JP6093942B2 - Radioactive liquid decontamination method - Google Patents
Radioactive liquid decontamination method Download PDFInfo
- Publication number
- JP6093942B2 JP6093942B2 JP2011289704A JP2011289704A JP6093942B2 JP 6093942 B2 JP6093942 B2 JP 6093942B2 JP 2011289704 A JP2011289704 A JP 2011289704A JP 2011289704 A JP2011289704 A JP 2011289704A JP 6093942 B2 JP6093942 B2 JP 6093942B2
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- Prior art keywords
- radioactive
- cesium
- fiber
- liquid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007788 liquid Substances 0.000 title claims description 63
- 230000002285 radioactive effect Effects 0.000 title claims description 48
- 238000005202 decontamination Methods 0.000 title description 21
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- 229910052792 caesium Inorganic materials 0.000 claims description 93
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 92
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- 238000000034 method Methods 0.000 claims description 46
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Description
東日本大震災によって発生した原子力発電所の事故によって、放射性物質が大量に環境中に放出された。本発明は放射性物質によって汚染した土壌、たまり水、水処理装置の沈殿汚泥及び建造物などから放射性物質を除去し除染するための方法に関する。 A large amount of radioactive material was released into the environment due to an accident at a nuclear power plant caused by the Great East Japan Earthquake. The present invention relates to a method for removing and decontaminating radioactive material from soil contaminated with radioactive material, pool water, precipitated sludge of water treatment equipment and buildings.
原子力発電所から放出された放射性物質にはウランー２３５の核***に由来するものと、原子炉構造材料に由来する元素からなる。前者にはセシウム、ストロンチウム、ヨウ素、バリウム、イットリウム、スズさらにプルトニウムなどのアクチニド系列元素、ランタニド系列に属する元素、後者にはコバルト、ニッケル、亜鉛、マンガンなどがある。 Radioactive materials released from nuclear power plants consist of those derived from nuclear fission of uranium-235 and elements derived from nuclear reactor structural materials. The former includes cesium, strontium, iodine, barium, yttrium, tin, and actinide series elements such as plutonium, elements belonging to the lanthanide series, and the latter includes cobalt, nickel, zinc, manganese, and the like.
セシウムの半減期は約30年と長く、汚染の影響が大きくかつ長期にわたる。ここでは、放射性セシウムによって汚染されたたまり水、例えばプール水を例にとり説明する。 The half-life of cesium is as long as about 30 years, and the impact of contamination is large and long. Here, a description will be given by taking, for example, pool water contaminated by radioactive cesium, for example, pool water.
放射性物質（主にセシウム）によって汚染されたプール水は通常、凝集沈殿―ろ過によって処理される。凝集沈殿を行う際、セシウムを吸着させるためのゼオライトやフェロシアン化物を加えさらにアルミニウム系の凝集剤を添加し、撹拌後に沈殿分離する。そして、上澄み液の放射能を測定後、所定の値以下であれば放流や別の用途に再利用される。沈殿汚泥は人力でかき集め、袋に入れて脱水後、所定の場所に保管される。 Pool water contaminated with radioactive material (mainly cesium) is usually treated by coagulation sedimentation-filtration. When performing coagulation precipitation, zeolite and ferrocyanide for adsorbing cesium are added, and an aluminum-based coagulant is added, followed by precipitation separation after stirring. And after measuring the radioactivity of a supernatant liquid, if it is below a predetermined value, it will be reused for discharge or another use. The precipitated sludge is collected manually, put in a bag, dehydrated, and stored in place.
一般的に凝集沈殿やろ過という水処理工程は、浄水場や下水処理場のように大流量の水処理を行う場合に採用される。水処理設備としては、取水槽―凝集設備―撹拌槽―沈殿槽―汚泥排出・脱水設備など大きな土木建築物や装置からなる。プール水や除染廃液のように非定常の液体を処理する場合、日本原子力研究開発機構がウェブサイト上に公開している「学校プール水の除染の手引き」（平成23年9月27日）によれば、１ｔタンクを5個程度用意し、それぞれのタンクにおいて、ゼオライト添加槽、凝集剤添加撹拌槽、上澄み液タンク（中和槽）、排水タンクと役割を受け持たせ、人力で処理している。このような操作を水深１ｍで２００ｍ3以上残留しているプール水に適用すると、200バッチの処理が必要である。広い場所、多くの作業者及び長時間を要する作業となる。 Generally, water treatment processes such as coagulation sedimentation and filtration are employed when water treatment at a large flow rate is performed as in water purification plants and sewage treatment plants. The water treatment facilities consist of large civil engineering buildings and equipment such as water intake tanks, agglomeration equipment, agitation tanks, sedimentation tanks, sludge discharge and dewatering equipment. When processing non-stationary liquids such as pool water and decontamination waste liquid, the “National Institute for Nuclear Water Decontamination” published on the website of the Japan Atomic Energy Agency (September 27, 2011) ), About 5 1t tanks are prepared, and each tank has a role as a zeolite addition tank, a flocculant addition stirring tank, a supernatant liquid tank (neutralization tank), and a drainage tank. doing. If such an operation is applied to pool water remaining at 200 m 3 or more at a depth of 1 m, 200 batches of treatment are required. It is a large place, many workers, and work that requires a long time.
また、処理効率を向上させるため、ゼオライト、凝集剤や凝集助剤を多量に用いると、減容固化が困難な無機汚泥が増える。また、汚泥の脱水も人力に頼らねばならず、汚泥の一時保管場所の確保という深刻な問題もある。 In addition, if a large amount of zeolite, a flocculant, or a flocculant aid is used to improve the processing efficiency, inorganic sludge that is difficult to reduce and solidify increases. In addition, the dewatering of sludge must depend on human power, and there is a serious problem of securing a temporary storage place for sludge.
本発明は、放射性物質、特に放射性セシウムを、簡易な方法で効率的に除去することができ、放射性セシウムを除去した後には減容固化が可能な有機材料を提供することを目的とする。 An object of the present invention is to provide an organic material which can efficiently remove radioactive substances, particularly radioactive cesium, by a simple method and which can be reduced in volume after the radioactive cesium is removed.
本発明者らは課題を解決するために、次の特徴を有する放射性液体の除染方法を提案する。 In order to solve the problems, the present inventors propose a method for decontaminating a radioactive liquid having the following characteristics.
態様１：放射性物質を含む液体を放射性物質除去機能が付与された有機高分子よりなるイオン交換繊維及び/又はキレート繊維と接触させて微粒子状及びイオン状の放射性物質を除去する放射性液体の除染方法。 Aspect 1: Decontamination of a radioactive liquid in which a liquid containing a radioactive substance is brought into contact with an ion exchange fiber and / or a chelate fiber made of an organic polymer provided with a radioactive substance removing function to remove particulate and ionic radioactive substances Method.
本発明の１の態様を、放射性セシウムを例にとり説明する。放射性セシウムは粒子等の固体に吸着したものと液体中にイオンとして溶解しているものの2種類に大別される。微粒子等に吸着したセシウムの割合が大きいと言われているが、イオン状のセシウムも存在するため、固形物を分離しただけでは、放射性セシウムを除去できない。従って、放射性セシウムを除去する場合は固体に吸着したセシウムとイオン状のセシウムの両方を除去する必要がある。 One embodiment of the present invention will be described by taking radioactive cesium as an example. Radioactive cesium is roughly classified into two types: those adsorbed on solids such as particles and those dissolved as ions in liquids. It is said that the proportion of cesium adsorbed on fine particles and the like is large. However, since ionic cesium is also present, radioactive cesium cannot be removed only by separating solids. Therefore, when removing radioactive cesium, it is necessary to remove both cesium adsorbed on the solid and ionic cesium.
繊維状吸着材の利点は組みひも、ロープやモールなどに成形加工が容易である点である。放射性セシウムで汚染された水に一端を固定して投入し、微粒子及びイオンを吸着後巻き取ることにより、放射性セシウムが除去できる。また、放射性物質の集まりやすい雨樋や側溝にロープやモールを置くだけでよい。固形物に吸着したセシウムはイオン交換繊維が保有する電荷によって除去できる。一般的には強酸性カチオン交換繊維は負に帯電しているため、正に帯電した微粒子を静電吸着できる。アニオン交換繊維は正に帯電しているため負に帯電した微粒子を吸着できる。放射性セシウムの化学状態によって、イオン交換繊維を選択することができる。この場合は、比較的大きな粒子や固体は吸着しにくいが、下記に示す使用方法がある。 The advantage of the fibrous adsorbent is that it can be easily molded into braids, ropes, moldings, and the like. By fixing one end into water contaminated with radioactive cesium, and adsorbing the fine particles and ions, the radioactive cesium can be removed. Moreover, it is only necessary to place ropes or moldings in rain gutters or gutters where radioactive materials tend to collect. Cesium adsorbed on the solid matter can be removed by the charge held by the ion exchange fiber. In general, since strongly acidic cation exchange fibers are negatively charged, positively charged fine particles can be electrostatically adsorbed. Since anion exchange fibers are positively charged, they can adsorb negatively charged fine particles. Depending on the chemical state of the radioactive cesium, the ion exchange fiber can be selected. In this case, relatively large particles and solids are difficult to adsorb, but there are the following usage methods.
繊維を長繊維のままか又は短繊維に切断し、カラムに充填して通常のカラム吸着方式で利用することも可能である。有機高分子繊維は成形加工性が良いため、ロープやモール以外にも撚糸を巻いたワインド型のフィルタに成形できる。また、不織布・織布などシート状の繊維はろ過膜として、プリーツ型のフィルタやのり巻き状のフィルタにも成形できる。この場合は、成形品が微粒子を除去できるため、汚染水をポンプ等によってフィルタに送水することにより、放射性セシウムを吸着した粒子とセシウムイオンが除去できる。微粒子に限らず大きな固形物も除去できる。 It is also possible to cut the fibers as long fibers or short fibers, fill the column, and use it in a normal column adsorption system. Since the organic polymer fiber has good moldability, it can be formed into a wind-type filter in which twisted yarn is wound in addition to ropes and moldings. Further, sheet-like fibers such as non-woven fabrics and woven fabrics can be formed as filtration membranes into pleated filters and glue-like filters. In this case, since the molded product can remove the fine particles, the particles adsorbed with radioactive cesium and the cesium ions can be removed by feeding the contaminated water to the filter by a pump or the like. Not only fine particles but also large solids can be removed.
また、短繊維の場合は長さにもよるが、スラリーとして利用できる。ポンプや撹拌機による流体中に混ぜることで、隅々まで吸着材を接触させることができる。スラリーから繊維を回収するには、有機高分子の布、メッシュや網などを利用することができる。金属製であってもよいが、放射性廃棄物処分の観点から有機高分子製が好ましい。 Moreover, in the case of a short fiber, depending on the length, it can be used as a slurry. The adsorbent can be brought into contact with every corner by mixing in the fluid using a pump or a stirrer. In order to recover the fibers from the slurry, an organic polymer cloth, mesh or net can be used. Although it may be made of metal, an organic polymer is preferable from the viewpoint of disposal of radioactive waste.
さらに、多孔性中空糸は本来1μｍ程度以下の微粒子を除去するために使われる素材である。したがって、イオン交換基を有する多孔性中空糸は微粒子及びイオン状のどちらのセシウムも非常によく除去できる。 Furthermore, the porous hollow fiber is originally a material used for removing fine particles of about 1 μm or less. Therefore, the porous hollow fiber having an ion exchange group can remove both fine particles and ionic cesium very well.
