減することができ、極めて安定した操炉が可能になる。 In the basicity adjustment aid addition amount determination step, the composition of the object to be treated is automatically measured, and based on the value, the addition amount of the basicity adjustment aid is automatically determined, and the basicity adjustment step according to the automatically determined addition amount Since the basicity adjustment aid is automatically added, the work load is greatly reduced compared to the case where the addition amount of the basicity adjustment aid is determined manually and the basicity adjustment aid is added. It is possible to increase the number of times the composition is measured for the processed material. As a result, it is possible to finely determine the amount of addition of the basicity adjustment aid to the variation in the composition of the object to be processed, and to reduce the variation in the actual volatilization rate relative to the volatilization rate of the target radioactive cesium. , Extremely stable operation is possible.
同第四の特徴構成は、同請求項4に記載した通り、上述した第一から第三の何れかの特徴構成に加えて、前記塩基度調整工程で添加される塩素系塩基度調整助剤は、無機塩化物または無機塩化物が含まれる物質の何れかから選択される単一または複数の物質である点にある。 The fourth feature configuration is the chlorine-based basicity adjustment aid added in the basicity adjustment step in addition to any of the first to third feature configurations described above, as described in claim 4. Is a single substance or a plurality of substances selected from either inorganic chlorides or substances containing inorganic chlorides.
無機塩化物または無機塩化物が含まれる物質を塩基度調整助剤として好適に用いることができ、放射性セシウムを揮散させるための別途の塩素系の揮散助剤を用いることによる薬剤コストの上昇を抑制することができる。 Inorganic chlorides or substances containing inorganic chlorides can be suitably used as basicity adjustment aids, suppressing the increase in drug costs due to the use of a separate chlorine-based volatilization aid for volatilizing radioactive cesium can do.
同第五の特徴構成は、同請求項6に記載した通り、上述の第四の特徴構成に加えて、前記塩基度調整工程で添加される塩素系塩基度調整助剤は、塩化カルシウム、塩化ナトリウム、塩化カリウム、塩化鉄の何れかから選択される単一または複数の物質である点にある。 In the fifth feature configuration, as described in claim 6 , in addition to the fourth feature configuration described above, the chlorine-based basicity adjusting aid added in the basicity adjusting step is calcium chloride, chloride. The substance is a single substance or a plurality of substances selected from sodium, potassium chloride, and iron chloride.
塩素系塩基度調整助剤として、塩化カルシウム、塩化ナトリウム、塩化カリウム、または塩化鉄が好適に利用できる。 Calcium chloride, sodium chloride, potassium chloride, or iron chloride can be suitably used as the chloric basicity adjusting aid.
同第六の特徴構成は、同請求項6に記載した通り、上述した第一から第五の何れかの特徴構成に加えて、前記塩基度調整工程で添加される非塩素系塩基度調整助剤は、非塩素系アルカリ金属化合物、非塩素系アルカリ土類金属化合物、非塩素系マグネシウム化合物、非塩素系ホウ素化合物、非塩素系鉄化合物、非塩素系鉛化合物の何れかから選択される単一または複数の物質である点にある。 The sixth characterizing feature of the can, as noted in the claim 6, in addition from the first described above in the fifth one of characteristic structure of, chlorine-base adjustment aid to be added in the basicity adjustment step The agent is selected from any of non-chlorine alkali metal compounds, non-chlorine alkaline earth metal compounds, non-chlorine magnesium compounds, non-chlorine boron compounds, non-chlorine iron compounds, and non-chlorine lead compounds. The point is that it is one or more substances.
非塩素系塩基度調整助剤として、非塩素系アルカリ金属化合物、非塩素系アルカリ土類金属化合物、非塩素系マグネシウム化合物、非塩素系ホウ素化合物、非塩素系鉄化合物、または非塩素系鉛化合物が好適に利用できる。 Non-chlorine basicity adjustment aids include non-chlorine alkali metal compounds, non-chlorine alkaline earth metal compounds, non-chlorine magnesium compounds, non-chlorine boron compounds, non-chlorine iron compounds, or non-chlorine lead compounds Can be suitably used.
同第七の特徴構成は、同請求項7に記載した通り、上述した第一から第六の何れかの特徴構成に加えて、前記塩基度調整助剤添加量決定工程では、還元剤が添加された被処理物に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合が決定される点にある。 The seventh characterizing feature of the can, as noted in the claim 7, in addition from the first described above in the sixth one characteristic feature of the, in the basicity adjustment aid amount determination step, the reducing agent is added The addition amount and the mixing ratio of the chlorine-based basicity adjusting aid and the non-chlorine basicity-adjusting aid are determined with respect to the treated object.
還元剤を被処理物に添加すれば、加熱処理工程で被処理物に含まれる放射性セシウムの酸化物が効果的にセシウムに還元処理され、還元された放射性セシウムが効率的に塩素と結合して塩化セシウムに移行し、放射性セシウムの揮散がより促進されるようになる。 If a reducing agent is added to the object to be treated, the oxide of radioactive cesium contained in the object to be treated is effectively reduced to cesium in the heat treatment process, and the reduced radioactive cesium is efficiently combined with chlorine. It shifts to cesium chloride, and the volatilization of radioactive cesium is further promoted.
本発明による放射性セシウム分離濃縮装置の第一特徴構成は、特許請求の範囲の請求項8に記載した通り、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤からなる塩基度調整助剤を添加する塩基度調整助剤添加装置と、塩基度調整助剤が添加された被処理物を加熱して放射性セシウムを揮散分離する加熱炉と、前記加熱炉で揮散分離された放射性セシウムを含む飛灰を捕集する集塵機と、を備えて構成される放射性セシウム分離濃縮装置であって、被処理物の塩基度が所定値になるように塩基度調整助剤の添加量を決定し、予め求める被処理物の塩基度が前記所定値のもとでの塩素系塩基度調整剤の添加割合とセシウム揮散率との関係に基づいて放射性セシウムの揮散率が最大となる範囲に入るように塩基度調整助剤である塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合を決定する塩基度調整助剤添加量決定装置を備え、前記塩基度調整助剤添加装置は前記塩基度調整助剤添加量決定装置で決定された塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合に従って、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤を添加する点にある。 The first characteristic configuration of the radioactive cesium separation and concentration apparatus according to the present invention includes a chlorine-based basicity adjusting aid and a non-chlorine-based basicity adjusting aid as described in claim 8. A basicity adjusting auxiliary addition device for adding basicity adjusting auxiliary, a heating furnace for heating and treating the object to which basicity adjusting auxiliary is added, and volatilizing and separating radioactive cesium, and volatilized and separated in the heating furnace. And a dust collector that collects fly ash containing radioactive cesium, and a radioactive cesium separation / concentration device comprising a basicity adjustment aid added so that the basicity of the object to be treated becomes a predetermined value The range in which the volatilization rate of radioactive cesium is maximized based on the relationship between the addition rate of the chlorine basicity adjusting agent and the cesium volatilization rate under the predetermined value is determined in advance. Chlorine is a basicity adjustment aid to enter Comprising a basicity adjustment aid amount determination device for determining a Blend ratio of basicity adjusting aid and non-chlorinated basicity adjustment aid, the basicity adjustment aid added device the basicity adjustment aid amount Chlorine basicity adjustment aid and nonchlorine basicity adjustment aid are added to the object to be treated according to the addition amount and blending ratio of chlorine basicity adjustment aid and nonchlorine basicity adjustment aid determined by the determination device. The point is to add.
以上説明した通り、本発明によれば、放射性セシウムの揮散を促進する塩素系助剤の使用量を抑制しながらも、放射性セシウムの揮散率を上昇させることができる放射性セシウム分離濃縮装置の運転方法を提供することができるようになった。 As described above, according to the present invention, the method of operating a radioactive cesium separation and concentration device that can increase the volatilization rate of radioactive cesium while suppressing the amount of chlorine-based auxiliary that promotes volatilization of radioactive cesium. Can now be provided.
以下、本発明による放射性セシウム分離濃縮方法、放射性セシウム分離濃縮装置、及び放射性セシウム分離濃縮装置の運転方法の実施形態を説明する。 Hereinafter, embodiments of the method for separating and concentrating radioactive cesium, the apparatus for separating and concentrating radioactive cesium, and the method for operating the apparatus for separating and concentrating radioactive cesium according to the present invention will be described.
図1には、本発明による放射性セシウム分離濃縮装置1が示されている。放射性セシウム分離濃縮装置1は、放射性セシウムで汚染された土壌を含む被処理物から放射性セシウムを分離濃縮する装置で、放射性セシウムを含有する被処理物を集積する受入部2と、被処理物を1200℃から1500℃の温度範囲で加熱溶融して放射性セシウムを揮散分離する溶融炉5と、溶融炉5で被処理物から揮散分離された放射性セシウムを含む飛灰を捕集する第1集塵機11を備えている。 FIG. 1 shows a radioactive cesium separation and concentration apparatus 1 according to the present invention. The radioactive cesium separation / concentration apparatus 1 is an apparatus for separating and concentrating radioactive cesium from an object to be processed containing soil contaminated with radioactive cesium, and an accepting unit 2 for collecting objects to be processed containing radioactive cesium, and an object to be processed A melting furnace 5 that volatilizes and separates radioactive cesium by heating and melting in a temperature range of 1200 ° C. to 1500 ° C., and a first dust collector 11 that collects fly ash containing radioactive cesium volatilized and separated from the object to be processed in the melting furnace 5. It has.
