JP3831107B2 - Radium adsorbent, method for producing the same, and method for treating radium-containing wastewater using the same - Google Patents
Radium adsorbent, method for producing the same, and method for treating radium-containing wastewater using the same Download PDFInfo
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- JP3831107B2 JP3831107B2 JP06971498A JP6971498A JP3831107B2 JP 3831107 B2 JP3831107 B2 JP 3831107B2 JP 06971498 A JP06971498 A JP 06971498A JP 6971498 A JP6971498 A JP 6971498A JP 3831107 B2 JP3831107 B2 JP 3831107B2
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- radium
- adsorbent
- titanium
- zirconium
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- 229910052705 radium Inorganic materials 0.000 title claims description 83
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 title claims description 83
- 239000003463 adsorbent Substances 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 33
- 239000002351 wastewater Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010936 titanium Substances 0.000 claims description 38
- 230000002378 acidificating effect Effects 0.000 claims description 37
- 229910052719 titanium Inorganic materials 0.000 claims description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 35
- 229910052726 zirconium Inorganic materials 0.000 claims description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 29
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000003729 cation exchange resin Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000003755 zirconium compounds Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 229910001868 water Inorganic materials 0.000 description 30
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 8
- 229920003303 ion-exchange polymer Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052770 Uranium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- -1 titanium halide Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 201000008968 osteosarcoma Diseases 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ラジウム含有廃水中よりラジウムを効率よく吸着除去することができ、さらに、繰り返し使用可能なラジウム吸着剤、その製造方法及びそれを用いたラジウム含有廃水の処理方法に関するものである。
【０００２】
【従来の技術】