態様２：放射性物質が除去された液体を環境中に放流するか除染用水として再利用するとともに、放射性物質が捕捉されたイオン交換繊維及び/又はキレート繊維を放射性固体廃棄物として減容固化及び/又は焼却処分する上記１に記載の放射性液体の除染方法。 Aspect 2: The liquid from which the radioactive material has been removed is discharged into the environment or reused as decontamination water, and the ion exchange fiber and / or chelate fiber from which the radioactive material has been trapped is reduced in volume and solidified as radioactive solid waste. The method for decontaminating a radioactive liquid as described in 1 above, which is / or incinerated.
放射性物質が除去された液体は放射能を測定し、所定の基準を満たしていれば放流できる。そして、放射性物質を除去した後のイオン交換繊維材料は有機高分子であるため、圧縮固化や溶融固化が可能である。溶融固化の場合は吸着材以外の融点の低い材料を加え減容化する。減容化の程度は、用いた繊維材料の種類、適用箇所、使用条件等により決まるが、１/２以下にすることも容易である。融点が低いポリエチレンを用いて溶融固化した場合、繊維材料からの放射性物質のリークは極めて少なくなると期待できる。疎水性のポリエチレンで被覆されるためである。また、焼却処分も容易なため減容化率が高い。従来のゼオライトやフェロシアン化物を利用した凝集沈殿方式では達成困難な減容化率である。 The liquid from which the radioactive material has been removed can be discharged if the radioactivity is measured and a predetermined standard is satisfied. And since the ion exchange fiber material after removing a radioactive substance is an organic polymer, it can be compression-solidified and melt-solidified. In the case of melting and solidifying, a material having a low melting point other than the adsorbent is added to reduce the volume. The degree of volume reduction depends on the type of fiber material used, application location, use conditions, etc., but it is also easy to make it 1/2 or less. When melted and solidified using polyethylene having a low melting point, leakage of radioactive substances from the fiber material can be expected to be extremely small. This is because it is coated with hydrophobic polyethylene. In addition, the volume reduction rate is high because incineration is easy. This is a volume reduction rate that is difficult to achieve with the conventional coagulation precipitation method using zeolite or ferrocyanide.
態様３：イオン交換繊維及び/又はキレート繊維にはイオン状の放射性セシウム、ストロンチウム、ヨウ素、バリウム、イットリウム、スズさらにプルトニウムなどのアクチニド系列元素、ランタニド系列元素に代表されるウランー２３５の核***に由来する元素、そしてコバルト、ニッケル、亜鉛、マンガンなど原子炉構造材料に由来する元素から選択されるいずれかの元素を除去する機能が付与されているもののである上記１または２に記載の放射性液体の除染方法。 Aspect 3: The ion exchange fiber and / or chelate fiber is derived from the nuclear fission of uranium-235 represented by ionic radioactive cesium, strontium, iodine, barium, yttrium, tin, and actinide series elements such as plutonium, and lanthanide series elements. 3. Removal of the radioactive liquid according to 1 or 2 above, which is provided with a function of removing any element selected from the elements and elements derived from nuclear reactor structural materials such as cobalt, nickel, zinc, and manganese. Dyeing method.
放射性セシウムはカチオンであるためカチオン交換繊維で除去できる。また、放射性ヨウ素はヨウ素（I2）、次亜ヨウ素酸（HIO）、ヨウ化メチル（CH3I）の３種類の形態が主成分と言われている。これらはアニオン交換繊維で除去できる。例えば、ヨウ素（I2）や次亜ヨウ素酸（HIO）は４級アンモニウム基や３級アミノ基以下の低級アミノ基で除去できる。 ヨウ化メチル（CH3I）はイオン交換反応ではなく、３級アミノ基の非共有電子対に付加することで除去できる。また、放射性物質を含む液体の形態にもよるが、イミノジ酢酸基に代表されるアミノポリカルボン酸基、リン酸基、アミドキシム基およびポリエチレンイミン基などキレート機能も利用できる。イオン交換繊維及び/又はキレート繊維では放射性セシウム、ストロンチウム、ヨウ素、バリウム、イットリウム、スズさらにプルトニウムなどのアクチニド系列元素、ランタニド系列元素に代表されるウランー２３５の核***に由来する元素、そしてコバルト、ニッケル、亜鉛、マンガンなどイオン状である場合は、カチオン交換又はアニオン交換繊維で除去でき、キレート繊維は多価金属の吸着に適している。イオン状でない場合は、酸化物や水酸化物等の微粒子及び他の粒子や固形物に吸着している場合多い。この場合は、粒子は負に帯電している場合が多いため、繊維の荷電と粒子の荷電との静電吸着が有効に働く。また、織布や不織布はそれ自体がフィルタとしての機能を有しており、これを基材としたイオン交換繊維やキレート繊維は粒子とイオンの同時除去材として使用できる。多孔性中空糸膜はさらに微小の粒子を除去できるため、そのような用途に向いている。 Since radioactive cesium is a cation, it can be removed with a cation exchange fiber. Radioactive iodine is said to have three main forms of iodine (I2), hypoiodous acid (HIO), and methyl iodide (CH3I). These can be removed with anion exchange fibers. For example, iodine (I2) and hypoiodous acid (HIO) can be removed with a quaternary ammonium group or a lower amino group below a tertiary amino group. Methyl iodide (CH3I) can be removed not by ion exchange reaction but by adding to the lone pair of tertiary amino group. Further, although depending on the form of a liquid containing a radioactive substance, a chelating function such as aminopolycarboxylic acid group represented by iminodiacetic acid group, phosphoric acid group, amidoxime group and polyethyleneimine group can also be used. In the ion exchange fiber and / or chelate fiber, radioactive cesium, strontium, iodine, barium, yttrium, tin and actinide series elements such as plutonium, elements derived from uranium-235 fission represented by lanthanide series elements, and cobalt, nickel, In the case of an ionic form such as zinc or manganese, it can be removed by cation exchange or anion exchange fiber, and the chelate fiber is suitable for adsorption of polyvalent metals. When it is not ionic, it is often adsorbed on fine particles such as oxides and hydroxides and other particles and solids. In this case, since the particles are often negatively charged, electrostatic adsorption between the charge of the fibers and the charge of the particles works effectively. In addition, woven fabrics and non-woven fabrics themselves have a function as a filter, and ion exchange fibers and chelate fibers based on them can be used as a material for removing particles and ions simultaneously. Since the porous hollow fiber membrane can further remove fine particles, it is suitable for such a use.
態様４：前記イオン交換繊維及び/又はキレート繊維は繊維を基材として放射線グラフト重合法を利用してフェロシアン酸金属が担持されたものである上記１〜３のいずれかに記載の放射性液体の除染方法。 Aspect 4: The radioactive liquid according to any one of the above 1 to 3, wherein the ion exchange fiber and / or the chelate fiber is a fiber on which a ferrocyanate metal is supported using a radiation graft polymerization method. Decontamination method.
イオン交換基を利用してセシウムに対する選択性の特に大きいフェロシアン化金属を担持したものも利用できる。例えば、フェロシアン化コバルトを担持したアニオン交換繊維は、先ずフェロシアン酸イオンをイオン交換吸着させ、次いで塩化コバルト等の金属塩水溶液に接触させることでフェロシアン酸コバルト等の不溶化物を担持することができる。また、カチオン交換繊維の場合は、コバルトを先ず吸着させておき、次にフェロシアン化カリウム等の水溶性フェロシアン酸塩水溶液と接触させ、フェロシアン酸コバルト等の不溶化物を担持することができる。ここで、アニオン交換基としては、４級アンモニウム基、３級以下の低級アミノ基が利用できる。カチオン交換基としては、スルホン酸基、リン酸基、カルボキシル基が利用できる。また、これらイオン交換基を複数有するキレート基も本発明のイオン交換基に含まれる。これらキレート基にはイミノジ酢酸基、ポリアミノ基等が含まれる。 A material carrying a metal ferrocyanide having a particularly high selectivity to cesium using an ion exchange group can also be used. For example, an anion exchange fiber carrying cobalt ferrocyanide carries an insolubilized material such as cobalt ferrocyanate by first allowing the ferrocyanate ions to be ion exchange adsorbed and then contacting with an aqueous metal salt solution such as cobalt chloride. Can do. In the case of a cation exchange fiber, cobalt can be adsorbed first and then brought into contact with a water-soluble ferrocyanate aqueous solution such as potassium ferrocyanide to carry an insolubilized material such as cobalt ferrocyanate. Here, as the anion exchange group, a quaternary ammonium group or a tertiary or lower lower amino group can be used. As the cation exchange group, a sulfonic acid group, a phosphoric acid group, or a carboxyl group can be used. In addition, chelate groups having a plurality of these ion exchange groups are also included in the ion exchange groups of the present invention. These chelate groups include iminodiacetic acid groups, polyamino groups and the like.
このような方法により、フェロシアン酸コバルト等の非常に高いセシウムに対する選択性と担持用基材のイオン交換機能との両方の機能を有する複合素材ができる。特に海水のような塩類濃度の高い液に放射性セシウムが含まれている場合は、イオン交換機能が有効ではなく、本発明のフェロシアン酸コバルト担持材料の効果が顕著に働く。使用環境や使用方法によりどの機能を重視するか適宜選択できる。 By such a method, the composite material which has both the selectivity with respect to very high cesiums, such as cobalt ferrocyanate, and the ion exchange function of the support base material, can be obtained. In particular, when radioactive cesium is contained in a liquid having a high salt concentration such as seawater, the ion exchange function is not effective, and the effect of the cobalt ferrocyanate-supporting material of the present invention works remarkably. Depending on the usage environment and usage method, it is possible to appropriately select which function is important.