受入部2に集積された被処理物を溶融炉5に搬送する搬送機構3が設けられ、搬送機構3で搬送される被処理物に塩基度調整助剤を添加する塩基度調整助剤添加装置4が設置されている。塩基度調整助剤として、被処理物に含まれる放射性セシウムを揮散させる助剤としても機能する塩素系塩基度調整助剤が好適に用いられ、塩素系塩基度調整助剤に加えて非塩素系塩基度調整助剤が必要量添加される。 A basicity adjusting auxiliary agent adding device that includes a conveying mechanism 3 that conveys the workpieces accumulated in the receiving unit 2 to the melting furnace 5 and adds a basicity adjusting aid to the workpieces conveyed by the conveying mechanism 3. 4 is installed. As a basicity adjustment aid, a chlorine-based basicity adjustment aid that also functions as an auxiliary for volatilizing radioactive cesium contained in the object to be treated is preferably used. A necessary amount of basicity adjusting aid is added.
塩基度調整助剤添加装置4により添加される塩基度調整助剤の添加量、つまり塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合を決定する塩基度調整助剤添加量決定装置16がさらに設けられている。塩基度調整助剤添加量決定装置16によって、被処理物に対して放射性セシウムの揮散率が所定の範囲に入るように当該添加量及び配合割合が決定される。 Basicity adjustment that determines the amount of basicity adjustment aid added by the basicity adjustment aid addition device 4, that is, the addition amount and blending ratio of the chlorine basicity adjustment aid and the non-chlorine basicity adjustment aid An auxiliary agent addition amount determination device 16 is further provided. The basicity adjustment assistant addition amount determination device 16 determines the addition amount and the mixing ratio so that the volatilization rate of radioactive cesium falls within a predetermined range with respect to the object to be processed.
溶融炉5で溶融され、所定の揮散率で放射性セシウムが揮散された被処理物は溶融スラグとして下方に設置された冷却水槽6に滴下され、急冷されて水砕スラグとなり、排出機構7により槽外に排出される。排出されたスラグは、例えばコンクリート骨材、セメント材料、道路舗装材等の産業用資源として有効利用される。一方、溶融の過程で発生した排ガスは煙道8から流出し、煙道8に沿って配置された冷却装置9、剥離剤添加装置10、第1集塵機11、中和剤添加装置12、第2集塵機13、ヒータ14、触媒塔15、煙突を経て排出される。尚、溶融炉5の炉室及び煙道8は耐火レンガや耐火セメント等の耐火物で被覆されている。 An object to be treated, which is melted in the melting furnace 5 and volatilized with radioactive cesium at a predetermined volatilization rate, is dropped as a molten slag into a cooling water tank 6 installed below, rapidly cooled to become a granulated slag, and the tank is discharged by a discharge mechanism 7. Discharged outside. The discharged slag is effectively used as industrial resources such as concrete aggregate, cement material, road pavement and the like. On the other hand, the exhaust gas generated in the melting process flows out from the flue 8 and is provided with a cooling device 9, a stripping agent adding device 10, a first dust collector 11, a neutralizing agent adding device 12, and a second arranged along the flue 8. It is discharged through a dust collector 13, a heater 14, a catalyst tower 15, and a chimney. The furnace chamber and the flue 8 of the melting furnace 5 are covered with a refractory material such as refractory bricks and refractory cement.
冷却装置9により冷却されて排ガス中で析出し、固化された放射性セシウム化合物を含む飛灰が第1集塵機11で集塵され、排ガスに含まれる塩化水素ガスやSOx等の酸性ガスが中和剤添加装置12から添加される中和剤としての消石灰で中和されてカルシウム塩化物やカルシウム硫化物として第2集塵機13で集塵される。第1集塵機11及び第2集塵機13は主にバグフィルタで構成され、潮解性を有する飛灰が濾布に強固に付着しないように、剥離剤添加装置10から添加された剥離剤が濾布表面にコーティングされ、パルスジェット等による清掃時の剥離性が確保される。尚、乾式で中和する場合には中和剤として消石灰が好適に用いられるが、例えば湿式洗浄装置を利用する場合には水酸化ナトリウム(NaOH)も用いられる。 The fly ash containing the radioactive cesium compound that has been cooled by the cooling device 9 and deposited in the exhaust gas is collected by the first dust collector 11, and acid gases such as hydrogen chloride gas and SOx contained in the exhaust gas are neutralized. Neutralized with slaked lime as a neutralizing agent added from the adding device 12 and collected as calcium chloride or calcium sulfide by the second dust collector 13. The first dust collector 11 and the second dust collector 13 are mainly composed of bag filters, and the release agent added from the release agent addition device 10 is applied to the filter cloth surface so that fly ash having deliquescence does not adhere firmly to the filter cloth. It is coated to ensure releasability during cleaning with a pulse jet or the like. In the case of neutralization by dry method, slaked lime is preferably used as a neutralizing agent, but sodium hydroxide (NaOH) is also used when, for example, a wet cleaning apparatus is used.
図2には、上述の放射性セシウム分離濃縮装置1によって実行される本発明の放射性セシウム分離濃縮装置の運転方法が示されている。
即ち、塩基度調整助剤添加量決定装置16によって被処理物に対して放射性セシウムの揮散率が所定の範囲に入るように塩基度調整助剤である塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合を予め決定する塩基度調整助剤添加量決定工程が実行され、塩基度調整助剤添加装置4によって被処理物に塩基度調整助剤を添加する塩基度調整工程が実行され、溶融炉5によって塩基度調整助剤が添加された被処理物を溶融して溶融スラグから放射性セシウムを揮散分離する分離工程が実行され、第1集塵機11によって排ガスに含まれる放射性セシウムを捕集する捕集工程が実行される。
FIG. 2 shows a method for operating the radioactive cesium separation and concentration apparatus of the present invention, which is executed by the above-described radioactive cesium separation and concentration apparatus 1.
That is, the basicity adjusting auxiliary agent addition amount determining device 16 uses a basicity adjusting auxiliary agent and a non-chlorine basicity adjusting auxiliary agent so that the volatilization rate of radioactive cesium falls within a predetermined range with respect to the object to be processed. A basicity adjusting auxiliary agent addition amount determining step for predetermining the adding amount and blending ratio of the basicity adjusting auxiliary agent is executed, and the basicity adjusting auxiliary agent adding device 4 adds the basicity adjusting auxiliary agent to the workpiece. A degree adjustment step is executed, a separation step is performed in which the material to which the basicity adjustment aid is added is melted by the melting furnace 5 to volatilize and separate radioactive cesium from the molten slag, and is contained in the exhaust gas by the first dust collector 11 A collection step for collecting radioactive cesium is performed.
土壌を汚染した放射性セシウムは、土壌中の粘土鉱物成分等への吸着性が高く、一旦吸着されてしまうと物理的に分離除去することが難しい。また、強固な結合状態で土壌に吸着されているため、そのままでは加熱しても揮散分離しにくい。 The radioactive cesium contaminating the soil has a high adsorptivity to clay mineral components and the like in the soil, and once adsorbed, it is difficult to physically separate and remove it. In addition, since it is adsorbed to the soil in a strongly bonded state, it is difficult to volatilize and separate even if heated as it is.
従来は、加熱処理時にセシウムが揮散しやすいように、揮散促進剤として塩化ナトリウム等の塩素系助剤を被処理物に添加することにより、放射性セシウムと結合して沸点の低い塩化セシウムに移行させる方法が採用されていたが、加熱処理で塩化ナトリウム由来の腐食性ガスである塩化水素ガスが大量に発生するため、排ガスへの中和剤の添加量が増して薬剤コストの上昇を招いたり、飛灰量の増加のため大型のバグフィルタを構成することによる設備コストの上昇を招いたりするという問題があった。 Conventionally, by adding a chlorine-based auxiliary agent such as sodium chloride as a volatilization accelerator to the object to be treated so that cesium is easily volatilized during heat treatment, it is combined with radioactive cesium and transferred to cesium chloride having a low boiling point. Although the method was adopted, hydrogen chloride gas, which is a corrosive gas derived from sodium chloride, is generated in large amounts by heat treatment, so the amount of neutralizing agent added to the exhaust gas increases, leading to an increase in drug cost, There has been a problem in that the equipment cost is increased due to the construction of a large bag filter for increasing the amount of fly ash.
また、沸点が溶融温度に近い塩化ナトリウムは、セシウムと化合する前に揮散し易く、塩化水素ガスの発生量が増し易いという特性があるため、効率的にセシウムを揮散させるという観点でさらなる改良の余地があった。 In addition, sodium chloride whose boiling point is close to the melting temperature tends to volatilize before combining with cesium, and the amount of hydrogen chloride gas generated tends to increase, so that further improvement can be achieved from the viewpoint of efficiently volatilizing cesium. There was room.
ところで、塩素系助剤を添加して被処理物を加熱溶融する際に被処理物に塩基度調整助剤を添加するとスラグの骨格構造が脆弱化して、スラグからセシウムが遊離し易くなる。 By the way, when the basicity adjusting aid is added to the object to be treated when the chlorine-based assistant is added and the object to be treated is heated and melted, the slag skeleton structure becomes weak and cesium is easily released from the slag.
そこで、塩基度調整工程で被処理物に添加する塩基度調整助剤として塩素系の塩基度調整助剤を用いることにより、好ましい塩基度への調整のみならず、放射性セシウムの揮散促進剤としても機能させ、別途の塩化ナトリウム等の塩素系助剤を添加しなくても、分離工程で高効率に放射性セシウムを揮散させることができ、捕集工程で効率的に放射性セシウムを捕集できるようになる。つまり、塩素系塩基度調整助剤は、塩基度の調整と塩素による揮散促進の両方の機能を兼ね備えた高機能の塩基度調整助剤である。 Therefore, by using a chlorine-based basicity adjustment aid as a basicity adjustment aid added to the object to be treated in the basicity adjustment step, not only adjustment to a preferable basicity but also a volatilization accelerator for radioactive cesium It is possible to function, and even without adding a chlorine-based auxiliary agent such as sodium chloride, the radioactive cesium can be volatilized with high efficiency in the separation process, and the radioactive cesium can be efficiently collected in the collection process. Become. That is, the chlorine-based basicity adjustment aid is a high-functionality basicity adjustment aid that has both functions of adjusting basicity and promoting volatilization by chlorine.
