JP5058373B2 - Processing method of used ion exchange resin - Google Patents

Processing method of used ion exchange resin Download PDF

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JP5058373B2
JP5058373B2 JP2011282813A JP2011282813A JP5058373B2 JP 5058373 B2 JP5058373 B2 JP 5058373B2 JP 2011282813 A JP2011282813 A JP 2011282813A JP 2011282813 A JP2011282813 A JP 2011282813A JP 5058373 B2 JP5058373 B2 JP 5058373B2
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ion exchange
exchange resin
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佳子 春口
陵太 高橋
昌章 金子
雄生 山下
龍明 佐藤
通孝 三倉
由紀 有馬
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Toshiba Corp
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Description

本発明は、原子力施設の運転廃棄物の1つである使用済みイオン交換樹脂の処理方法に関する。   The present invention relates to a method for treating used ion exchange resin, which is one of operating wastes of nuclear facilities.

原子力施設の運転廃棄物の1つに使用済みイオン交換樹脂がある。この使用済みイオン交換樹脂は、多量の放射性核種を吸着していることから被ばくへの寄与が大きく、余裕深度処分対象廃棄物としての処理が検討されている。   One of the operating wastes of nuclear facilities is used ion exchange resin. Since this used ion exchange resin adsorbs a large amount of radionuclide, it contributes greatly to exposure, and its treatment as a waste subject to marginal disposal is being studied.

しかしながら、余裕深度処分対象廃棄体は、処分にコストと労力がかかるため、使用済みイオン交換樹脂すべてを余裕深度処分対象廃棄体として処分することは、効率的とはいえない。   However, since wastes subject to marginal depth disposal are costly and laborious to dispose, it is not efficient to dispose of all used ion exchange resins as wastes subject to marginal depth disposal.

このため、使用済みイオン交換樹脂の処理・処分に当たっては、処分に先立ち、処分対象廃棄物を減容することを目的とした技術の開発が行われている。このような技術の一例として、スチームリフォーマ処理、ICプラズマによる焼却処理等がある。しかしながら、これらの処理では、イオン交換樹脂を完全に処理することが困難であるとともに、減容後廃棄物のほぼ全量が、余裕深度処分対象となるという問題点がある。   For this reason, in the treatment and disposal of used ion exchange resins, development of technology aimed at reducing the volume of waste to be disposed of has been performed prior to disposal. Examples of such techniques include steam reformer processing, incineration processing using IC plasma, and the like. However, in these treatments, it is difficult to completely treat the ion exchange resin, and there is a problem that almost the entire amount of waste after volume reduction becomes a target for disposal at a sufficient depth.

また、使用済みイオン交換樹脂を超臨界水で完全に分解処理し、放射性核種は溶液の中に閉じ込める技術も開発されている(例えば、特許文献1参照。)。この技術の場合、分解処理液の放射性核種の化学分離操作が可能であるため、分離操作を行った後、余裕深度処分対象廃棄物とそれ以外に分けて処分することが可能であり、余裕深度処分廃棄物の減容には効果的である。   In addition, a technique has been developed in which a used ion exchange resin is completely decomposed with supercritical water and a radionuclide is confined in a solution (for example, see Patent Document 1). In the case of this technology, the radionuclide chemical separation operation of the decomposition treatment liquid is possible, so after performing the separation operation, it is possible to dispose the waste separately for the extra depth disposal target and the other, and the extra depth It is effective for volume reduction of disposal waste.

特開平11−23793号公報Japanese Patent Laid-Open No. 11-23793

上記したとおり、使用済みイオン交換樹脂を超臨界水で完全に分解処理し、放射性核種を溶液の中に閉じ込める技術は、余裕深度処分廃棄物の減容には効果的である。しかしながら、超臨界水処理には、高温・高圧を担保するための大型の機器が必要となり、コストがかさむという課題がある。   As described above, the technique of completely decomposing used ion exchange resin with supercritical water and confining the radionuclide in the solution is effective for reducing the volume of waste disposal waste. However, supercritical water treatment requires a large-scale device for ensuring high temperature and high pressure, and there is a problem that costs increase.