本発明において、イオン交換基及び／又はキレート基を有するグラフト鎖を導入する方法である放射線グラフト重合法とは、γ線や電子線等の電離性放射線を基材に照射し、基材表面あるいは基材内部に生成したラジカルを利用して重合性単量体（以下、「モノマー」と称する。）を重合させ、基材からグラフト鎖を成長させる方法である。放射線グラフト重合法の特徴として、放射線の照射により、基材の表面のみならず基材の内部にまでラジカルを容易に発生させることができることが挙げられる。よって、基材表面だけではなく基材内部にまでモノマーを重合させることができるので、基材に導入されるグラフト鎖の数が多くなり、したがって基材に導入される官能基の数も多くなる。グラフト（graft）とは「接ぎ木」という意味であり、グラフト鎖の一端が基材に固定されていて、他端が固定されていない自由端である状態を表す。グラフト鎖がこのような形態的特徴を有するので、グラフト鎖間にはサイズの小さなイオンから大きな分子まで容易に侵入することができる。この点は、架橋構造を有するイオン交換樹脂と比較して、大きく異なる特徴である。特にグラフト鎖中にイオン交換基やキレート基のような固定電荷が存在すると、固定電荷同士が静電的に反発するため、グラフト鎖が延び、グラフト鎖同士も反発しあう。このため、グラフト鎖間に広いスペースが形成される。放射性セシウムに対して特に選択性の大きなフェロシアン酸金属塩不溶化物を形成させるための金属イオンやフェロシアン化物イオンなども、このように形成されたグラフト鎖間スペースに容易に侵入することが可能であり、ここで有機高分子成形体への吸着ならびにフェロシアン酸金属塩微粒子形成が起こることになる。 In the present invention, the radiation graft polymerization method, which is a method for introducing a graft chain having an ion exchange group and / or a chelate group, irradiates a substrate with ionizing radiation such as γ rays or electron beams, This is a method of growing a graft chain from a base material by polymerizing a polymerizable monomer (hereinafter referred to as “monomer”) using radicals generated inside the base material. A characteristic of the radiation graft polymerization method is that radicals can be easily generated not only on the surface of the substrate but also inside the substrate by irradiation with radiation. Therefore, since the monomer can be polymerized not only on the substrate surface but also inside the substrate, the number of graft chains introduced into the substrate increases, and thus the number of functional groups introduced into the substrate also increases. . The term “graft” means “grafting” and represents a state in which one end of the graft chain is fixed to the base material and the other end is a free end that is not fixed. Since the graft chains have such morphological characteristics, small ions to large molecules can easily enter between the graft chains. This is a feature that is greatly different from that of an ion exchange resin having a crosslinked structure. In particular, when a fixed charge such as an ion exchange group or a chelate group is present in the graft chain, the fixed charges repel each other electrostatically, so that the graft chain extends and the graft chains repel each other. For this reason, a wide space is formed between the graft chains. Metal ions and ferrocyanide ions for forming ferrocyanate metal salt insolubilized materials with particularly high selectivity to radioactive cesium can easily enter the inter-graft space formed in this way. Here, adsorption to the organic polymer molded body and formation of ferrocyanic acid metal salt fine particles occur.
有機高分子成形体に照射する電離性放射線は、α線、β線、γ線、電子線、中性子線などが含まれるが、基材である有機高分子成形体の表面から深い部分まで透過する能力を有するγ線および電子線を用いることが好ましい。放射線の照射条件は、特に限定はないが、次の工程において充分なグラフト効率を得るためには、脱酸素状態で、5〜200kGy、特に30〜100kGyとすることが好ましい。この際、酸素濃度は、必要とされる重合率でのグラフト重合が達成される濃度であればよく、好ましくは、酸素濃度1％以下、より好ましくは、酸素濃度100ppm以下である。 The ionizing radiation applied to the organic polymer molded body includes α rays, β rays, γ rays, electron beams, neutron rays, etc., but penetrates from the surface of the organic polymer molded body as a base material to a deep portion. It is preferable to use gamma rays and electron beams having the ability. The irradiation condition of radiation is not particularly limited, but in order to obtain sufficient graft efficiency in the next step, it is preferable to set it to 5 to 200 kGy, particularly 30 to 100 kGy in a deoxygenated state. At this time, the oxygen concentration may be a concentration at which graft polymerization can be achieved at a required polymerization rate, and is preferably 1% or less, more preferably 100 ppm or less.
有機高分子成形体に電離性放射線を照射すると、有機高分子成形体表面ならびに内部にラジカルが発生する。ここにカチオン交換基及び/又はキレート基を有するモノマーを接触させると、発生したラジカルを基点としてカチオン交換基及び/又はキレート基を有するモノマーが重合する。ここで、放射線の照射のタイミングにより、前照射グラフト重合法と同時照射グラフト重合法とに分けられる。本発明はどちらの照射方法をも採用できる。前照射グラフト重合法とは、あらかじめ基材に放射線を照射した後、モノマーと接触させる重合方法であり、単独重合物の生成量が少ないため一般的には分離材料の製造方法にふさわしい方法である。同時照射グラフト重合法とは、基材とモノマーとの共存下に放射線を照射するグラフト重合法である。本発明においては単独重合物（ホモポリマー）生成量の少ない前照射グラフト重合法を用いることがより好ましい。 When the organic polymer molded body is irradiated with ionizing radiation, radicals are generated on the surface and inside of the organic polymer molded body. When a monomer having a cation exchange group and / or a chelate group is brought into contact therewith, the monomer having a cation exchange group and / or a chelate group is polymerized from the generated radical as a base point. Here, the pre-irradiation graft polymerization method and the simultaneous irradiation graft polymerization method are classified according to the timing of radiation irradiation. The present invention can employ either irradiation method. The pre-irradiation graft polymerization method is a polymerization method in which a base material is irradiated with radiation and then brought into contact with a monomer, and is generally suitable for a method for producing a separation material because the amount of homopolymer is small. . The simultaneous irradiation graft polymerization method is a graft polymerization method in which radiation is irradiated in the presence of a substrate and a monomer. In the present invention, it is more preferable to use a pre-irradiation graft polymerization method that produces a small amount of homopolymer (homopolymer).
ここで、接触させるモノマーが液体である場合は液相グラフト重合法となり、モノマーが気体である場合は気相グラフト重合法となる。本発明では液相または気相グラフト重合のいずれのグラフト重合方法も利用できる。すなわち、放射線を照射した有機高分子成形体に液体のモノマーを接触させることもできるし、気体のモノマーを接触させることもできる。また、含浸重合法を行うことも可能である。この方法は、予め所定のグラフト率が得られるようモノマー量を計算し、必要量のモノマーを予め有機高分子成形体に浸み込ませておくグラフト重合法である。 Here, the liquid phase graft polymerization method is used when the monomer to be contacted is a liquid, and the gas phase graft polymerization method is used when the monomer is a gas. In the present invention, any of the graft polymerization methods of liquid phase or gas phase graft polymerization can be used. That is, a liquid monomer can be brought into contact with the organic polymer molded body irradiated with radiation, or a gaseous monomer can be brought into contact therewith. It is also possible to perform an impregnation polymerization method. This method is a graft polymerization method in which a monomer amount is calculated in advance so that a predetermined graft ratio is obtained, and a necessary amount of monomer is immersed in an organic polymer molded body in advance.
内部までイオン交換基の導入が可能であるため、フェロシアン酸金属塩不溶化物を繊維表面のみならず内部にまで担持することができ好ましい。そして、グラフト鎖は一端が固定され、他端が固定されていないため、グラフト鎖間がイオン交換基の同一荷電反発により、広がっている。このイオン交換基を利用して、フェロシアン酸金属塩不溶化物を担持するため、非常に微小な粒子の状態でグラフト鎖に保持される。 Since ion exchange groups can be introduced into the interior, the ferrocyanic acid metal salt insolubilized product can be supported not only on the fiber surface but also inside. Since one end of the graft chain is fixed and the other end is not fixed, the graft chain is spread by the same charge repulsion of the ion exchange group. Since the ion-exchange group is used to carry the ferrocyanic acid metal salt insolubilized material, it is held in the graft chain in the form of very fine particles.
カチオン交換基やアニオン交換基を導入する場合、カチオン交換基又はアニオン交換基を有するモノマーをグラフト重合により容易に導入できる。 When a cation exchange group or an anion exchange group is introduced, a monomer having a cation exchange group or an anion exchange group can be easily introduced by graft polymerization.
カチオン交換基を有するモノマーとして、アクリル酸、メタクリル酸、スチレンスルホン酸、ビニルスルホン酸、メタクリルスルホン酸、アリルスルホン酸およびこれらのアルカリ金属塩が挙げられる。キレート基を有するモノマーとして、マレイン酸、ビニルイミダゾールなどが挙げられる。 Examples of the monomer having a cation exchange group include acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid, allyl sulfonic acid, and alkali metal salts thereof. Examples of the monomer having a chelate group include maleic acid and vinylimidazole.
アニオン交換基を有するモノマーとして、ビニルベンジルトリメチルアンモニウムクロライド、アリールアミン、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドが挙げられる。また、キレート基を有するモノマーとして、ビニルイミダゾールなどが挙げられる。 As monomers having an anion exchange group, vinylbenzyltrimethylammonium chloride, arylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide may be mentioned. Moreover, vinyl imidazole etc. are mentioned as a monomer which has a chelate group.
イオン交換基および／またはキレート基に転換可能な官能基を有するモノマーとして、アクリロニトリル、アクロレイン、ビニルピリジン、スチレン、クロロメチルスチレン、メタクリル酸グリシジル、アクリル酸グリシジル、グリシジルソルベート、グリシジルメタイタコナート、グリシジルビニルスルホナート、エチルグリシジルマレアート、2−ビニルピロリドン、ジビニルベンゼン、1−ビニル−2−ピペリドン、Ｎ−ビニル−Ｎ−メチルアセタミドやこれらの誘導体が挙げられる。メタクリル酸グリシジルは、スルホン酸基やアミノ基をはじめキレート基など各種官能基導入が容易であるため、特に好適に利用できる。スチレンやクロロメチルスチレンも、イオン交換基およびキレート基の導入が容易であり、好適に利用できる。例えば、有機高分子成形体にメタクリル酸グリシジルをグラフト重合させ、次いで亜硫酸ナトリウムを反応させると、グラフト鎖中に存在するグリシジル基がスルホン基（カチオン交換基）に転換される。 Monomers having functional groups that can be converted to ion exchange groups and / or chelate groups include acrylonitrile, acrolein, vinylpyridine, styrene, chloromethylstyrene, glycidyl methacrylate, glycidyl acrylate, glycidyl sorbate, glycidyl metaitaconate, glycidyl. Examples include vinyl sulfonate, ethyl glycidyl maleate, 2-vinyl pyrrolidone, divinyl benzene, 1-vinyl-2-piperidone, N-vinyl-N-methylacetamide, and derivatives thereof. Glycidyl methacrylate is particularly suitable because it can easily introduce various functional groups such as a sulfonic acid group, an amino group, and a chelate group. Styrene and chloromethylstyrene can also be suitably used because ion exchange groups and chelate groups can be easily introduced. For example, when glycidyl methacrylate is graft-polymerized on an organic polymer molded body and then sodium sulfite is reacted, the glycidyl group present in the graft chain is converted into a sulfone group (cation exchange group).
スチレンやクロロメチルスチレンも、イオン交換基およびキレート基の導入が容易であり、好適に利用できる。例えば、有機高分子成形体にクロロメチルスチレンをグラフト重合させ、次いでトリメチルアミンを反応させると、グラフト鎖中に存在するクロロメチル基が４級アンモニウム基（アニオン交換基）に転換される
態様５：イオン交換繊維及び/又はキレート繊維が単繊維、単繊維の集合体である撚糸、織布、不織布、短繊維、短繊維塊状物、中空糸、スポンジ状の空隙材料、組みひも、ロープ、袋よりなる上記１〜４のいずれかに記載の放射性液体の除染方法。
Styrene and chloromethylstyrene can also be suitably used because ion exchange groups and chelate groups can be easily introduced. For example, when chloromethylstyrene is graft-polymerized on an organic polymer molded body and then reacted with trimethylamine, the chloromethyl group present in the graft chain is converted to a quaternary ammonium group (anion exchange group). Exchange fiber and / or chelate fiber is composed of single fiber, twisted yarn that is an aggregate of single fibers, woven fabric, non-woven fabric, short fiber, short fiber lump, hollow fiber, sponge-like void material, braid, rope, bag The decontamination method of the radioactive liquid in any one of said 1-4.