そして、塩基度の調整に際して塩素系の塩基度調整助剤に加えて非塩素系の塩基度調整助剤を加えることにより、添加する塩素量を減らすことで、塩化水素ガスの発生を抑制しながらも、放射性セシウムの揮散率をさらに上昇させることができるようになる。特に、被処理物に添加する塩基度調整助剤の量や塩基度を略一定とした条件で、放射性セシウムの揮散率を向上させるときに有用である。 In addition, by adding a non-chlorine basicity adjustment aid in addition to a chlorine-based basicity adjustment aid when adjusting the basicity, while reducing the amount of chlorine to be added, while suppressing the generation of hydrogen chloride gas However, the volatilization rate of radioactive cesium can be further increased. In particular, it is useful when the volatilization rate of radioactive cesium is improved under conditions where the amount and basicity of the basicity adjusting aid added to the object to be processed are substantially constant.
具体的に、塩基度調整助剤添加量決定工程では、少量の被処理物に対して、塩素系塩基度調整助剤及び非塩素系塩基度調整助剤の添加量及び配合割合を異ならせた試験サンプルを試験装置で加熱溶融して得られたスラグの成分分析を行ない、放射性セシウムの揮散率が所定の範囲(ここでは下限値及び上限値の双方であってもよいし、下限値のみであってもよい。)に入る添加量及び配合割合に決定される。 Specifically, in the basicity adjustment aid addition amount determination step, the addition amount and the blending ratio of the chlorine-based basicity adjustment aid and the non-chlorine-based basicity adjustment aid are varied with respect to a small amount of the object to be processed. Component analysis of the slag obtained by heating and melting the test sample with a test device is performed, and the volatilization rate of radioactive cesium may be within a predetermined range (here, both the lower limit value and the upper limit value, or only the lower limit value) The amount of addition and the mixing ratio may be determined.
塩基度調整助剤の添加率は放射性セシウムの揮散率、つまり、加熱処理前後の放射性物質の減少率と相関する。被処理物の放射性物質の量は、地域、固形物の種類により異なることから、その濃度が、例えば法定の使用可能値以下または処分可能値以下、あるいは自主規制される使用可能値以下または処分可能値以下となるように、地域、固形物の種類に応じて揮散率の目標値を算出すればよく、その値を達成できるように、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合を決定すればよい。 The addition rate of the basicity adjusting aid correlates with the volatilization rate of the radioactive cesium, that is, the decrease rate of the radioactive material before and after the heat treatment. The amount of radioactive material in the material to be treated varies depending on the region and the type of solid matter. For example, the concentration is below the legally usable value or below the disposable value, or below the voluntary regulated usable value or at the disposal. The target value of volatilization rate may be calculated according to the region and the type of solid matter so that it is below the value. Chlorine basicity adjustment aid and non-chlorine basicity adjustment aid so that the value can be achieved. What is necessary is just to determine the addition amount and compounding ratio of an agent.
土壌のように被処理物の塩基度(CaO(重量%)/SiO2(重量%))が低い場合には、被処理物に塩基度調整助剤を添加することによって、溶融スラグからの放射性セシウムの分離効率を向上させることができる。尚、一般的な土壌の塩基度(CaO(重量%)/SiO2(重量%))は0.03〜0.1程度、土壌の光学的塩基度は0.50〜0.52程度である。 If the basicity of the object to be treated as the soil (CaO (wt%) / SiO 2 (wt%)) is low, by adding a base adjustment aid to be treated, the radioactive from molten slag The separation efficiency of cesium can be improved. Incidentally, the general soil basicity (CaO (wt%) / SiO 2 (wt%)) is about 0.03 to 0.1, the optical basicity of the soil is about 0.50 to 0.52 .
被処理物の塩基度(CaO(重量%)/SiO2(重量%))が低いと、SiO2を主成分として陽イオン結合で構成されるスラグの骨格構造の結合が強く、骨格構造と結合しているセシウムとの結合力も強い。そのため、塩素成分がセシウムと結合しようとしてもセシウムは骨格構造から離れることが出来ず、塩素とセシウムの結合は阻害され、結果として溶融スラグに放射性セシウムが残存する傾向が強くなる。 When the basicity of the object to be treated (CaO (wt%) / SiO 2 (wt%)) is low, strong binding of the skeletal structure composed slug cation binding SiO 2 as the main component, combined with the skeletal structure Strong binding strength with cesium. Therefore, even if the chlorine component tries to combine with cesium, cesium cannot leave the skeletal structure, the bond between chlorine and cesium is inhibited, and as a result, there is a strong tendency for radioactive cesium to remain in the molten slag.
そのような場合でも、塩基度調整助剤を添加することによって、スラグの塩基度が上昇する。より低い温度で被処理物が溶融して流動性が上昇する。つまり、スラグの骨格構造の結合が弱くなり、セシウムはスラグの骨格構造から離れやすくなる。添加された塩素系塩基度調整助剤に含まれる塩素と放射性セシウムはイオン結合の機会が増加し、塩化セシウムに移行する反応が促進されるためである。そのため、放射性セシウムの揮散が促進される。 Even in such a case, the basicity of the slag is increased by adding the basicity adjusting aid. The workpiece is melted at a lower temperature and the fluidity is increased. That is, the bond of the slag skeleton structure is weakened, and cesium is easily separated from the slag skeleton structure. This is because the chlorine and radioactive cesium contained in the added chlorine-based basicity adjusting aid increase the chance of ionic bonding and promote the reaction to transfer to cesium chloride. Therefore, volatilization of radioactive cesium is promoted.
塩基度として簡易的な2成分塩基度(CaO(重量%)/SiO2(重量%))を指標として用いる場合を説明したが、塩基度はこれ以外にも様々な定義があり、廃棄物学会論文誌(Vol.19,No19,pp17-25,2008)に開示されている。例えば、以下の式で示すように、複数の成分で表すものもある。
(CaO+MgO+Fe2O3+K2O+Na2O)/(SiO2+Al2O3)
Simple binary basicity as basicity (CaO (wt%) / SiO 2 (wt%)) and has been described the case of using as an index, basicity has also various definitions in addition to this, waste Society It is disclosed in the journal (Vol.19, No19, pp17-25,2008). For example, some are represented by a plurality of components as shown in the following formula.
(CaO + MgO + Fe 2 O 3 + K 2 O + Na 2 O) / (SiO 2 + Al 2 O 3 )
光学的塩基度は、対応可能な成分の数を大幅に増やし、ほぼ全ての酸化物を加味することのできる塩基度であるため、様々な組成を有する処理対象固形物に対して共通的に使用可能な塩基度指標である。 Optical basicity is a basicity that can greatly increase the number of components that can be handled and can take into account almost all oxides, so it is commonly used for solids to be processed having various compositions. It is a possible basicity index.
光学的塩基度は、DuffyとIngramによって見出された指標であり、紫外光吸収ピークがガラス組成に対して敏感に変化することに注目し、多成分系酸化物ガラスについて、ガラスの組成とそれらを構成するカチオンの電気陰性度とから、以下の数式に基づいて導き出される指標である。 Optical basicity is an index found by Duffy and Ingram, focusing on the fact that the ultraviolet light absorption peak changes sensitively with respect to the glass composition. Is an index that is derived from the electronegativity of the cation constituting s based on the following formula.
光学的塩基度Λ=1−Σ(zi・ri/2)・(1−1/γi)
但し、γi=1.36(χi−0.26)
ここに、ziはi種カチオンの原子価であり、riは酸素1個あたりで表現したときのi種カチオンの数であり、χiはi種カチオンの電気陰性度である。
Optical basicity Λ = 1−Σ (zi · ri / 2) · (1-1 / γi)
However, γi = 1.36 (χi−0.26)
Here, zi is the valence of the i-type cation, ri is the number of the i-type cation expressed per oxygen, and χi is the electronegativity of the i-type cation.
塩基度は塩素系、非塩素系のどちらの塩基度調整助剤を添加しても同様に増加する。したがって、塩素系と非塩素系の両者の添加比率は被処理物の塩素濃度を指標として調整する。塩基度が同一な値であっても、塩素濃度が高いほど塩素系塩基度調整助剤の比率が高く、塩素濃度が低いほど非塩素系塩基度調整助剤の比率が高い添加条件となる。 The basicity increases in the same manner regardless of whether a chlorine-based or non-chlorine-based basicity adjusting aid is added. Therefore, the addition ratio of both chlorine and non-chlorine is adjusted using the chlorine concentration of the object to be treated as an index. Even if the basicity is the same value, the higher the chlorine concentration, the higher the ratio of the chloric basicity adjusting aid, and the lower the chlorine concentration, the higher the ratio of the non-chlorine basicity adjusting aid.
つまり、塩基度調整助剤添加後の被処理物の塩基度、光学的塩基度、塩素濃度、被処理物の加熱処理工程後の塩基度、光学的塩基度の何れかから選択される単一または複数の指標が所定の範囲に収まるように、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合を決定することも可能である。 In other words, the basicity, optical basicity, chlorine concentration, basicity after the heat treatment step of the object to be processed, and optical basicity are selected from the basicity of the object to be processed after the addition of the basicity adjusting aid. Alternatively, it is also possible to determine the addition amount and the blending ratio of the chlorine-based basicity adjusting aid and the non-chlorine basicity-adjusting aid so that a plurality of indices fall within a predetermined range.