ラジウムは主にウランが崩壊する過程で生成し、自然界ではウラン鉱石中にウランと共存している。このようなラジウムを含有する廃水としては、例えば、科学研究所から発生する廃水、地下水、ウラン鉱山開発に伴って発生する廃水等があげられる。
ラジウムは半減期が長く、多量に摂取すると体内に蓄積される性質があり、骨肉腫や白血病が疾病すると言われており、水中のラジウム濃度は原子力規制法等により公衆に対して３．０Ｂｑ／Ｌ以下に規制され、地元との安全協定により上乗せで０．０３７Ｂｑ／Ｌ以下に厳しく規制されている事業所もある。
【０００３】
この様なラジウム含有廃水の処理方法としては、廃水に塩化バリウム等と硫酸又はその塩を添加し、発生した硫酸バリウムにより共沈除去する方法が知られている。しかし、この方法では、沈殿池、濾過設備等に大きなスペースを必要とするうえ、発生するラジウム含有固形廃棄物が多量になる等の問題点があった。
また、吸着剤を用いてラジウムを選択的に吸着除去する方法が知られており、吸着剤としては例えば、特開昭５６−１１１０４３号公報には、無定型チタン酸を水、無機酸、無機結合体、有機結合体の少なくとも一つで結合させた吸着剤が、特開平３−５６７８３号公報には、フェノール樹脂に鉄、チタン等の多価金属の水酸化物を分散させた吸着剤が開示されている。
【０００４】
【発明が解決しようとする課題】
しかし、これらの吸着剤は、吸着剤中のチタンが分散状態で緩やかな結合であるため、空気攪拌等の物理的な作用で容易に脱落し、脱落したチタン酸化物は通水時の圧力損失を増加させるうえラジウムと共に流出し、処理水のラジウム濃度を０．０３７Ｂｑ／Ｌ以下の厳しい規制値まで処理できない場合があり、また、ラジウム吸着速度が遅いため、高流速で処理すると破過までの処理量が大幅に低下し、このため再生を頻繁に行うことが必要となり、再生費用が高くなる等の問題があった。
本発明は、ラジウム吸着能に優れ、かつ、鉱酸等を用いて再生処理することにより繰り返し使用が可能なラジウム吸着剤、その製造方法及びそれを用いたラジウム含有廃水の処理方法を提供することを目的とするものである。
【０００５】
【課題を解決するための手段】
本発明者等は、このような課題を解決するために鋭意検討の結果、強酸性陽イオン交換樹脂にチタン及びジルコニウムの含水酸化物を化学的に結合させたラジウム吸着剤がラジウム吸着能に優れ、さらに、鉱酸による再生処理後も優れたラジウム吸着能を示すということを見出し、本発明に到達した。
すなわち、第１の発明は、強酸性陽イオン交換樹脂とチタン及びジルコニウムの含水酸化物とからなり、チタン及びジルコニウムの含水酸化物が強酸性陽イオン交換樹脂に化学的に結合していることを特徴とするラジウム吸着剤を要旨とするものである。
また、第２の発明は、強酸性陽イオン交換樹脂に、チタン化合物の酸性水溶液及びジルコニウム化合物の酸性水溶液を接触させた後、熱処理及びアルカリ処理を行うことを特徴とする上記ラジウム吸着剤の製造方法を要旨とするものである。
さらに、第３の発明は、上記ラジウム吸着剤を、ラジウム含有廃水と接触させて吸着剤にラジウムを吸着させることを特徴とするラジウム含有廃水の処理方法を要旨とするものである。
【０００６】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明でいう強酸性陽イオン交換樹脂としては、例えば、通常の状態で固体の水不溶性の有機ポリマーから形成されたマトリックス樹脂を母体とし、水溶液からイオン交換を司るに十分な陰イオン交換基を持ち、陰イオン交換基がスルホン酸基であるものがあげられ、具体的には、フェノール・ホルマリン系、スチレン系、アクリル系のポリマーの中にスルホン酸基を交換基として有するものがあげられる。強酸性陽イオン交換樹脂の代わりにカルボン酸系の弱酸性陽イオン交換樹脂を用いると、チタン及びジルコニウムの結合量が少なくなり、また、イミノ二酢酸系、アミノメチルホスホン酸系の交換基を有するキレート樹脂を用いると、チタン及びジルコニウムは良好に結合するが、結合したチタン及びジルコニウムのラジウム吸着活性が低下し、ラジウム吸着能が悪くなるという問題点がある。
【０００７】
強酸性陽イオン交換樹脂は、製造条件で物理的、化学的な性能が異なるものが市販されている。本発明においては、これらの任意の樹脂を使用することができるが、高分子の母体がポーラス型の樹脂を用いると、吸着剤のラジウムを吸着する速度が速いことから好ましい。ポーラス型の強酸性陽イオン交換樹脂とは、高分子の母体が多孔性の物理構造のものであり、例えば、ゲル型の多孔度が１％未満に対して、ポーラス型の多孔度は５〜３０％と言われており、重合段階でトリブチルホスフェート、イソドデカン、メチルイソブチルケトン等の孔形成剤を添加して製造することができる。
【０００８】