本発明で使用する基材となる有機高分子成形体は、市販品のものを自由に選択できることである。例えば、繊維、不織布、織布、撚糸、膜、多孔性膜など、用途に応じて自由に選択することができる。これらの中でも繊維は表面積が大きいため、放射性物質の捕集材料として利用した場合に、大きな吸着速度を見込むことができる。また、繊維は、繊維集合体である撚糸の他、不織布、織布などのシート状にも容易に成形加工することができるので、本発明の用途には好適である。特に、放射性同位元素取扱事業所の事故時の放射性物質の除去のように、放射性物質の種類、発生個所、存在量、ならびに使用環境等が定常時と大きく変わる場合は、使用方法や使用形態を自在に選択、あるいは変更できる点が非常に有利である。本発明の放射性物質捕集材の基材として有用な繊維素材として、合成繊維の他、綿などのセルロース系繊維、動物性繊維若しくは再生繊維、またはそれらの混合繊維が挙げられる。合成繊維にはポリエステル系、ポリアミド系、アクリル系、ポリ塩化ビニル系、ポリ塩化ビニリデン系、ポリエチレン系、ポリプロピレン系、ポリウレタン系、ポリビニルアルコール系、フッ素系等が含まれる。セルロース系繊維には、綿、麻等の天然セルロース系繊維、ビスコースレーヨン、銅アンモニア法レーヨン、ポリノジック等の再生セルロース繊維、テンセル等の精製セルロース繊維、アセテート、ジアセテート等の半合成繊維が含まれる。動物性繊維には、羊毛等の獣毛繊維、絹等が含まれる。再生繊維には、キチン・キトサン繊維、コラーゲン繊維などが含まれる。これら繊維素材の混紡を用いることもまた可能である。 The organic polymer molding used as the base material used in the present invention is a commercially available product. For example, fibers, non-woven fabrics, woven fabrics, twisted yarns, membranes, porous membranes and the like can be freely selected according to the application. Among these, since the fiber has a large surface area, a high adsorption rate can be expected when used as a radioactive material collection material. In addition to the twisted yarn that is a fiber assembly, the fiber can be easily formed into a sheet shape such as a nonwoven fabric or a woven fabric, and thus is suitable for the use of the present invention. In particular, if the type, location, abundance, usage environment, etc. of the radioactive material are significantly different from those in the normal state, such as the removal of radioactive material at the time of an accident at a radioisotope handling facility, change the usage method and mode of use. It is very advantageous that it can be freely selected or changed. Examples of the fiber material useful as a base material for the radioactive material collecting material of the present invention include synthetic fibers, cellulosic fibers such as cotton, animal fibers or regenerated fibers, or mixed fibers thereof. Synthetic fibers include polyester, polyamide, acrylic, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyvinyl alcohol, fluorine, and the like. Cellulosic fibers include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon, regenerated cellulose fibers such as polynosic, purified cellulose fibers such as tencel, and semi-synthetic fibers such as acetate and diacetate. It is. Animal fibers include animal hair fibers such as wool, silk and the like. The recycled fiber includes chitin / chitosan fiber, collagen fiber and the like. It is also possible to use blends of these fiber materials.
態様６：放射性液体がプール水、家屋、ビル等建造物それに付属する雨樋、雨水桝、雨水溝、雨水導管、車両又は農産物、植物の洗浄用排水、海水、放射性汚染土壌から放射性物質を除去した廃液、放射性汚染物質を含む液体を移送する配管又は管路、側溝に存在するもの、水処理汚泥から排出させた放射性物質を含む液、放射性物質吸着材の溶離廃液、放射性物質を含む液体の貯留部及び配管から床、地面及び路面に漏出した液体、が含まれる上記１〜５のいずれかに記載の放射性液体の除染方法。
本発明の効果を発揮できる場所としては、学校プール水の除染がある。プール水には枯葉やごみなど比較的大きな固体から砂などの降下物に至るまで、様々の大きさの固形物が認められる。大きな固形物と微粒子はプレフィルタでろ過し、通過したイオン状のセシウムは後段の吸着材で除去できる。
建造物を除染した後の洗浄排水には放射性物質が含まれるため、本発明の除染後の液体を洗浄用水として再利用することが好ましい。洗浄排水量を少なくすることができる。
雨樋や側溝などには、放射性物質を含む雨水や洗浄排水が集まり、高濃度の汚染が発生している。この流路にロープ状、モール状、組みひも状あるいはネットに繊維を入れた袋を設置すれば、充填塔やポンプなどを利用しなくとも簡単に繊維状吸着材と流体とを接触させることができる。
土壌の除染廃液には固形物が大量に含まれるため、プレフィルタなど予め固形物を除去する手段が効果的である。固形物の量が多い場合は固形物ろ過用のプレフィルタを採用し、後段で繊維状吸着材を用いることができる。
別の方法としては、次のようにバッチ処理に適した方法も採用できる。まず、プレフィルタで固形物ろ過を行い、ろ過済みの処理液を戻す。この操作で大半の固形物が除去される。次に、固形物が除去されたろ液に繊維状吸着材を投入して撹拌し、イオン状のセシウムを吸着した後、プレフィルタでろ過すれば、イオン状セシウムが吸着した繊維状吸着材がプレフィルタで捕捉できる。このようにして、固形物に吸着した放射性セシウムとイオン状の放射性セシウムの両方ともプレフィルタ1個で除去でき、減容固化処理に有利である。
Aspect 6: Radioactive liquid removes radioactive substances from pool water, houses, buildings and other structures, rain gutters, rain gutters, rain ditches, rain water conduits, vehicles or agricultural products, waste water for washing plants, sea water, radioactive contaminated soil Waste liquids, pipes or pipelines that transport liquids containing radioactive pollutants, those present in side grooves, liquids containing radioactive substances discharged from water treatment sludge, elution waste liquids of radioactive material adsorbents, liquids containing radioactive substances The decontamination method for a radioactive liquid according to any one of 1 to 5 above, wherein the liquid leaked from the reservoir and the pipe to the floor, the ground, and the road surface.
As a place where the effect of the present invention can be exhibited, there is decontamination of school pool water. The pool water has solids of various sizes ranging from relatively large solids such as dead leaves and garbage to falling objects such as sand. Large solids and fine particles are filtered through a pre-filter, and the ionic cesium that has passed therethrough can be removed by a subsequent adsorbent.
Since the cleaning waste water after decontamination of the building contains radioactive substances, it is preferable to reuse the liquid after the decontamination of the present invention as cleaning water. The amount of waste water for washing can be reduced.
In rain gutters and gutters, high-concentration pollution occurs due to rainwater and washing wastewater containing radioactive materials. If a bag with ropes, moldings, braids, or nets is placed in this flow path, the fibrous adsorbent can be easily brought into contact with the fluid without using a packed tower or pump. it can.
Since the soil decontamination waste liquid contains a large amount of solid matter, means for removing the solid matter in advance, such as a prefilter, is effective. When there is much quantity of a solid substance, the pre filter for solid substance filtration is employ | adopted and a fibrous adsorbent can be used in a back | latter stage.
As another method, a method suitable for batch processing can be employed as follows. First, solid filtration is performed with a prefilter, and the filtered treatment liquid is returned. This operation removes most of the solid matter. Next, the fibrous adsorbent is added to the filtrate from which the solid matter has been removed and stirred to adsorb the ionic cesium, and then filtered through a prefilter, so that the fibrous adsorbent adsorbed with the ionic cesium is pretreated. Can be captured with a filter. In this way, both the radioactive cesium adsorbed on the solid and the ionic radioactive cesium can be removed with one prefilter, which is advantageous for volume reduction solidification treatment.
態様７：少なくとも（１）取水槽（２）プレフィルタ（３）繊維状吸着材を用いた吸着部（４）放射性物質を含む液体を吸引・送水するためのポンプ（４）除染済み液体貯留部（１）〜（４）を接続し、かつ（４）から汚染個所へ除染済み液体を戻すための配管（５）発電機（６）（１）〜（５）を積載する可動式架台を主要構成部とする放射性物質を含む液体の処理装置。 Aspect 7: At least (1) water intake tank (2) prefilter (3) adsorbing part using fibrous adsorbent (4) pump for sucking and feeding liquid containing radioactive substance (4) decontaminated liquid storage Piping for connecting the parts (1) to (4) and returning the decontaminated liquid from (4) to the contaminated part (5) Movable mount for loading the generators (6) (1) to (5) The processing apparatus of the liquid containing the radioactive substance which uses as a main component.
放射性液体の除染装置は取水槽、プレフィルタ、繊維状吸着材を用いた吸着部、放射性物質を含む液体を吸引・送水するためのポンプ、除染済み液体貯留部、そしてこれら機器を接続するための配管、配管の一部を除染用水として再利用するための配管、発電機及びこれらの機器を装荷するための可動式架台からなる。 Radioactive liquid decontamination equipment connects water tanks, prefilters, adsorption parts using fibrous adsorbents, pumps for sucking and feeding liquids containing radioactive substances, decontaminated liquid storage parts, and these devices. Piping, a pipe for reusing a part of the pipe as decontamination water, a generator, and a movable gantry for loading these devices.
放射性液体の存在形態によっていくつかの組合せが考えられるが、基本構成は取水槽、繊維状吸着材を収納した吸着部、除染済み液体貯留部と配管・ポンプからなる。例えばプール水を除染する場合を例に説明する。ゴミや砂・土壌などで汚染が激しい場合、ポンプで吸引した後、取水タンク等で滞留させ比較的大きなごみ等を除去する方が好ましい。また必要によりスクリーン等を利用することもできる。また、吸着部に入る前にプレフィルタを用い、微粒子を予め取り除くことが後段の繊維状吸着材の汚染を防ぐ意味で好ましい。プレフィルタとしては、PP及びPE等の高分子からなるワインド型フィルタやプリーツ型フィルタが利用できるが他のフィルタも利用できる。様々な開口径のものを利用することができる。 Although some combinations can be considered depending on the existence form of the radioactive liquid, the basic configuration is composed of a water intake tank, an adsorbing part containing a fibrous adsorbent, a decontaminated liquid storage part, and a pipe / pump. For example, a case where pool water is decontaminated will be described as an example. If the contamination is severe due to dust, sand, soil, etc., it is preferable to remove the relatively large waste by retaining it in a water intake tank after sucking with a pump. In addition, a screen or the like can be used if necessary. In addition, it is preferable to use a pre-filter before entering the adsorbing portion and to remove the fine particles in advance in order to prevent contamination of the fibrous adsorbent in the subsequent stage. As the prefilter, a wind filter or a pleat filter made of a polymer such as PP and PE can be used, but other filters can also be used. A thing with various opening diameters can be utilized.
また、先に述べたように繊維状吸着材を用いてワインド型フィルタを作製すれば、機械的ろ過とイオンの吸着を同時にでき、減容化に有利である。また、カートリッジフィルタを収納するハウジングの中に繊維状吸着材を充填すれば、カートリッジフィルタが微粒子除去と繊維流出防止の支持床の役割を果たし、プロセスが簡単になる。繊維や繊維の集合体である織布又は不織布を適当な長さで切断し、袋やかごに収納したものを配置してもよい。 Further, as described above, if a wind filter is produced using a fibrous adsorbent, mechanical filtration and ion adsorption can be performed simultaneously, which is advantageous for volume reduction. If the fibrous adsorbent is filled in the housing that houses the cartridge filter, the cartridge filter serves as a support bed for removing fine particles and preventing fiber outflow, thereby simplifying the process. A woven fabric or a nonwoven fabric which is a fiber or an aggregate of fibers may be cut at an appropriate length and stored in a bag or a basket.