塩素系塩基度調整助剤として、無機塩化物または無機塩化物が含まれる物質の何れかから選択される単一または複数の物質を採用することが好ましく、塩化カルシウム、塩化ナトリウム、塩化カリウム、塩化鉄の何れかから選択される単一または複数の物質を採用することがさらに好ましく、特に高沸点の塩化物として塩化カルシウム等が好適に用いられ、第2集塵機13で回収された塩化カルシウム等を含む飛灰や、ごみ焼却炉で発生した塩化カルシウム等を含む飛灰を使用することも可能である。 As the chloric basicity adjusting aid, it is preferable to employ a single substance or a plurality of substances selected from either inorganic chlorides or substances containing inorganic chlorides, such as calcium chloride, sodium chloride, potassium chloride, chloride. It is more preferable to employ a single substance or a plurality of substances selected from any one of iron, and calcium chloride or the like is preferably used as a high boiling point chloride, and calcium chloride or the like recovered by the second dust collector 13 is preferably used. It is also possible to use fly ash containing fly ash or calcium ash generated in a garbage incinerator.
非塩素系塩基度調整助剤として、非塩素系アルカリ金属化合物、非塩素系アルカリ土類金属化合物、非塩素系マグネシウム化合物、非塩素系ホウ素化合物、非塩素系鉄化合物、及び非塩素系鉛化合物の何れかから選択される単一または複数の物質を好適に用いることができる。 Non-chlorine basicity adjustment aids include non-chlorine alkali metal compounds, non-chlorine alkaline earth metal compounds, non-chlorine magnesium compounds, non-chlorine boron compounds, non-chlorine iron compounds, and non-chlorine lead compounds. A single substance or a plurality of substances selected from any of the above can be suitably used.
特に、酸化カルシウム、水酸化カルシウム、炭酸カルシウム、炭酸ナトリウム、炭酸リチウム、炭酸カリウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、酸化ホウ素、ホウ砂、ホウ酸、酸化第一鉄、四酸化三鉄、酸化第二鉄、一酸化鉛、二酸化鉛等の何れかから選択される単一または複数の物質が好適に用いられる。 In particular, calcium oxide, calcium hydroxide, calcium carbonate, sodium carbonate, lithium carbonate, potassium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, boron oxide, borax, boric acid, ferrous oxide, triiron tetroxide, A single substance or a plurality of substances selected from any one of ferric oxide, lead monoxide, lead dioxide and the like are preferably used.
塩基度調整工程で添加される塩素系塩基度調整助剤と非塩素系塩基度調整助剤を添加した後の被処理物の塩基度が略一定であることが好ましく、塩基度を略一定に保つ限り、塩基度調整工程で添加される塩素系塩基度調整助剤または非塩素系塩基度調整助剤の種類や添加割合を変えても、スラグの骨格の脆弱化による放射性セシウムの揮散率の上昇という効果が恒常的に得られる。特に、同じ元素の塩素系塩基度調整助剤と非塩素系塩基度調整助剤の組み合わせの場合に、添加割合をモル比で変更すると、塩基度が変化することなく、調整をすることが可能となる。尚、塩基度調整助剤の添加量の制御性を向上させるため、塩基度調整効果のない物質を混合して塩基度調整助剤とすることも可能である。また、一定の塩基度の条件の下で、塩素の量(塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加割合)を変えて、放射性セシウムの揮散率を変化させることも可能である。塩素の量を減らしても、放射性セシウムの揮散率が上がる場合があり、放射性セシウムの揮散率を最大とする添加割合が存在する。 It is preferable that the basicity of the object to be treated after adding the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid added in the basicity adjusting step is substantially constant, and the basicity is made substantially constant. As long as it is maintained, the volatilization rate of radioactive cesium due to the weakening of the slag skeleton may be changed even if the type and addition ratio of the chlorine-based basicity adjusting aid or non-chlorine-based basicity adjusting aid added in the basicity adjusting step are changed. The effect of rising is always obtained. In particular, in the case of a combination of a chlorine basicity adjustment aid and a non-chlorine basicity adjustment aid of the same element, adjustment can be made without changing the basicity by changing the addition ratio in molar ratio It becomes. In addition, in order to improve the controllability of the addition amount of the basicity adjusting aid, it is possible to use a basicity adjusting aid by mixing a substance having no basicity adjusting effect. It is also possible to change the volatilization rate of radioactive cesium by changing the amount of chlorine (addition ratio of chlorine-based basicity adjusting aid and non-chlorine-based basicity adjusting aid) under the condition of constant basicity. Is possible. Even if the amount of chlorine is reduced, the volatilization rate of radioactive cesium may increase, and there is an addition ratio that maximizes the volatilization rate of radioactive cesium.
塩基度調整工程で添加される塩素系塩基度調整助剤が塩化カルシウムであり非塩素系塩基度調整助剤が水酸化カルシウムであることが好ましく、放射性セシウムで汚染された広範囲に広がる土壌に対して好適に放射性セシウムを分離除去でき、しかも塩基度調整工程で添加される塩素系塩基度調整助剤として塩化カルシウムを用いれば効果的に塩基度を調整できるとともに放射性セシウムの揮散率を上昇させることができ、非塩素系塩基度調整助剤として水酸化カルシウムを用いれば、塩化カルシウムに代替して効果的に塩基度を調整できるようになる。 It is preferable that the chlorine-based basicity adjusting aid added in the basicity adjusting step is calcium chloride and the non-chlorine-based basicity adjusting aid is calcium hydroxide, for a wide area of soil contaminated with radioactive cesium. In addition, it is possible to separate and remove radioactive cesium suitably, and when calcium chloride is used as a chlorine-based basicity adjustment aid added in the basicity adjustment step, basicity can be adjusted effectively and the volatilization rate of radioactive cesium can be increased. If calcium hydroxide is used as a non-chlorine basicity adjusting aid, basicity can be effectively adjusted instead of calcium chloride.
塩素系塩基度調整助剤として塩化カルシウムを用い、非塩素系塩基度調整助剤として水酸化カルシウムを用いる場合には、塩化カルシウムを塩素系塩基度調整助剤の合計量の30重量%から50重量%の割合で添加し、被処理物である地土壌に対する塩基度調整助剤全体の添加割合を30重量%から45重量%に調整することで、塩素系ガスの発生量を抑制しながらも放射性セシウムを高い揮散率で揮散させることができるようになる。 When calcium chloride is used as the chlorine-based basicity adjusting aid and calcium hydroxide is used as the non-chlorine basicity-adjusting aid, the calcium chloride is used in an amount of 30% to 50% of the total amount of the chlorine-based basicity adjusting aid. While adding at a percentage by weight, and adjusting the addition ratio of the basicity adjustment aid to the soil to be treated as a whole from 30% to 45% by weight, while suppressing the generation of chlorine-based gas Radiocesium can be volatilized at a high volatilization rate.
塩基度調整助剤添加量決定工程では、還元剤が添加された被処理物に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合が決定されることが好ましい。還元剤を被処理物に添加すれば、加熱処理工程で被処理物に含まれる放射性セシウムの酸化物が効果的にセシウムに還元処理され、還元された放射性セシウムが効率的に塩素と結合して塩化セシウムに移行し、放射性セシウムの揮散がより促進されるようになる。 In the basicity adjusting auxiliary agent addition amount determining step, the addition amount and the mixing ratio of the chlorine basicity adjusting auxiliary agent and the non-chlorine basicity adjusting auxiliary agent are determined with respect to the object to which the reducing agent is added. It is preferable. If a reducing agent is added to the object to be treated, the oxide of radioactive cesium contained in the object to be treated is effectively reduced to cesium in the heat treatment process, and the reduced radioactive cesium is efficiently combined with chlorine. It shifts to cesium chloride, and the volatilization of radioactive cesium is further promoted.
塩基度調整助剤添加量決定工程で好ましい還元剤の添加量を求め、溶融炉に投入される被処理物に還元剤を添加する還元剤添加装置を備えればよい。還元剤として、活性炭、グラファイト、カーボンブラック、コークス、木炭、プラスチック、草木、及び下水汚泥の何れかから選択される単一または複数の物質が好適に用いられる。下水汚泥には生物処理によって有機物が分解された炭素成分が含まれているため、還元剤として好適に利用できる。尚、プラスチックのうち廃プラスチックを用いれば経済性が上がり、より好適に用いられる。 What is necessary is just to provide the reducing agent addition apparatus which calculates | requires the preferable addition amount of a reducing agent in a basicity adjustment adjuvant addition amount determination process, and adds a reducing agent to the to-be-processed object thrown into a melting furnace. As the reducing agent, a single substance or a plurality of substances selected from activated carbon, graphite, carbon black, coke, charcoal, plastic, vegetation, and sewage sludge are preferably used. Since sewage sludge contains a carbon component obtained by decomposing organic matter by biological treatment, it can be suitably used as a reducing agent. In addition, if waste plastic is used among plastics, economical efficiency will improve and it will be used more suitably.
塩基度調整助剤添加量決定装置16として、試験炉及び試験炉で溶融されたスラグの成分分析装置を備え、さらに、受入部2に受け入れられた被処理物を定量サンプルして所定量の塩基度調整助剤、好ましくは還元剤をも自動添加し、試験炉で溶融処理し、得られたスラグの成分を成分分析して、好ましい塩基度調整助剤の添加量及び塩素系と非塩素系の添加割合を自動決定して、決定した添加量及び添加割合を塩基度調整助剤添加装置4に出力する制御装置を備えることが好ましい。 The basicity adjusting auxiliary agent addition amount determination device 16 includes a test furnace and a component analysis device for slag melted in the test furnace. Further, a predetermined amount of base is obtained by quantitatively sampling the object to be processed received in the receiving unit 2. A degree-adjusting assistant, preferably a reducing agent, is automatically added, melted in a test furnace, and the components of the obtained slag are analyzed to determine the preferred basicity-adjusting assistant addition amount and chlorine-based and non-chlorine-based It is preferable to include a control device that automatically determines the addition ratio of and outputs the determined addition amount and addition ratio to the basicity adjusting aid adding device 4.