本発明は、上記従来の事情に対処してなされたもので、従来に比べて使用済みイオン交換樹脂を低コストで効率良く処分することのできる使用済みイオン交換樹脂の処理方法を提供することを目的とする。   The present invention has been made in response to the above-described conventional circumstances, and provides a method for treating a used ion exchange resin that can efficiently dispose of a used ion exchange resin at a lower cost than in the past. Objective.

本発明の一態様は、放射性物質が吸着した使用済みイオン交換樹脂を処理する使用済みイオン交換樹脂の処理方法において、強塩基性塩によるアルカリ融解により前記使用済みイオン交換樹脂の吸着部位であるイオン交換基を不能化するイオン交換基不能化処理工程と、イオン交換基を不能化した前記使用済みイオン交換樹脂と、前記放射性物質とを分離する分離工程とを具備したことを特徴とする。   One embodiment of the present invention is a treatment method of a used ion exchange resin in which a radioactive substance is adsorbed, in the method for treating a used ion exchange resin, an ion that is an adsorption site of the used ion exchange resin by alkali melting with a strong basic salt An ion exchange group disabling treatment step for disabling an exchange group, a separation step for separating the used ion exchange resin in which the ion exchange group is disabled, and the radioactive substance are provided.

本発明によれば、従来に比べて使用済みイオン交換樹脂を低コストで効率良く処分することのできる使用済みイオン交換樹脂の処理方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the processing method of used ion exchange resin which can dispose of used ion exchange resin efficiently at low cost compared with the former can be provided.

本発明の使用済みイオン交換樹脂の処理方法の実施形態の概略構成を模式的に示す説明図。Explanatory drawing which shows typically schematic structure of embodiment of the processing method of the used ion exchange resin of this invention. 本発明の実施形態に使用する装置の概略構成を模式的に示す説明図。Explanatory drawing which shows typically schematic structure of the apparatus used for embodiment of this invention. イオン交換樹脂のイオン交換容量変化の水熱分解処理時温度依存性を示すグラフ。The graph which shows the temperature dependence at the time of the hydrothermal decomposition process of the ion exchange capacity change of an ion exchange resin.

以下、本発明の実施の形態について図面を参照して説明する。図1は、本実施形態に係る使用済みイオン交換樹脂の処理方法の概略構成を模式的に示したものである。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 schematically shows a schematic configuration of a method for treating a used ion exchange resin according to the present embodiment.

図1(a)に示すように、使用済みイオン交換樹脂(スルホン酸系)1には、放射性核種(放射性物質)2(図1(a)中下部に示すA)が吸着されている。本実施形態では、まず、この使用済みイオン交換樹脂1を反応容器内部で反応用液体と混合させて反応させ、イオン交換基を不能化する(官能基を離脱させて電気的に中性化する)イオン交換基不能化処理工程を行う。   As shown in FIG. 1A, a used radionuclide (radioactive substance) 2 (A shown in the lower part of FIG. 1A) is adsorbed on the used ion exchange resin (sulfonic acid series) 1. In the present embodiment, first, the used ion exchange resin 1 is mixed with the reaction liquid in the reaction vessel and reacted to disable the ion exchange group (disengage the functional group and neutralize electrically). ) Ion exchange group disabling treatment process is performed.

上記イオン交換基不能化処理工程としては、水熱条件下での加水分解、強塩基性塩によるアルカリ融解、還元処理のいずれかを用いることができる。このイオン交換基不能化処理工程により、使用済みイオン交換樹脂1に吸着していた放射性核種2は、使用済みイオン交換樹脂1から離脱して反応用液体中に移行する。   As the ion exchange group disabling treatment step, any of hydrolysis under hydrothermal conditions, alkali melting with a strong basic salt, and reduction treatment can be used. Through this ion exchange group disabling treatment step, the radionuclide 2 adsorbed on the used ion exchange resin 1 leaves the used ion exchange resin 1 and moves into the reaction liquid.