また、短繊維をスラリーとして取り扱うことができる。この場合は、短繊維が流体中でイオンと微粒子を吸着する。そして、吸着終了後はメッシュやスクリーンなど網状のろ過機でこしとることができる。減容化を考えれば、布や織布・不織布などのウエスに受け、水切りしておけば、減容化工程への操作が容易である。また、除染対象にもよるが、予めプレフィルタで比較的大きな固形物や微粒子を除去し、その後、短繊維を入れ、撹拌後先のプレフィルタでろ過することもできる。この場合は、1個のフィルタ及びフィルタハウジングでセシウムを除去でき、減容化に有利である。プレフィルタの代わりに金網やスクリーンなどの篩も利用できる。 Moreover, a short fiber can be handled as a slurry. In this case, the short fibers adsorb ions and fine particles in the fluid. And after completion | finish of adsorption | suction, it can scrape off with a net-like filter, such as a mesh and a screen. If volume reduction is considered, if it receives on wastes, such as cloth, a woven fabric, and a nonwoven fabric, and drains, operation to the volume reduction process will be easy. Although depending on the object of decontamination, relatively large solids and fine particles can be removed in advance with a prefilter, and then short fibers can be added and filtered with a prefilter after stirring. In this case, cesium can be removed with a single filter and filter housing, which is advantageous for volume reduction. A screen such as a wire mesh or a screen can be used instead of the prefilter.
除染された液体は放射能測定を行ったうえで、放流することができる。また、処理済みの液体を除染用液体として再利用することが可能である。別の用途に利用できる。必要であれば、ポンプ等を介して除染用ジェットとすることもできる。 The decontaminated liquid can be released after measuring the radioactivity. Further, the treated liquid can be reused as a decontamination liquid. Can be used for other purposes. If necessary, it may be a decontamination jet via a pump or the like.
これら一式架台に設置すれば吸着部、ポンプ、処理水タンク、発電機、制御盤を基本構成として、プレフィルタや取水タンクを追加する場合であっても、非常にコンパクトにできる。 If installed on these sets, it is possible to make the system very compact even when a pre-filter and a water intake tank are added with the adsorption part, pump, treated water tank, generator, and control panel as basic components.
態様８：モップ、雑巾、ブラシ及びワイパー等の掃除用具に放射性物質除去機能が付与された有機高分子よりなるイオン交換繊維及び/又はキレート繊維を用いた除染用具であって、使用後に着脱可能な除染用具。 Aspect 8: Decontamination tool using ion exchange fiber and / or chelate fiber made of organic polymer provided with radioactive substance removal function to cleaning tools such as mop, rag, brush and wiper, which can be detached after use Decontamination tool.
モップ、雑巾、ブラシ及びワイパー等の掃除用具は、長い柄の先の取付部に繊維束、織布、不織布を取付け、乾燥又は湿潤状態で使用される。壁、天井、床などの汚れや液だまりを除くために使用される。放射性物質を吸着し、汚染の拡大を防ぐには、ふき取った放射性物質を強固に保持する必要がある。本発明の繊維状吸着材は湿潤、乾燥のどちらの使用方法にも適用できる。本発明のモップ、雑巾、ブラシ及びワイパーの先から垂れるしずくには放射性物質が除去されているため、汚染の拡大が防止できる。また、乾燥状態で使用する場合、水に濡れて静電気がなくなることはない。使用後の繊維状吸着材を着脱可能な構造にすることで、減容化も容易である。洗車用のモールにも本発明が適用できる。 Cleaning tools such as mops, rags, brushes, and wipers are used in a dry or wet state by attaching a fiber bundle, woven fabric, or non-woven fabric to a long handle tip attachment portion. Used to remove dirt and liquid pools on walls, ceilings, floors, etc. In order to adsorb radioactive material and prevent the spread of contamination, it is necessary to firmly hold the wiped radioactive material. The fibrous adsorbent of the present invention can be applied to both wet and dry usage methods. Since the radioactive material is removed from the drops dripping from the tip of the mop, dust cloth, brush and wiper of the present invention, the spread of contamination can be prevented. In addition, when used in a dry state, it does not get wet by getting wet with water. By making the fibrous adsorbent after use detachable, volume reduction is easy. The present invention is also applicable to a car wash mall.
除染対象物のおかれた環境により、放射性セシウムの存在割合、即ち液中にイオン状で溶解しているセシウムと固形物に付着しているセシウムとの割合が異なる。また、枯葉や土などのごみの質や混入量も変わる。プレフィルタ、繊維状吸着材などをどの段階で利用するか除染現場に即して、適切な方法を採用することができる。また、繊維状吸着材の基材として、中空糸や不織布を選択することで、これら基材の微粒子等の固形物除去性能を生かすことができる。 Depending on the environment in which the object to be decontaminated is placed, the ratio of radioactive cesium present, that is, the ratio of cesium dissolved in an ionic form in the liquid and cesium adhering to the solid matter is different. In addition, the quality and amount of garbage such as dead leaves and soil will change. An appropriate method can be adopted in accordance with the decontamination site at which stage the prefilter, the fibrous adsorbent, etc. are used. Further, by selecting a hollow fiber or non-woven fabric as the base material of the fibrous adsorbent, it is possible to make use of the solids removal performance such as fine particles of these base materials.
放射性セシウムを例にとり説明したが、他の放射性元素を除去する場合にも適用できる。 Although radioactive cesium has been described as an example, the present invention can be applied to the case where other radioactive elements are removed.
以下、本発明の実施例を示すが、本発明の態様は以下の実施例に限らない。
［実施例１］ セシウムの除去
（１）強塩基性アニオン交換繊維の製造
繊維径約35μｍのナイロン繊維よりなる撚糸500gをポリエチレン袋に入れ、減圧排気−窒素ガス導入という窒素置換操作を3回繰り返した。この袋に、ガンマ線30kGyを照射した。照射後、照射済みのナイロン繊維を袋のまま発泡スチロールの箱に入れ、ここにドライアイスも入れて冷温保存した。一方、ビニルベンジルトリメチルアンモニウム塩酸塩（以下、VBTAC 、AGCセイミケミカル社製）を純水に溶解し１０％液１Lを作製した。この溶液に窒素をバブリングし、脱酸素した。先の放射線照射済みナイロン繊維をガラスアンプルにいれ、真空ポンプにて10分間吸引し、ガラスアンプル内を真空にした。ここに脱酸素したVBTAC水溶液をアンプル内の真空を利用して導入した。40℃の恒温水槽中で５時間グラフト重合を行った。重合後、ナイロン繊維を取り出し、50℃の純水で3回洗浄した後、真空乾燥後の重量を測定した。重量増加率から、VBTACのグラフト率は34％であることがわかった。グラフト重合後のナイロン繊維のイオン交換容量を測定すると中性塩分解容量は1.3meq/gであった。
（２）フェロシアン酸コバルト金属塩担持ナイロン繊維の製造
（１）で得られた繊維をフェロシアン酸カリウム2％水溶液に1時間浸漬し、繊維にフェロシアン酸イオンを吸着させた。このフェロシアン酸イオンを吸着したナイロン繊維に塩化コバルト0.1Mと塩化カリウム0.3Mとなるよう調製した液に1時間浸漬した。フェロシアン酸コバルトをはじめ、フェロシアン酸塩不溶化物が繊維状に担持した。
（３）セシウム除去試験
１５０Lのプラスチックタンク、ポンプ、プレフィルタ（PP製ワインド型フィルタ、孔径10μｍ）、50φアクリル製カラム、50L処理水タンクからなる除去装置を作製した。（２）で作製したセシウム吸着材200gを長さ約５０ｍｍに切断し、充填した。次に、千葉大学構内の表層の土48gをとり、プラスチック製ドラム缶に入れ、さらに水道水150ｌを加え撹拌した。この後、塩化セシウムをセシウムで10ｍｇ/Ｌとなるよう加えた。このCs含有水をポンプにてプレフィルタ、セシウム吸着材及び処理水タンクの順に約４０ｌ/ｈで通液した。通液初期から１，２，３及び４時間後の処理水中のCs濃度をICP-MSにより測定した。結果はいずれもCs濃度0.2mg/ｌ以下であった。また、水道試験法による濁度及び色度測定値はそれぞれ1度以下、５度以下であり、清澄な液体が得られた。
操作が煩雑な凝集沈殿操作を行うことなく、ろ過操作のみで土の粒子に付着したセシウムとイオン状のセシウムが除去できた。フィルタ部は有機系高分子素材からなり、圧縮操作や焼却操作が可能であった。
Examples of the present invention will be described below, but the embodiments of the present invention are not limited to the following examples.
[Example 1] Removal of cesium (1) Production of strongly basic anion exchange fiber 500 g of twisted yarn made of nylon fiber having a fiber diameter of about 35 μm was put in a polyethylene bag, and the nitrogen substitution operation of evacuating and introducing nitrogen gas was repeated three times. It was. This bag was irradiated with 30 gGy of gamma rays. After the irradiation, the irradiated nylon fiber was put in a foamed polystyrene box as a bag, and dry ice was also put here and stored at a low temperature. On the other hand, vinylbenzyltrimethylammonium hydrochloride (hereinafter, VBTAC, manufactured by AGC Seimi Chemical Co., Ltd.) was dissolved in pure water to prepare 1 L of a 10% solution. Nitrogen was bubbled through the solution to deoxygenate. The previously irradiated nylon fiber was put into a glass ampule and sucked with a vacuum pump for 10 minutes to evacuate the inside of the glass ampule. The deoxygenated VBTAC aqueous solution was introduced here using the vacuum in the ampoule. Graft polymerization was carried out in a constant temperature water bath at 40 ° C. for 5 hours. After the polymerization, the nylon fiber was taken out, washed three times with 50 ° C. pure water, and then the weight after vacuum drying was measured. From the weight increase rate, it was found that the grafting rate of VBTAC was 34%. When the ion exchange capacity of the nylon fiber after graft polymerization was measured, the neutral salt decomposition capacity was 1.3 meq / g.
(2) Production of Cobalt Ferrocyanate Metal Salt-Supporting Nylon Fiber The fiber obtained in (1) was immersed in a 2% aqueous potassium ferrocyanate solution for 1 hour to adsorb ferrocyanate ions to the fiber. This nylon fiber adsorbed with ferrocyanate ions was immersed in a solution prepared to be 0.1M cobalt chloride and 0.3M potassium chloride for 1 hour. Cobalt ferrocyanate and ferrocyanate insolubilized material were supported in a fibrous form.
(3) Cesium removal test A removal device comprising a 150 L plastic tank, a pump, a prefilter (PP wind filter, pore diameter 10 μm), a 50φ acrylic column, and a 50 L treated water tank was prepared. 200 g of the cesium adsorbent prepared in (2) was cut into a length of about 50 mm and filled. Next, 48 g of the surface soil in the Chiba University campus was taken and placed in a plastic drum, and 150 l of tap water was further added and stirred. After this, cesium chloride was added to 10 mg / L with cesium. This Cs-containing water was passed through a prefilter, a cesium adsorbent, and a treated water tank in this order at a rate of about 40 l / h using a pump. The Cs concentration in the treated water at 1, 2, 3 and 4 hours after the initial flow was measured by ICP-MS. As a result, the Cs concentration was 0.2 mg / l or less. Moreover, the turbidity and chromaticity measured values by the water test method were 1 degree or less and 5 degrees or less, respectively, and a clear liquid was obtained.