以上の説明の通り、本発明による放射性セシウム分離濃縮方法は、土壌を含む被処理物に含まれる放射性セシウムを加熱処理により分離濃縮する放射性セシウム分離濃縮方法であって、少なくとも塩素系塩基度調整助剤を含む塩基度調整助剤を被処理物に添加する塩基度調整工程と、塩基度調整助剤が添加された被処理物を1200℃から1500℃に加熱して被処理物から放射性セシウムを揮散分離する分離工程と、前記分離工程で揮散分離された放射性セシウムを捕集する捕集工程と、を含む点にある。 As described above, the method for separating and concentrating radioactive cesium according to the present invention is a method for separating and concentrating radioactive cesium contained in an object to be treated including soil by heat treatment, and is at least a chlorine-based basicity adjustment aid. A basicity adjustment step of adding a basicity adjusting aid containing an agent to the object to be treated, and heating the object to which the basicity adjusting aid is added from 1200 ° C. to 1500 ° C. to remove radioactive cesium from the object to be treated It is in the point including the separation process which volatilizes and separates, and the collection process which collects the radioactive cesium volatilized and separated by the said separation process.
また、塩基度調整工程は、塩素系塩基度調整助剤と非塩素系塩基度調整助剤を所定の添加割合で配合する工程であり、前記所定の添加割合は、前記分離工程で被処理物から揮散する放射性セシウムの揮散率に基づいて決定される値であることが好ましいが、少なくとも塩基度調整助剤として塩素系塩基度調整助剤を用いることが好ましい。 The basicity adjustment step is a step of blending a chlorine basicity adjustment aid and a non-chlorine basicity adjustment aid at a predetermined addition ratio, and the predetermined addition ratio is the object to be treated in the separation step. Although it is preferable that it is a value determined based on the volatilization rate of the radioactive cesium volatilized from, it is preferable to use a chlorine basicity adjustment aid as at least a basicity adjustment aid.
塩基度調整工程で添加される塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加割合は、塩素系塩基度調整助剤が塩基度調整助剤全体の25重量%から85重量%であることが好ましく、これにより塩素系塩基度調整助剤を単独で用いるよりも放射性セシウムの揮散率を上昇させながらも、排ガスに含まれる塩素系の腐食ガスの発生量を抑制することができるようになる。 The addition ratio of the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid added in the basicity adjusting step is 25% by weight to 85% by weight of the basic basicity adjusting aid. It is preferable to suppress the generation amount of chlorine-based corrosive gas contained in the exhaust gas while increasing the volatilization rate of radioactive cesium rather than using a chlorine-based basicity adjusting aid alone. become able to.
塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加割合は、被処理物の光学的塩基度を指標にする場合には、0.6以上になるように決定される値であることが好ましく、2成分塩基度CaO(重量%)/SiO2(重量%)を指標にする場合には、0.7以上になるように決定されることが好ましく、どちらも上限は特に制限されることはない。また、光学的塩基度を指標にする場合には、0.61以上0.68以下になるように決定することがより好ましく。2成分塩基度CaO(重量%)/SiO2(重量%)を指標にする場合には、0.8以上1.6以下になるように決定することがより好ましい。 The addition ratio of the chlorine basicity adjusting aid and the non-chlorine basicity adjusting aid is a value determined to be 0.6 or more when the optical basicity of the object to be processed is used as an index. It is preferable that the two-component basicity CaO (wt%) / SiO 2 (wt%) is used as an index, and it is preferably determined to be 0.7 or more. It will never be done. Further, when optical basicity is used as an index, it is more preferable to determine the optical basicity to be 0.61 or more and 0.68 or less. When the two-component basicity CaO (% by weight) / SiO 2 (% by weight) is used as an index, it is more preferably determined to be 0.8 or more and 1.6 or less.
さらに、塩基度調整工程で添加される塩基度調整助剤の添加割合は、被処理物に対して25重量%から50重量%であることが好ましく、30重量%から50重量%であることがさらに好ましい。このような値を採用すれば放射性セシウムの揮散率を上昇させながらも、塩基度調整助剤の使用量を適正量に調整することができる。 Further, the addition ratio of the basicity adjusting aid added in the basicity adjusting step is preferably 25% by weight to 50% by weight, and preferably 30% by weight to 50% by weight with respect to the object to be processed. Further preferred. If such a value is employ | adopted, the usage-amount of basicity adjustment adjuvant can be adjusted to an appropriate quantity, raising the volatilization rate of radioactive cesium.
さらに、所定の添加割合は、前記分離工程で被処理物から揮散する放射性セシウムの揮散率が99%以上になるように決定される値であることが好ましい。放射性セシウムの揮散率が99%以上になれば、分離工程の後に被処理物に残存する放射線量が許容値、例えば一般廃棄物として許容される値に調整されるようになる。 Furthermore, the predetermined addition ratio is preferably a value determined such that the volatilization rate of radioactive cesium volatilized from the object to be processed in the separation step is 99% or more. If the volatilization rate of radioactive cesium is 99% or more, the radiation dose remaining on the object to be treated after the separation step is adjusted to an allowable value, for example, a value allowable as general waste.
また、被処理物が放射性物質を5000Bq/kg以上含む高濃度に汚染された被処理物であっても、放射性セシウムが効率よく分離濃縮されるので、分離工程の後に被処理物に残存する放射性物質の量が許容値、例えば土木資材などとして有効に利用できる値に調整されたり、例えば残存する放射性物質が100Bq/kg(クリアランスレベル)以下となり被処理物は放射性物質を含まないものとして取り扱うことができるようになる。 Even if the object to be processed is contaminated to a high concentration containing a radioactive substance of 5000 Bq / kg or more, radioactive cesium is efficiently separated and concentrated, so that the radioactive material remaining on the object to be processed after the separation step The amount of the substance is adjusted to an allowable value, for example, a value that can be used effectively as a civil engineering material, or, for example, the remaining radioactive material is 100 Bq / kg (clearance level) or less, and the object to be treated is treated as containing no radioactive material. Will be able to.
更に、放射性セシウムの揮散率が99%以上であると、被処理物に含まれる放射性物質が10000Bq/kgであっても、処理後の放射性物質が100Bq/kg(クリアランスレベル)以下となり被処理物は放射性物質を含まないものとして取り扱うことができる。上述の実施形態では被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤を同一の装置で纏めて投入する機構を備えた例を説明したが、塩素系塩基度調整助剤と非塩素系塩基度調整助剤を異なる装置で別個に投入してもよい。 Furthermore, if the volatilization rate of radioactive cesium is 99% or more, even if the radioactive material contained in the object to be processed is 10000 Bq / kg, the radioactive material after treatment becomes 100 Bq / kg (clearance level) or less and the object to be processed Can be treated as containing no radioactive material. In the above-described embodiment, an example has been described in which a chlorine-based basicity adjustment aid and a non-chlorine basicity-adjustment aid are collectively added to a workpiece using the same apparatus. The agent and the non-chlorine basicity adjusting aid may be added separately in different apparatuses.
煙道8では、排ガスの温度低下とともに揮散した放射性セシウムの一部が析出し、耐火物へ浸透する虞がある。上述の通り煙道8は耐火レンガや耐火セメント等の耐火物で被覆されているので、耐火物の張替えメンテナンス時に汚染された耐火物を粉砕して被処理物として同様に処理することも可能である。 In the flue 8, a part of the radioactive cesium volatilized with a decrease in the temperature of the exhaust gas may be deposited and penetrate into the refractory. As described above, since the flue 8 is covered with a refractory material such as refractory bricks or refractory cement, it is also possible to pulverize the refractory material contaminated during the refractory maintenance and to treat it as a material to be treated. is there.
上述の実施形態では加熱炉として溶融炉の形式は限定せずに説明したが、必要な温度まで加温できれば燃料式、電気式、連続式とバッチ式の何れでもよい。例えば回転式表面溶融炉、固定式表面溶融炉、シャフト式溶融炉、キルン式溶融炉、電気溶融炉、高周波炉、プラズマ溶融炉等、何れの形式であってもいい。 In the above-described embodiment, the type of the melting furnace as the heating furnace has been described without limitation, but any of a fuel type, an electric type, a continuous type, and a batch type may be used as long as it can be heated to a necessary temperature. For example, any type such as a rotary surface melting furnace, a fixed surface melting furnace, a shaft melting furnace, a kiln melting furnace, an electric melting furnace, a high-frequency furnace, a plasma melting furnace, and the like may be used.
尚、回転式表面溶融炉は被処理物に可燃物を含む下水汚泥、各種バイオマス等であっても安定して処理することができ、可燃物を燃料の補助として利用することができる、より良い形式である。また、加熱炉として十分な加熱が行われば、溶融炉に限らずどのような形式であってもよい。 In addition, the rotary surface melting furnace can stably treat even sewage sludge containing various combustible materials, various biomass, etc., and the combustible material can be used as an auxiliary fuel. Format. Moreover, as long as sufficient heating is performed as a heating furnace, not only a melting furnace but any type may be used.
以上の説明では、土壌を含む被処理物を対象に本発明を説明したが、本発明による放射性セシウム分離濃縮方法は、土壌に限らず下水汚泥、浚渫汚泥、一般廃棄物、産業廃棄物、農業系バイオマス、木質系バイオマス、草本系バイオマス若しくはそれらの焼却残さから選択される単一または複数の物質と土壌との混合物であっても適用可能であり、土壌を除く上述の被処理物であっても適用可能である。 In the above description, the present invention has been described for an object to be treated including soil. However, the method for separating and concentrating radioactive cesium according to the present invention is not limited to soil, but includes sewage sludge, straw sludge, general waste, industrial waste, agriculture. It can be applied to a mixture of a single substance or a plurality of substances selected from a biomass, a woody biomass, a herbaceous biomass, or a residue from incineration thereof, and soil, and is the above-described object to be treated excluding soil. Is also applicable.