この結果、図1(b)に示すように、上記のイオン交換基不能化処理工程を経た使用済みイオン交換樹脂1aは、放射性核種2が離脱した状態となる。なお、このような放射性核種2としては、例えば、イオン交換樹脂に高線量率をもたらすCo−60等が含まれている。   As a result, as shown in FIG. 1B, the used ion exchange resin 1a that has undergone the ion exchange group disabling process is in a state in which the radionuclide 2 has been detached. In addition, as such a radionuclide 2, Co-60 etc. which bring about a high dose rate to an ion exchange resin are contained, for example.

次に、上記のイオン交換基不能化処理工程によって放射性核種2が離脱した状態となった使用済みイオン交換樹脂1aと、離脱した放射性核種2を含む反応用液体を分離し、使用済みイオン交換樹脂1aは、比較的低レベルの浅地中処分対象廃棄物として処理する。これによって、多量に発生する使用済みイオン交換樹脂1を余裕深度処分対象廃棄物外とすることができる。一方、分離後のCo−60等の放射性核種2を含む放射性廃液は、必要に応じて濃縮、あるいは希釈の上、比較的高レベルの余裕深度処分対象廃棄物として処理する。   Next, the used ion exchange resin 1a in which the radionuclide 2 is released from the ion exchange group deactivation process is separated from the reaction liquid containing the released radionuclide 2, and the used ion exchange resin is separated. 1a is treated as a waste subject to disposal in a shallow area at a relatively low level. Thereby, the used ion exchange resin 1 which generate | occur | produces abundantly can be made outside the waste object for marginal depth disposal. On the other hand, the radioactive waste liquid containing the radionuclide 2 such as Co-60 after separation is treated as a relatively high level waste subject to disposal at a relatively high level after being concentrated or diluted as necessary.

図2は、本実施形態に用いる使用済みイオン交換樹脂の処理装置の一例の概略構成を模式的に示す図である。   FIG. 2 is a diagram schematically illustrating a schematic configuration of an example of a processing apparatus for used ion exchange resin used in the present embodiment.

同図に示すように、使用済みイオン交換樹脂の処理装置10は、放射性核種を捕捉した使用済みイオン交換樹脂1を貯留するための樹脂貯留槽11と、薬液(反応用液体)12を貯留する薬液タンク13と、イオン交換基不能化処理を行うための反応槽14と、イオン交換樹脂の官能基とともに脱離した放射性核種を含む水溶液とイオン交換基不能化処理済みの使用済みイオン交換樹脂とを分離する分離槽15と、放射性核種を含む水溶液を濃縮減容する濃縮槽16とを具備している。なお、図2において、20は、薬液タンク13と反応槽14とを接続する配管、21は、樹脂貯留槽11と反応槽14とを接続する配管、22は、分離槽15と濃縮槽16とを接続する配管である。   As shown in the figure, a used ion exchange resin processing apparatus 10 stores a resin storage tank 11 for storing a used ion exchange resin 1 that has captured a radionuclide, and a chemical (reaction liquid) 12. A chemical tank 13, a reaction tank 14 for performing ion exchange group disabling treatment, an aqueous solution containing a radionuclide desorbed together with a functional group of the ion exchange resin, and a used ion exchange resin that has been subjected to ion exchange disabling treatment And a concentrating tank 16 for concentrating and reducing an aqueous solution containing a radionuclide. In FIG. 2, 20 is a pipe connecting the chemical tank 13 and the reaction tank 14, 21 is a pipe connecting the resin storage tank 11 and the reaction tank 14, and 22 is a separation tank 15 and a concentration tank 16. It is the piping which connects.

上記構成の使用済みイオン交換樹脂の処理装置10では、樹脂貯留槽11から使用済みイオン交換樹脂1を、所定量反応槽14内に導入するとともに、反応槽14内に薬液タンク13から所定量の薬液12を導入し、反応槽14内において、上述したイオン交換基不能化処理工程を行う。   In the spent ion exchange resin processing apparatus 10 having the above-described configuration, the spent ion exchange resin 1 is introduced from the resin storage tank 11 into the reaction tank 14 and a predetermined amount from the chemical tank 13 to the reaction tank 14. The chemical | medical solution 12 is introduce | transduced and the ion exchange group disabling process process mentioned above in the reaction tank 14 is performed.