Cesium and ionic cesium adhering to the soil particles could be removed only by filtration operation without performing complicated coagulation sedimentation operation. The filter part was made of an organic polymer material and could be compressed or incinerated.
［実施例２］ ストロンチウムの除去
（１）ストロンチウム繊維の製造
繊維径約35μｍのナイロン繊維よりなる撚糸500gをポリエチレン袋に入れ、減圧排気−窒素ガス導入という窒素置換操作を3回繰り返した。この袋に、ガンマ線30kGyを照射した。照射後、照射済みのナイロン繊維を袋のまま発泡スチロールの箱に入れ、ここにドライアイスも入れて冷温保存した。一方、メタクリル酸グリシジル（以下、GMA 和光化学製）１０％メタノール溶液を純水に溶解し１０％液を作製した。この溶液に窒素をバブリングし、脱酸素した。先の放射線照射済みナイロン繊維をガラスアンプルにいれ、真空ポンプにて10分間吸引し、ガラスアンプル内を真空にした。ここに窒素バブリングにより、脱酸素したGMA溶液をアンプル内の真空を利用して導入した。45℃の恒温水槽中で6時間グラフト重合を行った。重合後、反応済みGMA溶液を排出した。アセトンで3回洗浄し、乾燥後の重量を測定した。重量増加率から、GMAのグラフト率は143％であることがわかった。次にこの繊維をイミノジ酢酸ナトリウム10％、イソプロピルアルコール30％及び水60％の液１Lを加え、反応温度80℃、反応時間16時間でイミノジ酢酸基を導入した。反応後の導入率は重量増加率から、1.9mmol/gのイミノジ酢酸基を有するキレート繊維が製造された。
（２）ストロンチウム、カルシウム除去試験
実施例１−（３）において、カラムにセシウム吸着繊維の代わりにストロンチウム吸着繊維を200ｇ充填した。セシウムの代わりに塩化ストロンチウムをストロンチウム1mg/Ｌとなるよう加えた。この含有水をポンプにてプレフィルタ、キレート繊維充填カラム及び処理水タンクの順に約40ｌ/ｈで通液した。通液初期から１，２，３及び４時間後の処理水中のストロンチウム及びカルシウムをICP-MSにより測定した。結果はいずれもストロンチウム濃度及びカルシウム濃度共に0.2mg/ｌ以下であった。また、水道試験法による濁度及び色度測定値はそれぞれ1度以下、５度以下であり、清澄な液体が得られた。
ろ過操作のみで、イオン状及び土の粒子に付着したストロンチウムとカルシウムなどのアルカリ土類金属が効果的に除去された。
[Example 2] Removal of strontium (1) Production of strontium fiber 500 g of twisted yarn made of nylon fiber having a fiber diameter of about 35 µm was placed in a polyethylene bag, and the nitrogen substitution operation of evacuating and introducing nitrogen gas was repeated three times. This bag was irradiated with 30 gGy of gamma rays. After the irradiation, the irradiated nylon fiber was put in a foamed polystyrene box as a bag, and dry ice was also put here and stored at a low temperature. On the other hand, a 10% solution was prepared by dissolving a 10% methanol solution of glycidyl methacrylate (hereinafter, GMA Wako Chemical) in pure water. Nitrogen was bubbled through the solution to deoxygenate. The previously irradiated nylon fiber was put into a glass ampule and sucked with a vacuum pump for 10 minutes to evacuate the inside of the glass ampule. The GMA solution deoxygenated by nitrogen bubbling was introduced here using the vacuum in the ampoule. Graft polymerization was performed in a constant temperature water bath at 45 ° C. for 6 hours. After polymerization, the reacted GMA solution was discharged. It was washed 3 times with acetone and the weight after drying was measured. From the weight increase rate, it was found that the graft ratio of GMA was 143%. Next, 1 L of a solution of 10% sodium iminodiacetate, 30% isopropyl alcohol and 60% water was added to this fiber, and iminodiacetate groups were introduced at a reaction temperature of 80 ° C. and a reaction time of 16 hours. From the weight increase rate after the reaction, a chelate fiber having an iminodiacetic acid group of 1.9 mmol / g was produced.
(2) Strontium and calcium removal test In Example 1- (3), 200 g of strontium-adsorbing fiber was packed in the column instead of cesium-adsorbing fiber. Instead of cesium, strontium chloride was added to a concentration of 1 mg / L strontium. This contained water was passed through the prefilter, the chelate fiber packed column, and the treated water tank in this order at a rate of about 40 l / h with a pump. Strontium and calcium in the treated water at 1, 2, 3 and 4 hours after the initial flow were measured by ICP-MS. As a result, both the strontium concentration and the calcium concentration were 0.2 mg / l or less. Moreover, the turbidity and chromaticity measured values by the water test method were 1 degree or less and 5 degrees or less, respectively, and a clear liquid was obtained.
Only by filtration, alkaline earth metals such as strontium and calcium adhering to ionic and soil particles were effectively removed.
[実施例3] ワインド型フィルタ
（１）強塩基性アニオン交換繊維ボビンの製造
直径約35μｍのナイロン繊維の撚糸500gをボビンに巻いた状態でポリエチレン袋に入れ、減圧排気−窒素ガス導入という窒素置換操作を3回繰り返した。この袋を発泡スチロールの箱にドライアイス5kgとともに入れ、冷却下で発泡スチロールの箱にγ線40ｋＧｙを照射した。照射後、ポリエチレン袋の中のボビンを取り出し、ナイロン繊維撚糸を取り出し、容積20Lのステンレス製重合装置に入れた。予め窒素ガスでバブリング操作により脱酸素しておいたVBTAC10％水溶液に浸漬し、40℃でグラフト重合を行った、5時間後に装置の蓋を開き、重合を停止すると同時に、約１ｇのダミーサンプルを取り出した。ダミーサンプルのイオン交換容量を測定したところ、中性塩分解容量で1.03meq/ｇの値が得られた。
（２）フェロシアン酸コバルトの担持とワインド型フィルタの製造
実施例１−（２）の方法に準じてフェロシアン酸コバルトの不溶化物を担持したボビンを製造した。さらに、このボビンを用いてセシウム除去用ワインド型フィルタカートリッジを作製した。
（３）セシウムの除去試験
実施例１−（３）の除去装置において、プレフィルタの中に取り付けてあるPP製ワインド型フィルタを取り外し、（２）のセシウム除去用ワインド型フィルタカートリッジを取り付けた。プレフィルタの下流に設置したカラムは撤去した。処理液を原水タンクに戻すバッチ処理を行った。10時間後のタンク内のセシウム濃度をICP-MSにより測定したところ、0.2mg/ｌ以下であった。
操作が煩雑な凝集沈殿操作を行うことなくろ過操作のみで、イオン状及び土の粒子に付着したセシウムが効果的に除去された。そして、フィルタ部はプレフィルタ部1個からなり、取扱いが極めて簡単であり、減容効果が高かった。
[Example 3] Wind filter (1) Manufacture of strong basic anion exchange fiber bobbin Nitrogen replacement of 500 g of nylon fiber with a diameter of about 35 μm in a polyethylene bag in a state of being wound on a bobbin, and vacuum exhaust-introduction of nitrogen gas The operation was repeated 3 times. This bag was placed in a foamed polystyrene box together with 5 kg of dry ice, and the foamed polystyrene box was irradiated with γ rays 40 kGy under cooling. After the irradiation, the bobbin in the polyethylene bag was taken out, the nylon fiber twisted yarn was taken out, and placed in a stainless steel polymerization apparatus having a volume of 20 L. Immerse it in a 10% aqueous solution of VBTAC that has been deoxygenated by bubbling with nitrogen gas in advance and perform graft polymerization at 40 ° C. After 5 hours, open the lid of the device and stop the polymerization. I took it out. When the ion exchange capacity of the dummy sample was measured, a value of 1.03 meq / g was obtained as the neutral salt decomposition capacity.
(2) Cobalt ferrocyanate loading and production of wind filter A bobbin carrying cobalt ferrocyanate insolubilized material was produced according to the method of Example 1- (2). Furthermore, a wind type filter cartridge for removing cesium was produced using this bobbin.
(3) Cesium removal test In the removal apparatus of Example 1- (3), the PP wind filter attached in the prefilter was removed, and the cesium removal wind filter cartridge of (2) was attached. The column installed downstream of the prefilter was removed. The batch process which returns a process liquid to a raw | natural water tank was performed. When the cesium concentration in the tank after 10 hours was measured by ICP-MS, it was 0.2 mg / l or less.
The cesium adhering to the ionic and soil particles was effectively removed only by the filtration operation without performing the complicated precipitation operation. The filter part consisted of a single pre-filter part, which was very easy to handle and had a high volume reduction effect.
[実施例４] ヨウ素イオンの除去
実施例３−（３）においてセシウムの代わりにヨウ化ナトリウムをヨウ素濃度が1mg/ｌとなるよう加えた。同様の実験を行った。10時間後のヨウ素濃度は0.1mg/ｌ以下であった。
イオン状及び土の粒子に付着したヨウ素イオンが強塩基性アニオン交換繊維によって効果的に除去された。そして、フィルタ部はプレフィルタ部1個からなり、取扱いが極めて簡単であった。
[Example 4] Removal of iodine ions In Example 3- (3), sodium iodide was added instead of cesium so that the iodine concentration would be 1 mg / l. A similar experiment was conducted. The iodine concentration after 10 hours was 0.1 mg / l or less.
Iodine ions adhering to ionic and soil particles were effectively removed by the strongly basic anion exchange fiber. The filter part is composed of a single pre-filter part, which is very easy to handle.
[実施例５] 弱塩基性アニオン交換繊維によるセシウムの除去
（１）弱塩基性アニオン交換繊維の製造
実施例1−（１）において、VBTACの代わりにジメチルアミノエチルメタクリレート（以下、DMAEMA）20％水溶液を使用した以外は同様の条件でDMAEMAをグラフト重合し、46％のグラフト率を得た。
（２）フェロシアン酸コバルトの担持
実施例４−（１）で製造した繊維を０．５Mの塩酸に30分間浸漬し、塩酸を吸着させた。その後は実施例１−（２）と同様の方法でフェロシアン酸コバルトを担持した弱塩基性アニオン交換繊維を製造した。
（３）セシウム除去試験
実施例１−（３）と同様のセシウム除去試験を行ったところ、セシウムは0.2mg/ｌ以下と除去されていた。
弱塩基性アニオン交換繊維を基材として用いたセシウム吸着繊維も強塩基性アニオン交換繊維の場合と同様、イオン状及び土の粒子に付着したセシウムが効果的に除去された。
[Example 5] Removal of cesium by weakly basic anion exchange fiber (1) Production of weakly basic anion exchange fiber In Example 1- (1), dimethylaminoethyl methacrylate (hereinafter referred to as DMAEMA) 20% instead of VBTAC DMAEMA was graft polymerized under the same conditions except that an aqueous solution was used, and a graft ratio of 46% was obtained.