上述した実施形態は、何れも本発明の一例であり、該記載により本発明が限定されるものではなく、各部の具体的な構成は本発明の作用効果が奏される範囲で適宜変更設計可能であることはいうまでもない。 Each of the above-described embodiments is an example of the present invention, and the present invention is not limited by the description, and the specific configuration of each part can be appropriately changed and designed within the range where the effects of the present invention are exhibited. Needless to say.
以下に実験例を説明する。尚、以下の実験例で揮発率を除いて「%」というときは、「重量%」を意味するものとする。
本実験では、試料の基材として模擬土壌を用いた。この模擬土壌は真砂土(砂成分)99.5%と炭酸セシウム(Cs2CO3)試薬0.5%を混合したもの(基材A)と、土壌(真砂土とベントナイトを重量比85:15で混合したもの)70%に下水汚泥焼却灰(可燃分)29%と炭酸セシウム(Cs2CO3)試薬1%を混合したもの(基材B)である。図3に基材A,Bの組成を示す。
An experimental example will be described below. In the following experimental examples, “%” excluding the volatilization rate means “% by weight”.
In this experiment, simulated soil was used as the base material of the sample. This simulated soil is a mixture of 99.5% pure sand (sand component) and 0.5% cesium carbonate (Cs 2 CO 3 ) reagent (base material A) and soil (mass sand and bentonite in a weight ratio of 85: 15) and 70% of sewage sludge incineration ash (combustible component) 29% and cesium carbonate (Cs 2 CO 3 ) reagent 1% (base material B). FIG. 3 shows the compositions of the substrates A and B.
この基材に塩素系塩基度調整助剤としてCaCl2若しくはNaCl、及び非塩素系塩基度調整助剤としてCa(OH)2若しくはNa2CO3を添加して試料とし、添加薬剤種、添加薬剤比率、放射性セシウムの揮散率を最大化する条件を変えて以下の実験を行った。 A sample is prepared by adding CaCl 2 or NaCl as a chlorine-based basicity adjusting aid and Ca (OH) 2 or Na 2 CO 3 as a non-chlorine basicity adjusting aid to the base material, and adding the added drug type and the added drug. The following experiment was conducted by changing the ratio and the conditions for maximizing the volatilization rate of radioactive cesium.
試験方法は、図4(a),(b),(c)に示すように、舟形形状の磁性ボートの一端部側に試験片を充填し、充填部が上方になるように磁性ボートを所定角度傾斜させた状態で、所定温度に保持された空気自然対流下の電気炉内に所定時間(15分)静置し、自然冷却させてスラグを作成し、スラグを磁性ボートから分離した。スラグの重量と元素含有濃度を分析し、各元素の揮散率を算出した。また、以下に示す一部の実験例では、スラグの状態を確認した。 As shown in FIGS. 4 (a), 4 (b), and 4 (c), the test method is such that a test piece is filled on one end side of a boat-shaped magnetic boat, and the magnetic boat is set so that the filling portion faces upward. With the angle inclined, the slag was left standing in an electric furnace under natural convection maintained at a predetermined temperature for a predetermined time (15 minutes), allowed to cool naturally, and slag was separated from the magnetic boat. The slag weight and element-containing concentration were analyzed, and the volatilization rate of each element was calculated. Further, in some experimental examples shown below, the state of slag was confirmed.
(実験例1〜8)
(塩素系塩基度調整助剤と非塩素系塩基度調整助剤の薬剤種による効果の検討)
塩素系塩基度調整助剤として、Ca系塩素系塩基度調整助剤(CaCl2)、Na系塩素系塩基度調整助剤(NaCl)を、非塩素系塩基度調整助剤として、Ca系非塩素系塩基度調整助剤(Ca(OH)2)、Na系非塩素系塩基度調整助剤(Na2CO3)をそれぞれ用いた。塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合は、基材と塩基度調整助剤を含めた組成全体に対して、非塩素系塩基度調整助剤15%に対して、塩素系塩基度調整助剤を10%または20%になるように配合した。処理対象物として基材Aを用い、処理対象物75%に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の合計が25%になるように配合して、1350℃にて溶融させた。配合条件は、図5の実施No.1〜8に示すとおりである。
(Experimental Examples 1-8)
(Examination of the effect of chlorinated basicity adjusting aid and non-chlorine basicity adjusting aid depending on the type of drug)
As a chlorine-based basicity adjusting aid, a Ca-based chlorine-based basicity adjusting aid (CaCl 2 ) and a Na-based chlorine-based basicity adjusting aid (NaCl) are used as non-chlorine-based basicity adjusting aids. Chlorine basicity adjusting aid (Ca (OH) 2 ) and Na non-chlorine basicity adjusting aid (Na 2 CO 3 ) were used. The blending ratio of the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid is 15% of the non-chlorine basicity adjusting aid with respect to the entire composition including the base material and the basicity adjusting aid. Then, a chlorine basicity adjusting aid was blended so as to be 10% or 20%. A base material A is used as a treatment target, and the total of chlorine-based basicity adjustment aid and non-chlorine basicity-adjustment aid is 25% with respect to 75% of the treatment target, and 1350 ° C. And melted. The blending conditions are as shown in FIG. As shown in 1-8.
図6は、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の種類と配合割合を変えた場合のセシウムの揮散率を算出した結果を表すグラフである。図6において、横軸は塩基度調整助剤の種類として、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の組み合わせを表し、縦軸はセシウムの揮散率(%)を表す。また、棒グラフは、各塩素系塩基度調整助剤と非塩素系塩基度調整助剤の組み合わせに対する、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合の相違によるセシウムの揮散率(%)を表している。 FIG. 6 is a graph showing the results of calculating the cesium volatilization rate when the types and blending ratios of the chlorine basicity adjusting aid and the non-chlorine basicity adjusting aid are changed. In FIG. 6, the horizontal axis represents a combination of a chlorine-based basicity adjusting aid and a non-chlorine-based basicity adjusting aid as the type of basicity adjusting aid, and the vertical axis represents the cesium volatilization rate (%). In addition, the bar graph shows the cesium content due to the difference in the blending ratio of the chlorine basicity adjustment aid and the nonchlorine basicity adjustment aid for each combination of the chlorine basicity adjustment aid and the nonchlorine basicity adjustment aid. It represents the volatilization rate (%).
尚、セシウムの揮散率は、下記の式から求めた。他の元素の揮散率も同様に求めた。セシウム揮散率=100×{1−(スラグの重量×スラグのセシウム含有濃度)/(試料の重量×試料のセシウム含有濃度)} In addition, the volatilization rate of cesium was calculated | required from the following formula. The volatilization rates of other elements were determined in the same manner. Cesium volatilization rate = 100 × {1− (weight of slag × concentration containing cesium in slag) / (weight of sample × concentration containing cesium in sample)}
図6から、塩素系塩基度調整助剤と非塩素系塩基度調整助剤として、CaCl2とCa(OH)2を用いたものが最もセシウムの揮散率(%)に優れ、次いで、CaCl2とNa2CO3を用いたものと、NaClとCa(OH)2を用いたものがほぼ同等にセシウムの揮散率(%)に優れ、NaClとNa2CO3を用いたものが続くことがわかる。これらの結果から、塩素系塩基度調整助剤と非塩素系塩基度調整助剤として、いずれもカルシウム系を用いるほうがセシウムの揮散率(%)に優れることがわかった。 From FIG. 6, as the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid, those using CaCl 2 and Ca (OH) 2 are most excellent in cesium volatilization rate (%), and then CaCl 2 And Na 2 CO 3 and those using NaCl and Ca (OH) 2 are almost equally excellent in cesium volatility (%), followed by using NaCl and Na 2 CO 3. Recognize. From these results, it was found that as the chlorine-based basicity adjusting aid and the non-chlorine basicity-adjusting aid, it is better to use calcium-based compounds in terms of volatilization rate (%) of cesium.
図7(a)は、基材と塩基度調整助剤を含めた組成全体に対して、非塩素系塩基度調整助剤15%に対して、塩素系塩基度調整助剤を10%配合した場合、図7(b)は、非塩素系塩基度調整助剤15%に対して、塩素系塩基度調整助剤を20%配合した場合の薬剤元素の揮散率を示すグラフである。図7(a),(b)において、横軸は塩基度調整助剤の種類として、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の組み合わせを表し、縦軸は薬剤元素の揮散率(%)を表す。また、棒グラフは、各塩素系塩基度調整助剤と非塩素系塩基度調整助剤の組み合わせに対する、CaとNaの揮散率(%)を表している。 In FIG. 7A, 10% of the chlorine-based basicity adjusting aid is blended with respect to 15% of the non-chlorine basicity adjusting aid with respect to the entire composition including the base material and the basicity adjusting aid. In this case, FIG. 7 (b) is a graph showing the volatilization rate of the drug element when 20% of the chlorine-based basicity adjustment aid is blended with 15% of the non-chlorine basicity-adjustment aid. 7 (a) and (b), the horizontal axis represents the combination of a chlorine basicity adjusting aid and a non-chlorine basicity adjusting aid as the type of basicity adjusting aid, and the vertical axis represents the drug element. Indicates the volatilization rate (%). Moreover, the bar graph represents the volatilization rate (%) of Ca and Na with respect to the combination of each chlorine basicity adjusting aid and non-chlorine basicity adjusting aid.