吸着剤中の強酸性イオン交換樹脂と化学的に結合しているチタンの含水酸化物の量としては、チタンとして２ｗｔ％以上であることが好ましく、さらに２〜２０ｗｔ％が好ましく、特に５〜１５ｗｔ％が好ましい。また、ジルコニウムの含水酸化物の量としては、ジルコニウムとして０．３ｗｔ％以上であることが好ましく、さらに０．３〜５ｗｔ％が好ましく、特に０．５〜３ｗｔ％が好ましい。チタンの量が上記範囲より少なくなると、ラジウム吸着量が大幅に低下する傾向があり、ジルコニウムの量が上記範囲より少なくなると、鉱酸等を用いて樹脂を再生した際にチタンのラジウム吸着活性が低下する傾向にある。また、ジルコニウムの量がチタンの量より多くなると吸着速度が低下するので、ジルコニウムの量はチタンの量より少なくすることが好ましい。なお、一般的なイオン交換樹脂の交換容量は、０．５〜２．５ｅｑ／Ｌ程度なので、イオン交換樹脂とチタンとの最大結合量は２０ｗｔ％程度になる。
【０００９】
次に、本発明のラジウム吸着剤の製造方法について説明する。
まず、本発明においては、水中に分散させたプロトン型あるいはナトリウム、カリウム等の塩型の強酸性陽イオン交換樹脂に、チタン化合物の酸性水溶液及びジルコニウム化合物の酸性水溶液を接触させて、チタン及びジルコニウムを強酸性陽イオン交換樹脂に化学的に結合させる。接触する際には、チタン化合物の酸性水溶液とジルコニウム化合物の酸性水溶液をそれぞれ接触させてもよいし、チタン化合物とジルコニウム化合物とを含有する酸性水溶液（混合溶液）を接触されてもよいが、混合溶液を用いた方が、樹脂に結合するチタンとジルコニウムの比率を調整しやすいために好ましい。
【００１０】
このような酸性水溶液は、例えば、チタン化合物としてハロゲン化チタン（ＴｉＸ3 、ＴｉＸ4 ）、硫酸チタン（Ｔｉ（ＳＯ4 ）2 ）、硝酸チタン（Ｔｉ（ＮＯ3 ）4 ）等を、また、ジルコニウム化合物としてオキシ塩化ジルコニウム（ＺｒＯＣｌ2 ）、オキシ硝酸ジルコニウム（ＺｒＯ（ＮＯ3 ）2 ）等を水に溶解することによって作製することができる。
【００１１】
接触させる酸性水溶液の量としては、吸着剤中のチタンの量が２〜２０ｗｔ％になる量が好ましいので、強酸性陽イオン交換樹脂の総交換量に対してチタンの量が０．３〜３０倍当量となる量が好ましい。また、吸着剤中のジルコニウムの量が０．３〜５ｗｔ％になる量が好ましいので、強酸性陽イオン交換樹脂の総交換容量に対してジルコニウムの量が０．１〜３倍当量となる量が好ましい。
このような酸性水溶液中のチタン濃度としては、特に限定されるものではないが、低濃度の水溶液を使用すると、チタンイオンが加水分解して不溶性になることから０．２５ｇ／Ｌ以上であることが好ましい。また、ジルコニウム濃度としては、特に限定されるものではない。
【００１２】
接触方法としては、強酸性陽イオン交換樹脂と酸性水溶液とを撹拌もしくは振盪するバッチ法、強酸性陽イオン交換樹脂を樹脂塔に充填し、酸性水溶液を通液するカラム法のいずれの方法でも可能である。バッチ法で行う場合には、２時間以上撹拌もしくは振盪することが好ましく、カラム法で行う場合には、酸性水溶液を循環通液すると、酸性水溶液を有効に活用できることから好ましい。
【００１３】
チタン及びジルコニウムを結合させた樹脂に余剰のチタン化合物及びジルコニウム化合物が残存していると、後のアルカリ処理により不溶性の含水酸化チタン及びジルコニウムが生成し、樹脂との分離が必要になるため、予め樹脂を水洗して、余剰のチタン化合物及びジルコニウム化合物をイオン交換樹脂から分離しておくことが好ましい。水洗は、通常樹脂体積の３０倍の水を使用して行えばよい。
【００１４】
次に、このようにしてチタン及びジルコニウムを結合させた樹脂を、熱処理及びアルカリ処理する。
熱処理の方法としては、熱風乾燥器等による乾熱処理による方法、水中で加熱しながら行う水熱処理による方法があげられる。乾熱処理による方法では、温度が１５０℃以上になるとイオン交換樹脂の分解が始まり、交換基の脱落、共重合体母体の分解が起こるので、８０〜１５０℃で０．５〜８時間処理することが好ましく、１００〜１２０℃で２〜４時間処理することがさらに好ましい。また、水熱処理による方法では、６０〜１００℃で０．５〜１０時間処理することが好ましく、７０〜９５℃で１〜６時間処理することがさらに好ましい。熱処理を行うことにより、イオン交換樹脂とチタン及びジルコニウムとの結合を強固にすることができる。
【００１５】
また、アルカリ処理とは、樹脂をアルカリ剤と接触させることにより、樹脂に結合したチタン及びジルコニウムを含水酸化物に変換させることである。このときに使用するアルカリ剤としては、例えば、リチウム、カリウム、ナトリウム等のアルカリ金属の水酸化物や炭酸塩、カルシウム、マグネシウム、ストロンチウム、バリウム等のアルカリ土類金属の水酸化物や炭酸塩の水溶液があげられるが、経済性、操作性の観点からアルカリ金属の水酸化物の水溶液が好ましい。接触方法としては、バッチ法又はカラム法で行うことができる。アルカリ剤の使用量としては、使用した強酸性陽イオン交換樹脂の総交換量の０．３当量倍以上が好ましく、０．５〜２当量倍がより好ましい。
このような熱処理及びアルカリ処理の順序としては、どちらの操作から行っても同様な吸着剤が得られるので、特に限定されない。
【００１６】
次に、本発明のラジウム含有廃水の処理方法について説明する。