このイオン交換基不能化処理工程を、水熱条件下での加水分解により行う場合、処理温度を250℃以上とすることが好ましく、処理温度を300℃程度とすることがさらに好ましい。これは以下に示す理由による。   When this ion exchange group disabling treatment step is performed by hydrolysis under hydrothermal conditions, the treatment temperature is preferably 250 ° C. or higher, more preferably about 300 ° C. This is for the following reason.

すなわち、図3は、縦軸をイオン交換容量(%)、横軸を温度(℃)としてスルホン酸系樹脂に対する分解処理結果として、水熱分解処理時のイオン交換容量の温度依存性を示したものである。この図3に示されるとおり、水熱分解処理時の温度の上昇とともにイオン交換容量が減少し、250℃の処理条件で約30%、300℃の処理条件で約90%程度のイオン交換容量が逸失することが判る。このような温度条件で水熱分解処理を行うことにより、使用済みイオン交換樹脂の官能基の部分が加水分解され、捕捉しているイオン性の放射性核種が有効に放出されると期待される。   That is, FIG. 3 shows the temperature dependence of the ion exchange capacity during the hydrothermal decomposition treatment as a result of the decomposition treatment for the sulfonic acid resin with the vertical axis representing the ion exchange capacity (%) and the horizontal axis representing the temperature (° C.). Is. As shown in FIG. 3, the ion exchange capacity decreases as the temperature during the hydrothermal decomposition treatment decreases, and the ion exchange capacity is about 30% under the 250 ° C. treatment condition and about 90% under the 300 ° C. treatment condition. It turns out that it is lost. By performing the hydrothermal decomposition treatment under such temperature conditions, it is expected that the functional group portion of the used ion exchange resin is hydrolyzed and the captured ionic radionuclide is effectively released.

また、上記イオン交換基不能化処理工程を、強塩基性塩によるアルカリ融解により行う場合は、例えば、使用済みイオン交換樹脂を、水酸化ナトリウム、あるいは水酸化カリウムへ曝露することにより行うことができる。この場合、処理温度は、例えば、200℃以上とすることが好ましい。   Moreover, when performing the said ion exchange group deactivation process process by the alkali fusion | melting by a strong basic salt, it can carry out by exposing a used ion exchange resin to sodium hydroxide or potassium hydroxide, for example. . In this case, the treatment temperature is preferably 200 ° C. or higher, for example.

さらに、上記イオン交換基不能化処理工程を、還元処理により行う場合、例えば、使用済みイオン交換樹脂を、ヨウ化水素溶液へ曝露することにより行うことができる。   Furthermore, when performing the said ion exchange group disabling process process by a reduction process, it can carry out by exposing used ion exchange resin to a hydrogen iodide solution, for example.

上記のように、反応槽14内において、水熱条件下での加水分解、強塩基性塩によるアルカリ融解、還元処理のいずれかによりイオン交換基不能化処理工程を行った後、分離槽15においてイオン交換基不能化処理済みの固体状の使用済みイオン交換樹脂と、放射性核種を含む溶液とを分離する。   As described above, in the reaction tank 14, after performing the ion exchange group disabling treatment step by any of hydrolysis under hydrothermal conditions, alkali melting with a strong basic salt, and reduction treatment, A solid spent ion exchange resin that has been subjected to ion exchange group deactivation treatment and a solution containing a radionuclide are separated.

そして、上記のようにして使用済みイオン交換樹脂と分離された放射性核種を含む溶液を、濃縮槽16において、必要に応じて濃縮減容する。この減容された放射性核種を含む廃棄物は、余裕深度処分対象廃棄物として処理する。一方、イオン交換基不能化処理済みの固体状の使用済みイオン交換樹脂は、浅地中処分対象廃棄物として処理する。   The solution containing the radionuclide separated from the used ion exchange resin as described above is concentrated and reduced in the concentration tank 16 as necessary. The waste containing the reduced radionuclide is treated as a waste subject to disposal at a sufficient depth. On the other hand, the solid used ion exchange resin that has been subjected to the ion exchange group disabling treatment is treated as a waste subject to disposal in shallow areas.