図7(a),(b)から、塩素系塩基度調整助剤と非塩素系塩基度調整助剤のいずれの組み合わせにおいてもCaの揮散率は小さく、Naの揮散率は30%から72%と大きいことがわかる。CaCl2とNaClの沸点は、それぞれ1935℃、1413℃であり、NaClの沸点は、CaCl2の沸点に比べ、500℃程度低く、溶融温度にも近いことから、NaClは、溶融温度における飽和蒸気圧が高く、セシウムと反応せずに、そのまま揮散したためであると考えられる。 7 (a) and 7 (b), the volatilization rate of Ca is small and the volatilization rate of Na is 30% to 72% in any combination of the chlorine-based basicity adjusting aid and the non-chlorine-based basicity adjusting aid. It can be seen that it is big. The boiling points of CaCl 2 and NaCl are 1935 ° C. and 1413 ° C., respectively. The boiling point of NaCl is about 500 ° C. lower than the boiling point of CaCl 2 and is close to the melting temperature. Therefore, NaCl is a saturated vapor at the melting temperature. This is probably because the pressure was high and it did not react with cesium and volatilized as it was.
(実験例9〜18)
(塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合による効果の検討)
塩素系塩基度調整助剤として、CaCl2を、非塩素系塩基度調整助剤として、Ca(OH)2を用いた。塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合が、基材と塩基度調整助剤を含めた組成全体に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の合計量35%、40%に対して、塩素系塩基度調整助剤を0%から35%になるように配合した。処理対象物として基材Bを用い、処理対象物65%および60%に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の合計が35%および40%になるように配合して、1400℃にて溶融させた。配合条件は、図5の実施No.9〜18に示すとおりである。
(Experimental Examples 9 to 18)
(Examination of the effect of blending ratio of chlorine-based basicity adjusting aid and non-chlorine-based basicity adjusting aid)
CaCl 2 was used as a chloric basicity adjusting aid, and Ca (OH) 2 was used as a non-chlorine basicity adjusting aid. The mixing ratio of the chlorine-based basicity adjusting aid and the non-chlorine basicity-adjusting aid is such that the chlorine-based basicity adjusting aid and the non-chlorine base are mixed with respect to the entire composition including the base material and the basicity adjusting aid. The chlorine-based basicity adjusting aid was mixed from 0% to 35% with respect to the total amount of the degree adjusting aid of 35% and 40%. The base material B is used as the treatment object, and the total of the chlorine-based basicity adjustment aid and the non-chlorine-based basicity adjustment aid is 35% and 40% with respect to the treatment object of 65% and 60%. Blended and melted at 1400 ° C. The blending conditions are as shown in FIG. As shown in 9-18.
実験例9〜18で溶融後のスラグの状態を目視で確認した。図8(a),(b)は、溶融後のスラグの状態を示す写真である。図8(a)は実験例9〜13の溶融後のスラグの状態を示し、図8(b)は実験例14〜18の溶融後のスラグの状態を示している。また、各スラグの写真において白丸で囲まれた部分が溶融後のスラグを示している。塩化カルシウムの添加濃度が20%以上の実験例(実験例9〜11,14〜16)においては、塩化カルシウムの白色粒子が表面に観察された。これは、塩化カルシウムの添加濃度が高いと、塩化カルシウムの一部が被処理物と均一なスラグ融液相を形成できずに塩化カルシウム融液相として遊離したと考えられる。 In Experimental Examples 9 to 18, the state of the slag after melting was visually confirmed. 8A and 8B are photographs showing the state of the slag after melting. FIG. 8A shows the state of the slag after melting in Experimental Examples 9 to 13, and FIG. 8B shows the state of the slag after melting in Experimental Examples 14 to 18. Moreover, the part surrounded by the white circle in the photograph of each slag has shown the slag after melting. In the experimental examples (experimental examples 9 to 11 and 14 to 16) in which the concentration of calcium chloride added was 20% or more, white particles of calcium chloride were observed on the surface. This is considered that when the addition concentration of calcium chloride is high, a part of calcium chloride cannot be formed as a uniform slag melt phase with the object to be processed and is released as a calcium chloride melt phase.
図9は、実験例9〜18おける塩素系塩基度調整助剤の添加量に対するセシウムの揮散率を算出した結果を表すグラフである。図9から、塩素系塩基度調整助剤であるCaCl2の添加量が15%の場合に、セシウムの揮散率が最大となり、塩基度調整助剤合計が35%の場合のセシウムの揮散率は99.80%、塩基度調整助剤合計が40%の場合のセシウムの揮散率は99.96%であることがわかる。塩基度調整助剤合計が同じであれば、塩基度はほぼ同じ値になると考えられる。この場合に、セシウムの揮散率は、塩素系塩基度調整助剤の添加量に従って増加するのではないことがわかった。 FIG. 9 is a graph showing the results of calculating the cesium volatilization rate with respect to the addition amount of the chlorine-based basicity adjusting aid in Experimental Examples 9 to 18. From FIG. 9, when the addition amount of CaCl 2 which is a chlorine-based basicity adjusting aid is 15%, the volatilization rate of cesium is maximized, and the volatilization rate of cesium when the total basicity adjusting aid is 35% is It can be seen that the cesium volatilization rate is 99.96% when 99.80% and the basicity adjusting aid total is 40%. If the total basicity adjusting aid is the same, the basicity is considered to be approximately the same value. In this case, it has been found that the volatilization rate of cesium does not increase according to the addition amount of the chloric basicity adjusting aid.
図10(a),(b)は、実験例9〜18おける塩素系塩基度調整助剤の添加量に対するセシウム、ナトリウム、カリウム、塩素の揮散率を算出した結果を表すグラフである。図10(a)は、塩基度調整助剤35%添加の場合の各元素の揮散率を表し、図10(b)は、塩基度調整40%添加の場合の各元素の揮散率を表す。図10(a),(b)から、ナトリウム、カリウムの揮散率は、セシウムの揮散率と同様の傾向を示すことがわかる。また、塩素の揮散率は、CaCl2の添加濃度が低いほど揮散率が低く、スラグに取り込まれる割合が多かったことがわかった。これらの結果は、上述のスラグの状態を示す写真の結果と一致する。すなわち、遊離した塩化カルシウム融液相がセシウムと反応をせずに、逆にセシウムの揮散を阻害したと考えられる。 10A and 10B are graphs showing the results of calculating the volatilization rates of cesium, sodium, potassium, and chlorine with respect to the addition amount of the chlorine-based basicity adjusting aid in Experimental Examples 9-18. FIG. 10A shows the volatilization rate of each element when 35% of the basicity adjusting aid is added, and FIG. 10B shows the volatilization rate of each element when the basicity adjustment of 40% is added. 10 (a) and 10 (b), it can be seen that the volatilization rate of sodium and potassium shows the same tendency as the volatilization rate of cesium. Moreover, the volatilization rate of chlorine was found to be lower as the additive concentration of CaCl 2 was lower, and the ratio of incorporation into slag was higher. These results are in agreement with the results of the photographs showing the slag state described above. That is, it is considered that the liberated calcium chloride melt phase did not react with cesium and conversely inhibited the volatilization of cesium.
以上の結果から、塩基度調整助剤の量が同じ、又は塩基度調整助剤を含む被処理物の塩基度が略一定の場合、塩素系塩基度調整助剤つまり塩素の添加量が多いほどセシウムの揮散率が高くなるわけではないことがわかる。また、塩素系塩基度調整助剤の添加量と非塩素系塩基度調整助剤の添加量との添加割合を調整することで、セシウムの揮散率が極大値となる添加割合が存在することがわかる。 From the above results, when the basicity adjustment aid is the same amount or the basicity of the object containing the basicity adjustment aid is substantially constant, the greater the amount of chlorine-based basicity adjustment aid, that is, the amount of chlorine added. It can be seen that the volatilization rate of cesium does not increase. In addition, by adjusting the addition ratio of the addition amount of the chlorine-based basicity adjustment aid and the addition amount of the non-chlorine basicity adjustment aid, there may be an addition ratio at which the volatilization rate of cesium becomes a maximum value. Recognize.
(実験例19〜22)
(還元剤添加による効果の検討)
塩素系塩基度調整助剤として、CaCl2を、非塩素系塩基度調整助剤として、Ca(OH)2を用いた。還元剤の添加割合を可燃分及び塩基度調整助剤を含む被処理物全体の40%、50%とした。塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合が、基材、塩基度調整助剤及び還元剤を含めた組成全体に対して、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の合計量35%に対して、塩素系塩基度調整助剤を15%、非塩素系塩基度調整助剤を20%になるものと、塩素系塩基度調整助剤と非塩素系塩基度調整助剤の合計量40%に対して、塩素系塩基度調整助剤を15%、非塩素系塩基度調整助剤を25%になるものを、基材Bに混合して、1400℃にて溶融させた。配合条件は、図5の実施No.19〜22に示すとおりである。
(Experimental Examples 19-22)
(Examination of the effect of reducing agent addition)
CaCl 2 was used as a chloric basicity adjusting aid, and Ca (OH) 2 was used as a non-chlorine basicity adjusting aid. The addition ratio of the reducing agent was set to 40% and 50% of the entire object to be processed including the combustible component and the basicity adjusting aid. The blending ratio of the chloric basicity adjusting aid and the non-chlorine basicity adjusting aid to the entire composition including the base material, the basicity adjusting aid and the reducing agent, A total of 35% of chlorine-based basicity adjusting aids, 15% of chlorine-based basicity adjusting aids and 20% of non-chlorine basicity-adjusting aids, and chlorine-based basicity adjusting aids The base B is mixed with 15% chlorine basicity adjustment aid and 25% nonchlorine basicity adjustment aid to the total amount of nonchlorine basicity adjustment aid of 40%. And melted at 1400 ° C. The blending conditions are as shown in FIG. As shown in 19-22.