本発明のラジウム吸着剤は、チタン及びジルコニウムの含水酸化物がイオン交換樹脂と化学的に安定に結合しており、ラジウムに対する吸着量が大きく、また、吸着速度が速いことから、ラジウム含有廃水と接触させることにより容易にラジウム含有廃水を処理することができる。接触させる方法としては、バッチ法、カラム法のいずれの方法を用いてもよいが吸着速度が速い特性が生かせるカラム法が好ましい。この吸着剤をカラムに充填し、ラジウムを５Ｂｑ／Ｌ含有する排水を空間速度が４０ｈ-1の高流速で処理した場合、ラジウムの破過濃度を０．０３７Ｂｑ／Ｌとした時の吸着剤の破過までの処理時間は約１２５時間と長く、再生間隔が長くなり再生に要する費用を安価にすることができる。
【００１７】
また、ラジウムを吸着させた後の吸着剤は、塩酸、硫酸等の鉱酸や鉱酸とアルカリ土類金属塩の混合溶液で処理することによってラジウムを脱離させることができる。本発明のラジウム吸着剤は、これらの溶液で処理してもイオン交換樹脂と結合しているチタン及びジルコニウムの含水酸化物が安定に保たれることから溶出が極めて少なく、さらに吸着活性の低下もほとんどないため、繰り返し使用が可能であり、長期に渡り樹脂を入れ替える必要がなくなり、安定してラジウムを吸着除去することができる。
【００１８】
【実施例】
次に、本発明を実施例によって具体的に説明する。
実施例１
交換基の末端が水素型でポーラス型の強酸性陽イオン交換樹脂ＰＫ−２１２（三菱化学製）６００ｍＬを水とともに内径が３０ｍｍφのガラス製のカラムに充填し、１０００ｇ／ＬのＴｉＣｌ4 と１５０ｇ／ＬのＺｒＯＣｌ2 を含む水溶液３８０ｍＬを４００ｍＬ／分で２０時間循環した。このカラムをイオン交換水１８Ｌで水洗した後、樹脂をガラス製の容器に移し、イオン交換水５Ｌを加えて８５℃に加熱し、４時間攪拌を行った。その後、樹脂を水とともに内径が３０ｍｍφのガラス製のカラムに再充填し、１６０ｇ／Ｌの苛性ソーダ液２２５ｍＬを４００ｍＬ／分で２時間循環した後、イオン交換水１８Ｌで水洗することによりラジウム吸着剤（以下Ｒ１吸着剤という）を得た。このＲ１吸着剤のチタン及びジルコニウム含有量を蛍光Ｘ線法で求めたところ、それぞれ１２ｗｔ％、０．８ｗｔ％であった。
【００１９】
次に、このＲ１吸着剤を用いて、ラジウム含有水の処理を行った。
Ｒ１吸着剤３００ｍＬを水とともに内径が２０ｍｍφのガラス製のカラムに充填し、ｐＨが６．５で 226Ｒａを５Ｂｑ／Ｌ含有する溶液を流量２００ｍＬ／分（空間速度４０ｈ-1）で下降流で１５０時間通液し、処理水を２５時間毎に採取して処理水のラジウム濃度をエマネーション法で測定した。
その結果を表１に示す。
【００２０】
【表１】
表１から明らかなようにラジウムを５Ｂｑ／Ｌで含有する溶液を空間速度４０ｈ-1で通液したとき、ラジウムの破過濃度を０．０３７Ｂｑ／Ｌとすると、破過時間は１２５時間であった。
このラジウム吸着処理後のＲ１吸着剤に、２容量％のＨＣｌと１００ｇ／ＬのＭｇＣｌ2 を含む溶液１．５Ｌを１０ｍＬ／分で通液してラジウムを脱着させた。処理水を全量採取し、ラジウム脱着率及びチタン、ジルコニウムの溶出率を測定したところ、吸着したラジウムの９８％が脱着されており、チタンの溶出率は０．４％、ジルコニウムの溶出率は０．１％以下であった。
【００２２】
実施例２
実施例１でラジウムを吸・脱着したＲ１吸着剤３００ｍＬをイオン交換水９Ｌで水洗した後、水とともに内径が３０ｍｍφのガラス製のカラムに再充填し、１６０ｇ／Ｌの苛性ソーダ液１２２．５ｍＬを２００ｍＬ／分で２時間循環した後、イオン交換水９Ｌで水洗することにより吸着剤の再生を行った。
次に、このカラムにｐＨが６．５で 226Ｒａを５Ｂｑ／Ｌ含有する溶液を流量２００ｍＬ／分（空間速度４０ｈ-1）で下降流で１５０時間通液し、処理水を２５時間毎に採取して処理水のラジウム濃度を実施例１と同様にして測定した。
その結果を表２に示す。
【００２３】
【表２】
表２から明らかなようにラジウムを５Ｂｑ／Ｌで含有する溶液を空間速度４０ｈ-1で通液したとき、ラジウムの破過濃度を０．０３７Ｂｑ／Ｌとすると、破過時間は１２５時間であり、未使用の吸着剤と同じ性能を保持したままであった。
【００２５】
比較例１
交換基の末端が水素型でポーラス型の強酸性陽イオン交換樹脂ＰＫ−２１２、６００ｍＬを水とともに内径が３０ｍｍφのガラス製のカラムに充填し、１０００ｇ／ＬのＴｉＣＬ4 液３８０ｍＬを４００ｍＬ／分で２０時間循環した。このカラムをイオン交換水１８Ｌで水洗した後、樹脂をガラス製の容器に移し、イオン交換水５Ｌを加えて８５℃に加熱し、４時間攪拌を行った。その後、樹脂を水とともに内径が３０ｍｍφのガラス製のカラムに再充填し、１６０ｇ／Ｌの苛性ソーダ液２２５ｍＬを４００ｍＬ／分で２時間循環した後、イオン交換水１８Ｌで水洗することによりラジウム吸着剤（以下Ｒ２吸着剤という）を得た。このＲ２吸着剤のチタン含有量を実施例１と同様にして求めたところ、１０ｗｔ％であった。
次に、このＲ２吸着剤を用い、実施例１と同様にしてラジウム含有水の処理を行った。
その結果を表３に示す。
【００２６】
【表３】