(2) Loading of cobalt ferrocyanate The fiber produced in Example 4- (1) was immersed in 0.5 M hydrochloric acid for 30 minutes to adsorb hydrochloric acid. Thereafter, weakly basic anion exchange fibers carrying cobalt ferrocyanate were produced in the same manner as in Example 1- (2).
(3) Cesium removal test When a cesium removal test similar to Example 1- (3) was performed, cesium was removed to 0.2 mg / l or less.
The cesium adsorbing fiber using the weakly basic anion exchange fiber as a base material effectively removed cesium adhering to the ionic and soil particles as in the case of the strong basic anion exchange fiber.
[実施例5] ひも状繊維吸着材の流路設置例
実施例３−（２）で製造したフェロシアン酸コバルト不溶化物を担持したボビンから、１ｍの長さにカットした撚糸２０本を作製した。20本の撚糸を束ね一端で結び、ほうきのように他端を自由にした。雨樋を模した内径約60φ、長さ４ｍの塩ビパイプの入り口側に撚糸の結んだ方が来るように挿入した。 水道水にセシウムを10mg/ｌとなるように溶解し、模擬雨樋の入り口側から５L/分の流量で通液した。流出液中のセシウム濃度は0.2mg/ｌ以下であった。吸着後のひも状繊維吸着材には、微粒子も吸着し、清澄な液体が得られた。
ひも状繊維を雨樋等の流路に設置するだけで、放射性セシウムが除去できた。従来のような凝集沈殿操作では、汚染水を先ず取水タンク等に貯留する必要があったが、そのような操作が不要であるため、タンク、ポンプ、電源など大掛かりな装置も不要であった。吸着後の繊維の取り扱いは極めて簡単であった。
[Example 5] Example of installation of flow path of string-like fiber adsorbent 20 twisted yarns cut to a length of 1 m were prepared from bobbins carrying cobalt ferrocyanate insolubilized material produced in Example 3- (2). . Twenty twisted yarns were bundled and tied at one end, and the other end was freed like a broom. It was inserted in such a way that a twisted yarn would come to the entrance side of a PVC pipe with an inner diameter of about 60φ and a length of 4m, imitating a rain gutter. Cesium was dissolved in tap water at 10 mg / l and passed through the simulated rain gutter at a flow rate of 5 L / min. The concentration of cesium in the effluent was 0.2 mg / l or less. Fine particles were also adsorbed to the cord-like fiber adsorbent after adsorption, and a clear liquid was obtained.
The radioactive cesium could be removed simply by installing a string-like fiber in a channel such as a rain gutter. In the conventional coagulation sedimentation operation, it is necessary to first store the contaminated water in a water intake tank or the like, but since such an operation is unnecessary, a large-scale apparatus such as a tank, a pump, and a power source is also unnecessary. Handling of the fibers after adsorption was very simple.
[実施例６] 繊維状吸着材充填ネット
実施例３−（２）で製造したフェロシアン酸コバルト不溶化物を担持したボビンから、30ｇを切り取り、綿塊状にほぐし、市販の洗濯用ネット袋入れた。これを10個作製した。水道水を利用して、150Lのタンクにセシウム濃度1mg/Lの合成原水を作製した。ネット10個をこのタンクに投入し、3時間撹拌機で接触させた。30分経過後、ネットをタンクから取出し、タンク内の液中のセシウム濃度を測定したところ。0.2mg/ｌ以下であった。
吸着後の繊維状吸着材充填ネットはそのまま、乾燥工程を経て、減容固化及び焼却処分が可能であった。
[Example 6] Fibrous adsorbent-filled net From the bobbin carrying the cobalt ferrocyanate insolubilized material produced in Example 3- (2), 30 g was cut out, loosened into a lump, and placed in a commercially available laundry net bag. . Ten of these were produced. Using tap water, synthetic raw water with a cesium concentration of 1mg / L was prepared in a 150L tank. Ten nets were put into this tank and contacted with a stirrer for 3 hours. After 30 minutes, the net was removed from the tank and the concentration of cesium in the liquid in the tank was measured. It was 0.2 mg / l or less.
The fibrous adsorbent-filled net after adsorption can be directly subjected to volume reduction and incineration through a drying process.
[実施例7] スラリー循環１
実施例３−（２）で製造したフェロシアン酸コバルト不溶化物を担持した繊維のボビンから、約500ｇを切り取り、ハサミを用いて、５ｍｍ前後のカット繊維を作製した。水道水でセシウム濃度1mg/Lに調製した合成原水150ｌに、カット繊維を投入し、水中ポンプを使用し1時間撹拌した。1時間経過後、図１に示すように水中ポンプの吐出側に布袋を設置し、カット繊維を濾別した。タンク内のセシウム濃度は0.2mg/ｌ以下であった。
水中ポンプの撹拌操作と網（又は布）で、イオン状及び土の微粒子に付着したセシウムが効果的に除去された。そして、布に集めたカット繊維は取扱いが極めて簡単であった。脱水・乾燥工程し、圧縮操作や焼却操作が可能であった。
[Example 7] Slurry circulation 1
About 500 g was cut from the bobbin of the fiber carrying the cobalt ferrocyanate insolubilized product produced in Example 3- (2), and cut fibers of about 5 mm were produced using scissors. Cut fibers were added to 150 liters of synthetic raw water prepared with tap water to a cesium concentration of 1 mg / L, and stirred for 1 hour using a submersible pump. After 1 hour, as shown in FIG. 1, a cloth bag was installed on the discharge side of the submersible pump, and the cut fibers were separated by filtration. The concentration of cesium in the tank was 0.2 mg / l or less.
Cesium adhering to the ionic and soil fine particles was effectively removed by the stirring operation of the submersible pump and the net (or cloth). The cut fibers collected on the fabric were very easy to handle. After dehydration and drying, compression and incineration operations were possible.
[実施例８] スラリー循環２
実施例３−（２）で製造したフェロシアン酸コバルト不溶化物を担持した繊維のボビンから、約300ｇを切り取り、ハサミを用いて、２〜３ｍｍ前後のカット繊維を作製した。実施例１−（３）と同様のセシウム除去実験装置において、土を１０ｇ加え、水道水でセシウム濃度1mg/Lに調製した合成原水150ｌを作成した。先ず、プレフィルターとタンクの循環を1時間行い、固形物をろ過した。次に、固形物のろ過されたタンク内の液にカット繊維を投入し、1時間撹拌した。撹拌後のタンク内の水をプレフィルタに通液し、タンク内のカット繊維をろ過した。この処理水はセシウム濃度0.2mg/ｌ以下であった。プレフィルターの下流側に設置したセシウム吸着カラムを使用しなくとも、十分なセシウム除去性能が得られた。この試験の場合、放射性汚染物質はプレフィルターのハウジング内に溜まり、放射性廃棄物が1個のハウジングで持ち運びでき、取扱が容易であった。
プレフィルターの運転時間を調整するだけで、イオン状及び土の微粒子に付着したセシウムが効果的に除去され、1個のプレフィルタ―内に集めることが可能であった。取扱いが極めて簡単であった。
[Example 8] Slurry circulation 2
About 300 g was cut from the bobbin of the fiber carrying the cobalt ferrocyanate insolubilized product produced in Example 3- (2), and cut fibers of about 2 to 3 mm were produced using scissors. In the same cesium removal experimental apparatus as in Example 1- (3), 10 g of soil was added, and 150 l of synthetic raw water prepared to a cesium concentration of 1 mg / L with tap water was prepared. First, the prefilter and the tank were circulated for 1 hour, and the solid matter was filtered. Next, the cut fiber was put into the liquid in the tank where the solid matter was filtered, and stirred for 1 hour. Water in the tank after stirring was passed through a prefilter, and cut fibers in the tank were filtered. This treated water had a cesium concentration of 0.2 mg / l or less. Sufficient cesium removal performance was obtained without using a cesium adsorption column installed downstream of the prefilter. In this test, radioactive contaminants accumulated in the prefilter housing, and radioactive waste could be carried in a single housing, making it easy to handle.
By adjusting the prefilter operating time, cesium adhering to ionic and soil particles was effectively removed and could be collected in a single prefilter. Handling was extremely simple.
[実施例９] 中空糸
外形１ｍｍ、孔径0.5μｍのPE製多孔性中空糸膜にガンマ線を50ｋGy照射した後、実施例４−（１）に記載した方法によりDMAEMAをグラフト重合し。31％のグラフト率を得た。さらに、実施例４−（２）の方法により、フェロシアン酸コバルト不溶化物を担持した。中空糸の一端を接着剤で埋め、他端を開口させたままとした。注射器のシリンジを開口部に差し込み、セシウム濃度1m/ｌを含有する水道水を５ｍｌ/分の流量で導入した。多孔性中空糸膜を透過した液体のセシウム濃度を測定したところ、セシウム濃度は0.2mg/ｌ以下であった。多孔性中空糸膜はもともと微粒子を除去できる材料であるため、この多孔性中空糸膜を複数本まとめたカートリッジフィルターはイオン状のセシウム及び微粒子に付着したセシウムも同時に除去できることが明らかである。
[Example 9] Hollow fiber After irradiating 50 kGy of gamma rays to a PE porous hollow fiber membrane having an outer diameter of 1 mm and a pore diameter of 0.5 µm, DMAEMA was graft-polymerized by the method described in Example 4- (1). A graft rate of 31% was obtained. Further, a cobalt ferrocyanate insolubilized product was supported by the method of Example 4- (2). One end of the hollow fiber was filled with an adhesive, and the other end was left open. A syringe of a syringe was inserted into the opening, and tap water containing a cesium concentration of 1 m / l was introduced at a flow rate of 5 ml / min. When the cesium concentration of the liquid that permeated through the porous hollow fiber membrane was measured, the cesium concentration was 0.2 mg / l or less. Since the porous hollow fiber membrane is originally a material from which fine particles can be removed, it is apparent that a cartridge filter in which a plurality of porous hollow fiber membranes are combined can simultaneously remove ionic cesium and cesium attached to the fine particles.
[実施例１０] 不織布
（１）強酸性カチオン交換不織布の製造
繊維径16μｍのポリエチレン（鞘）/ポリエチレンテレフタレート芯の芯鞘複合繊維よりなり、目付４５ｇ/m2、厚み０．５ｍｍの熱融着不織布を放射線グラフト重合の基材とした。30cm×20cmの不織布10枚を窒素雰囲気でガンマ線を30ｋGy照射した。次にGMA１０％メタノール溶液でグラフト重合を行い、グラフト率93％を得た。この不織布を亜硫酸ナトリウム１０％、イソプロピルアルコール１０％、水８０％（重量％）の液に浸漬し、80℃、12時間スルホン化反応を行った。重量増加率より、1.85meq/gの強酸性カチオン交換不織布が得られた。
（２）フェロシアン酸コバルト不溶化物担持不織布の製造
（１）の強酸性カチオン交換不織布を塩化コバルト０．５Mに３０分間浸漬した後、水洗した。次に、フェロシアン酸カリウム０．２M水溶液に浸漬し、繊維にフェロシアン酸コバルトの不溶化物を担持した。洗浄はバッチで塩化ナトリウム１M水溶液、純水3回の順に行った。
（３）カラム試験
実施例９−（２）で製造したフェロシアン酸コバルト不溶化物担持不織布から５０φの穴開け機で10枚の50φ円形シートをとり、内径50φのアクリル製カラムに積層充填した。実施例１−（３）と同様のセシウム除去試験を行った。結果はセシウム濃度0.2mg/ｌ以下、清澄な処理水が得られた。
[Example 10] Nonwoven fabric (1) Production of strong acid cation exchange nonwoven fabric Heat-sealed with a core-sheath composite fiber of polyethylene (sheath) / polyethylene terephthalate core having a fiber diameter of 16 µm, weight per unit area of 45 g / m 2 , and thickness of 0.5 mm. A nonwoven fabric was used as a base material for radiation graft polymerization. Ten non-woven fabrics of 30 cm × 20 cm were irradiated with gamma rays at 30 kGy in a nitrogen atmosphere. Next, graft polymerization was performed with a 10% methanol solution of GMA to obtain a graft ratio of 93%. This nonwoven fabric was immersed in a solution of 10% sodium sulfite, 10% isopropyl alcohol, and 80% (% by weight) water, and subjected to sulfonation reaction at 80 ° C. for 12 hours. From the weight increase rate, a strongly acidic cation exchange nonwoven fabric of 1.85 meq / g was obtained.