図11は、実験例12,17,19〜22おける塩素系塩基度調整助剤の添加量に対するセシウムの揮散率を算出した結果を表すグラフである。図11から、還元剤の添加量が多いほどセシウムの揮散率が高いことがわかる。特に、土壌に対して還元剤を50%含有する処理対象物を用い、塩基度調整助剤を40%添加する実験例22の場合は、セシウムの揮散率が99.99%に達することがわかった。
以上の結果から、塩素系塩基度調整助剤の添加条件と還元剤の添加割合を適宜調整すれば、セシウムの揮散率を高くすることができることがわかった。
FIG. 11 is a graph showing the results of calculating the volatilization rate of cesium with respect to the added amount of the chloric basicity adjusting aid in Experimental Examples 12, 17, and 19-22. FIG. 11 shows that the greater the amount of reducing agent added, the higher the cesium volatilization rate. In particular, in the case of Experimental Example 22 in which a treatment object containing 50% of the reducing agent is added to the soil and 40% of the basicity adjusting aid is added, the cesium volatilization rate reaches 99.99%. It was.
From the above results, it was found that the volatilization rate of cesium can be increased by appropriately adjusting the addition conditions of the chlorine basicity adjusting aid and the addition ratio of the reducing agent.
(実験例23〜25)
(プラントを用いた実験)
図1の装置を用いて、セシウムの揮散率および排ガス中のHCl濃度を測定した。図12に示すような処理対象物に塩素系塩基度調整助剤としてCaCl2を、非塩素系塩基度調整助剤としてCa(OH)2を図12に示す配合割合で配合して溶融処理を行った。処理後のスラグのセシウムの揮散率と排ガス中のHCL濃度を測定した。HCL濃度の測定は、第2集塵機13の入口で行った。結果を図12に示す。
(Experimental Examples 23 to 25)
(Experiment using plant)
Using the apparatus of FIG. 1, the cesium volatilization rate and the HCl concentration in the exhaust gas were measured. The treatment object as shown in FIG. 12 is blended with CaCl 2 as a chloric basicity adjusting aid and Ca (OH) 2 as a non-chlorine basicity adjusting aid at a blending ratio shown in FIG. went. The cesium volatilization rate of the slag after the treatment and the HCL concentration in the exhaust gas were measured. The HCL concentration was measured at the entrance of the second dust collector 13. The results are shown in FIG.
図12から、非塩素系塩基度調整助剤を含まない実験例23では、セシウムの揮散率が96.7%と低く、排ガス中のHCL濃度も、8,200ppmと高濃度であった。非塩素系塩基度調整助剤の添加割合が増加するに応じて、セシウムの揮散率が増加し、排ガス中のHCL濃度も低減することがわかる。 From FIG. 12, in Experimental Example 23 not including the non-chlorine basicity adjusting aid, the volatilization rate of cesium was as low as 96.7%, and the HCL concentration in the exhaust gas was as high as 8,200 ppm. It can be seen that as the addition ratio of the non-chlorine basicity adjusting aid increases, the cesium volatilization rate increases and the HCL concentration in the exhaust gas also decreases.
上記実験例9〜22で、最高のセシウム揮散率が得られる実験例22と同様の条件である実験例25においては、セシウムの揮散率が99.9%と高く、排ガス中のHCL濃度も、1,900ppmと低濃度で、実験室における実験結果と同様の結果がプラントを用いた実験においても得られることがわかった。 In Experimental Example 25, which is the same condition as Experimental Example 22 in which the highest cesium volatilization rate is obtained in Experimental Examples 9 to 22, the cesium volatilization rate is as high as 99.9%, and the HCL concentration in the exhaust gas is also high. It was found that the result similar to the experimental result in the laboratory can be obtained in the experiment using the plant at a low concentration of 1,900 ppm.
また、セシウムの揮散率が高い実験例25のスラグの光学塩基度および二成分塩基度(CaO(%)/SiO2(%))は、本発明における好ましい光学塩基度および二成分塩基度(CaO(%)/SiO2(%))の範囲に含まれる。 Further, the optical basicity and binary basicity (CaO (%) / SiO 2 (%)) of the slag of Experimental Example 25 having a high cesium volatilization rate are the preferable optical basicity and binary basicity (CaO (CaO) in the present invention. (%) / SiO 2 (%)).
従って、少量の処理対象物を用いて、塩素系塩基度調整助剤と非塩素系塩基度調整助剤を事前に決定した所定の添加割合で添加すれば、プラントを用いて同様の条件で放射性セシウムを分離濃縮することができることがわかった。
Therefore, if a small amount of processing object is used and a chlorine-based basicity adjusting aid and a non-chlorine basicity-adjusting aid are added at a predetermined addition ratio determined in advance, the plant is used for the same conditions. It was found that cesium can be separated and concentrated.
1:放射性セシウム分離濃縮装置
2:受入部
3:搬送機構
4:塩基度調整助剤添加装置
5:溶融炉
6:冷却水槽
7:排出機構
8:煙道
9:冷却装置
10:剥離剤添加装置
11:第1集塵機
12:中和剤添加装置
13:第2集塵機
14:ヒータ
15:触媒塔
16:塩基度調整助剤添加量決定装置
1: Radiocesium separation and concentration device 2: Receiving unit 3: Conveying mechanism 4: Basicity adjusting auxiliary agent adding device 5: Melting furnace 6: Cooling water tank 7: Discharging mechanism 8: Flue 9: Cooling device 10: Stripping agent adding device 11: 1st dust collector 12: Neutralizer addition device 13: 2nd dust collector 14: Heater 15: Catalyst tower 16: Basicity adjustment auxiliary agent addition amount determination device
Claims (8)
被処理物の塩基度が所定値になるように塩基度調整助剤の添加量を決定し、予め求める被処理物の塩基度が前記所定値のもとでの塩素系塩基度調整剤の添加割合とセシウム揮散率との関係に基づいて放射性セシウムの揮散率が最大となる範囲に入るように塩基度調整助剤である塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合を決定する塩基度調整助剤添加量決定工程と、
前記塩基度調整助剤添加量決定工程で決定された値に従って、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤を添加する塩基度調整工程と、
塩素系塩基度調整助剤と非塩素系塩基度調整助剤が添加された被処理物を前記加熱炉で加熱する加熱処理工程と、
前記集塵機で捕集された放射性セシウムを含む飛灰を回収する回収処理工程と、
を備えている放射性セシウム分離濃縮装置の運転方法。 Basicity adjusting auxiliary agent adding device for adding basicity adjusting auxiliary consisting of chlorine-based basicity adjusting auxiliary and non-chlorine basicity adjusting auxiliary to the object to be processed, and processing to which basicity adjusting auxiliary is added A heating furnace for volatilizing and separating radioactive cesium by heating an object, and a dust collector for collecting fly ash containing radioactive cesium that has been volatilized and separated in the heating furnace, and a method of operating a radioactive cesium separation and concentration device comprising: Because
The amount of basicity adjusting aid added is determined so that the basicity of the object to be processed becomes a predetermined value, and the basicity of the chlorine-based basicity adjusting agent is added under the condition that the basicity of the object to be processed is determined in advance. distribution ratio and cesium volatilization rate and chlorine basicity adjustment aid volatilization rate of radioactive cesium is basic adjustment aid to fall within the range of maximum based on the relationship of the chlorine-base adjustment aid A basicity adjusting auxiliary agent addition amount determining step for determining a combined ratio;
In accordance with the value determined in the basicity adjustment aid addition amount determination step, a basicity adjustment step of adding a chlorine-based basicity adjustment aid and a non-chlorine-based basicity adjustment aid to the workpiece,
A heat treatment step of heating the object to which the chlorine-based basicity adjusting aid and the non-chlorine basicity adjusting aid are added in the heating furnace;
A recovery process for recovering fly ash containing radioactive cesium collected by the dust collector;
The operation method of the radioactive cesium separation concentration apparatus provided with this.
被処理物の塩基度が所定値になるように塩基度調整助剤の添加量を決定し、予め求める被処理物の塩基度が前記所定値のもとでの塩素系塩基度調整剤の添加割合とセシウム揮散率との関係に基づいて放射性セシウムの揮散率が最大となる範囲に入るように塩基度調整助剤である塩素系塩基度調整助剤と非塩素系塩基度調整助剤の配合割合を決定する塩基度調整助剤添加量決定装置を備え、
前記塩基度調整助剤添加装置は前記塩基度調整助剤添加量決定装置で決定された塩素系塩基度調整助剤と非塩素系塩基度調整助剤の添加量及び配合割合に従って、被処理物に塩素系塩基度調整助剤と非塩素系塩基度調整助剤を添加する、
放射性セシウム分離濃縮装置。
Basicity adjusting auxiliary agent adding device for adding basicity adjusting auxiliary consisting of chlorine-based basicity adjusting auxiliary and non-chlorine basicity adjusting auxiliary to the object to be processed, and processing to which basicity adjusting auxiliary is added A radioactive cesium separation and concentration device comprising a heating furnace that volatilizes and separates radioactive cesium by heating an object, and a dust collector that collects fly ash containing radioactive cesium that has been volatilized and separated in the heating furnace. ,
The amount of basicity adjusting aid added is determined so that the basicity of the object to be processed is a predetermined value, and the basicity of the chlorine-based basicity adjusting agent is added when the basicity of the object to be processed is determined in advance distribution ratio and cesium volatilization rate and chlorine basicity adjustment aid volatilization rate of radioactive cesium is basic adjustment aid to fall within the range of maximum based on the relationship of the chlorine-base adjustment aid Equipped with a basicity adjusting auxiliary agent addition amount determining device for determining the total proportion,
The basicity adjusting auxiliary agent adding device is an object to be processed according to the addition amount and the mixing ratio of the chlorine basicity adjusting auxiliary agent and the non-chlorine basicity adjusting auxiliary agent determined by the basicity adjusting auxiliary agent addition amount determining device. Adding a chlorine-based basicity adjusting aid and a non-chlorine-based basicity adjusting aid,
Radioactive cesium separation and concentration equipment.
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