上記のように、本実施形態によれば、使用済みイオン交換樹脂にイオン交換基不能化処理を行って、その官能基を離脱させて電気的に中性化することにより、使用済みイオン交換樹脂に吸着した放射性核種を、使用済みイオン交換樹脂から分離させることができるので、大量に発生する使用済みイオン交換樹脂を、余裕深度処分対象廃棄物として処理するのではなく、浅地中処分対象廃棄物として処理することができる。これによって、処理コストのかさむ超臨界水処理等を行うことなく、余裕深度処分対象廃棄物の量を減少させることができ、低コストで効率良く使用済みイオン交換樹脂を処分することができる。   As described above, according to the present embodiment, the used ion exchange resin is subjected to the ion exchange group disabling treatment, and the functional group is released to neutralize the used ion exchange resin, thereby performing the used ion exchange resin. The radionuclide adsorbed on the waste can be separated from the used ion exchange resin. Can be processed as This makes it possible to reduce the amount of waste subject to disposal at a deeper depth without performing supercritical water treatment or the like that increases the processing cost, and to dispose of used ion exchange resin efficiently at a low cost.

以上説明したとおり、本実施形態によれば、従来に比べて使用済みイオン交換樹脂を低コストで効率良く処分することができる。   As described above, according to the present embodiment, the used ion exchange resin can be efficiently disposed of at a lower cost than in the past.

1,1a……使用済みイオン交換樹脂、2……放射性核種、10……使用済みイオン交換樹脂の処理装置、11……樹脂貯留槽、12……薬液(反応用液体)、13……薬液タンク、14……反応槽、15……分離槽、16……濃縮槽、20,21,22……配管。   DESCRIPTION OF SYMBOLS 1,1a ... Used ion exchange resin, 2 ... Radionuclide, 10 ... Used ion exchange resin processing apparatus, 11 ... Resin storage tank, 12 ... Chemical solution (reaction liquid), 13 ... Chemical solution Tank, 14 ... Reaction tank, 15 ... Separation tank, 16 ... Concentration tank, 20, 21, 22 ... Piping.

Claims (3)

放射性物質が吸着した使用済みイオン交換樹脂を処理する使用済みイオン交換樹脂の処理方法において、
強塩基性塩によるアルカリ融解により前記使用済みイオン交換樹脂の吸着部位であるイオン交換基を不能化するイオン交換基不能化処理工程と、
イオン交換基を不能化した前記使用済みイオン交換樹脂と、前記放射性物質とを分離する分離工程と
を具備したことを特徴とする使用済みイオン交換樹脂の処理方法。
In the processing method of the used ion exchange resin which processes the used ion exchange resin which the radioactive substance adsorbed,
An ion exchange group disabling treatment step of disabling the ion exchange group that is the adsorption site of the used ion exchange resin by alkali melting with a strong basic salt;
A method for treating a used ion exchange resin, comprising: the used ion exchange resin in which an ion exchange group is disabled; and a separation step of separating the radioactive substance.
請求項1に記載の使用済みイオン交換樹脂の処理方法において、
前記強塩基性塩によるアルカリ融解が、前記使用済みイオン交換樹脂の水酸化ナトリウム、あるいは水酸化カリウムへの曝露でなされることを特徴とする使用済みイオン交換樹脂の処理方法。
In the processing method of the used ion exchange resin of Claim 1,
A method for treating a used ion exchange resin, wherein the alkali melting with the strong base salt is performed by exposing the used ion exchange resin to sodium hydroxide or potassium hydroxide.
請求項1又は2に記載の使用済みイオン交換樹脂の処理方法において、
前記強塩基性塩によるアルカリ融解が、200℃以上の温度条件下でなされることを特徴とする使用済みイオン交換樹脂の処理方法。
In the processing method of the used ion exchange resin of Claim 1 or 2,
A method for treating a used ion exchange resin, wherein the alkali melting with the strong basic salt is performed under a temperature condition of 200 ° C. or higher.
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JPS54157000A (en) * 1978-05-31 1979-12-11 Tokyo Electric Power Co Inc:The Method of waste disposal of ion-exchange resin having radioactivity
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JP2005050734A (en) * 2003-07-30 2005-02-24 Japan Storage Battery Co Ltd Manufacturing method of electrode for solid polymer fuel cell

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