(2) Production of cobalt ferrocyanate-insolubilized nonwoven fabric-supported nonwoven fabric The strongly acidic cation exchange nonwoven fabric of (1) was immersed in 0.5 M cobalt chloride for 30 minutes and then washed with water. Next, it was immersed in a 0.2 M aqueous solution of potassium ferrocyanate, and the insolubilized product of cobalt ferrocyanate was supported on the fiber. Washing was performed in a batch in order of 1M sodium chloride aqueous solution and 3 times pure water.
(3) Column Test Ten 50φ circular sheets were taken from the non-woven fabric carrying cobalt ferrocyanate insolubilized material prepared in Example 9- (2) with a 50φ punch, and packed in an acrylic column having an inner diameter of 50φ. A cesium removal test similar to that in Example 1- (3) was performed. As a result, a clear treated water having a cesium concentration of 0.2 mg / l or less was obtained.
[実施例11] バッグフィルタ
実施例３−（１）及び（２）で製造したセシウム吸着材を数cmにカットした。実施例１−（３）のセシウム除去試験装置のアクリル製カラムの代わりに直径100ｍｍ、長さ約400mmのバッグフィルタ（含ハウジング）を設置し、カット繊維300ｇを充填した。実施例１−（３）と同様のセシウム除去試験を行ったところ、通液初期から１，２，３及び４時間後の処理水中のCs濃度は0.2mg/ｌ以下であった。
Example 11 Bag Filter The cesium adsorbent produced in Example 3- (1) and (2) was cut into several centimeters. In place of the acrylic column of the cesium removal test apparatus of Example 1- (3), a bag filter (including a housing) having a diameter of 100 mm and a length of about 400 mm was installed and filled with 300 g of cut fibers. When the same cesium removal test as in Example 1- (3) was performed, the Cs concentration in the treated water after 1, 2, 3 and 4 hours from the initial stage of liquid passing was 0.2 mg / l or less.
[実施例12] ウエス（ワイパー）
（１）強塩基性アニオン交換不織布の製造
芯/鞘がポリエチレンテレフタレート/ポリエチレンからなる直径約15μｍの芯鞘複合繊維より構成された熱融着不織布（目付50ｇ/m2、厚み0.35ｍｍ）を20cm×30cmの大きさで10枚カットした。この不織布に窒素雰囲気で電子線を50ｋGy照射した。VBTAC/N-ビニルピロリドン/水（重量比5/10/85）の混合モノマー溶液１kgを作製し、窒素バブリングを行いモノマー液中の脱酸素を行った。照射済み不織布をモノマー混合溶液に浸漬し、45℃、8時間グラフト重合を行った。グラフト重合終了後、不織布を取り出し、洗浄乾燥を行った。重量増加率からグラフト率を算出すると82％であった。
（２）フェロシアン酸コバルト金属塩担持不織布の製造
（１）で得られた不織布をフェロシアン酸カリウム2％水溶液に1時間浸漬し、不織布にフェロシアン酸イオンを吸着させた。このフェロシアン酸イオンを吸着した不織布に塩化コバルト0.1Mと塩化カリウム0.3Mとなるよう調製した液に1時間浸漬した。フェロシアン酸コバルト不溶化物が不織布に担持した。
（３）セシウム除去試験
住宅用床材（塩化ビニル製）１ｍ×１ｍにセシウム10mg/ｌを含有する水道水を50ｍｌこぼし、溜まりを作った。市販のワイパー（花王株式会社、クイックルワイパー）のワイパー取付け部に（２）で作成したフェロシアン酸コバルト不溶化物担持不織布20cm×20cmを取り付け、床を拭き取った。床上に残存したセシウムを洗浄瓶で集め、セシウム濃度を測定した。こぼしたセシウム量の９５％以上が除去されていた。また、この拭き取り試験を5回繰り返してもセシウムが除去された。この不織布を水に浸漬しても、除去したセシウムがリークすることはなかった。
[Example 12] Waste (wiper)
(1) Manufacture of strongly basic anion-exchange nonwoven fabric 20cm of heat-sealed nonwoven fabric (weight per unit area 50g / m 2 , thickness 0.35mm) composed of core-sheath composite fibers with a core / sheath made of polyethylene terephthalate / polyethylene with a diameter of about 15μm 10 sheets with a size of × 30 cm were cut. This nonwoven fabric was irradiated with an electron beam at 50 kGy in a nitrogen atmosphere. 1 kg of a mixed monomer solution of VBTAC / N-vinylpyrrolidone / water (weight ratio 5/10/85) was prepared and deoxygenated in the monomer solution by nitrogen bubbling. The irradiated non-woven fabric was immersed in the monomer mixed solution, and graft polymerization was performed at 45 ° C. for 8 hours. After the graft polymerization, the nonwoven fabric was taken out and washed and dried. The graft ratio calculated from the weight increase rate was 82%.
(2) Production of cobalt ferrocyanate metal salt-supported nonwoven fabric The nonwoven fabric obtained in (1) was immersed in a 2% aqueous potassium ferrocyanate solution for 1 hour to adsorb ferrocyanate ions to the nonwoven fabric. This non-woven fabric adsorbed with ferrocyanate ions was immersed in a solution prepared to be 0.1 M cobalt chloride and 0.3 M potassium chloride for 1 hour. The cobalt ferrocyanate insolubilized material was supported on the nonwoven fabric.
(3) Cesium removal test Residential flooring (made of vinyl chloride) 50 ml of tap water containing 10 mg / l of cesium was spilled into 1 m x 1 m to make a reservoir. The non-woven fabric carrying cobalt ferrocyanate insolubilized material 20cm × 20cm prepared in (2) was attached to the wiper attachment portion of a commercially available wiper (Kao Corporation, Quickle Wiper), and the floor was wiped off. The cesium remaining on the floor was collected in a washing bottle, and the cesium concentration was measured. More than 95% of the spilled cesium was removed. In addition, cesium was removed by repeating this wiping test five times. Even if this nonwoven fabric was immersed in water, the removed cesium did not leak.
［実施例１３］ 自動車洗車モール
実施例5で作成したひも状繊維吸着材を自動車洗車用モールに針金で固定し、自動車の洗浄を行った。また、洗浄水の排出流路に実施例１２の不織布を敷いた。自動車の除染及び洗車排水からセシウムの除去が同時に可能であった。
[Example 13] Automobile car wash mall The string-like fiber adsorbent prepared in Example 5 was fixed to an automobile car wash mall with a wire, and the automobile was washed. Further, the nonwoven fabric of Example 12 was laid in the washing water discharge channel. It was possible to remove cesium from automobile decontamination and car wash wastewater at the same time.
[比較例１]
実施例１−（３）で使用した１５０Lタンクにゼオライト２０ｇを加え10分間十分に撹拌した。次に水道用凝集剤であるポリ塩化アルミニウム（PAC）を３０ｍｌ加え撹拌し、5分経過後に撹拌を停止し、撹拌が自然停止するまで30分放置した。タンク底部には汚泥が沈殿し、上澄み液には小さなフロックが浮遊していた。上澄み液を実施例1−（３）で用いたプレフィルタでろ過し、ろ液のセシウム濃度を測定したところ、0.2mg/l以下であった。１５０Lタンクの底には汚泥が約５L溜まっていた。３Lポリビーカーで汚泥をすくい取り、円形定性ろ紙（直径40cm）でろ過した。汚泥をすくい取る際、フロックが破壊され小さくなったため、ろ過時間が1時間以上かかった。また、含水率を下げるため、別の新しいろ紙を使用して水分を吸い取らせた。このようにして、2人の作業者が付きっきりで作業開始から終了まで5時間以上かかり、操作も煩雑であった。また、減容固化の困難な無機化合物の汚泥残った。原水タンク、処理水タンク、プレフィルタ、汚泥脱水ろ過装置、ろ液回収タンク、凝集剤溶解槽、攪拌機などタンク、バケツ類が多いため、作業終了後も器具洗浄水が多量に必要であった。
[Comparative Example 1]
20 g of zeolite was added to the 150 L tank used in Example 1- (3) and stirred sufficiently for 10 minutes. Next, 30 ml of polyaluminum chloride (PAC), which is a flocculant for water supply, was added and stirred. After 5 minutes, stirring was stopped and left for 30 minutes until stirring stopped spontaneously. Sludge settled at the bottom of the tank, and a small floc floated in the supernatant. The supernatant was filtered through the prefilter used in Example 1- (3), and the cesium concentration of the filtrate was measured and found to be 0.2 mg / l or less. About 5L of sludge was collected at the bottom of the 150L tank. The sludge was scooped up with a 3 L poly beaker and filtered with a circular qualitative filter paper (diameter 40 cm). When scooping up the sludge, the flock was destroyed and reduced in size, so the filtration time took more than an hour. In order to lower the moisture content, another new filter paper was used to absorb moisture. In this way, two workers were involved and it took more than 5 hours from the start to the end of the work, and the operation was complicated. In addition, sludge of inorganic compounds that are difficult to reduce and solidify remained. Since there were many tanks and buckets such as raw water tanks, treated water tanks, prefilters, sludge dewatering filtration devices, filtrate collection tanks, flocculant dissolution tanks, stirrers, etc., a large amount of equipment washing water was required even after the work was completed.
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| JP6147531B2 (en) * | 2013-03-19 | 2017-06-14 | 東洋紡株式会社 | Recontamination control method |
| JP6162533B2 (en) * | 2013-08-16 | 2017-07-12 | ユニチカトレーディング株式会社 | Cesium ion adsorption cylindrical filter and method for producing the same |
| JP2015087369A (en) * | 2013-10-30 | 2015-05-07 | 株式会社 環境浄化研究所 | Strontium removal method by fiber formed by introducing iminodiacetic group to graft chain |
| JP6304537B2 (en) * | 2014-03-28 | 2018-04-04 | 清水建設株式会社 | Decontamination method for concrete |
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| JP6607485B2 (en) * | 2015-04-30 | 2019-11-20 | 国立大学法人名古屋大学 | Method for removing suspended cesium |
| JP6628313B2 (en) * | 2016-06-15 | 2020-01-08 | 日立Ｇｅニュークリア・エナジー株式会社 | Filter vent device |
| KR102104719B1 (en) * | 2018-07-09 | 2020-04-24 | 충남대학교산학협력단 | Cesium ion exchange resin and manufacturing method thereof |
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