このラジウム吸着処理後のＲ２吸着剤から実施例１と同様にしてラジウムを脱着させたところ、吸着したラジウムは９８％脱着されており、チタンの溶出率は０．５％であった。
このラジウムを吸・脱着したＲ２吸着剤を実施例２と同様にして再生した後、この再生したＲ２吸着剤を用い、実施例２と同様にしてラジウム含有水の処理を行った。
その結果を表４に示す。
【００２８】
【表４】
表４から明らかなようにラジウムを５Ｂｑ／Ｌで含有する溶液を空間速度４０ｈ-1で通液したとき、ラジウムの破過濃度を０．０３７Ｂｑ／Ｌとすると、通液初期から破過濃度を越える値となり、性能の低下が認められた。
以上の結果から明らかなように、本発明のラジウム吸着剤（Ｒ１吸着剤）は、鉱酸を用いて樹脂を再生した後でも優れたラジウム吸着能を有しているのに対して、チタンの含水酸化物のみを保持するラジウム吸着剤（Ｒ２吸着剤）では、再生処理によりラジウム吸着能が著しく低下する。
【００３０】
【発明の効果】
本発明のラジウム吸着剤は、ラジウム吸着能が高く、空気逆洗等の物理的な作用に対しても安定であり、さらに、チタン、ジルコニウムの含水酸化物を保持したままラジウムを脱着でき、ラジウム脱着処理後も優れたラジウム吸着能を示すので繰り返し使用が可能である。
また、本発明のラジウム吸着剤の製造方法によれば、このようなラジウム吸着剤を容易に製造することができる。
さらに、本発明のラジウム含有廃水の処理方法によれば、ラジウム含有廃水を効率よく処理することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a radium adsorbent that can efficiently adsorb and remove radium from radium-containing wastewater, and further relates to a method for producing the same, and a method for treating radium-containing wastewater using the same.
[0002]
[Prior art]
Radium is mainly produced in the process of uranium decay, and coexists with uranium in uranium ore in nature. Examples of such wastewater containing radium include wastewater generated from scientific laboratories, groundwater, and wastewater generated in connection with uranium mine development.
Radium has a long half-life and accumulates in the body when ingested in large amounts. It is said that osteosarcoma and leukemia are ill. The radium concentration in water is 3.0 Bq / Some offices are regulated to L or less and strictly regulated to 0.037 Bq / L or less by the safety agreement with the local community.
[0003]
As a method for treating such radium-containing wastewater, a method is known in which barium chloride or the like and sulfuric acid or a salt thereof are added to the wastewater, and coprecipitation is removed with the generated barium sulfate. However, this method has problems such as requiring a large space for a sedimentation basin, a filtration facility and the like, and generating a large amount of radium-containing solid waste.
Further, a method of selectively adsorbing and removing radium using an adsorbent is known. As an adsorbent, for example, JP-A 56-111043 discloses amorphous titanic acid as water, inorganic acid, inorganic An adsorbent bonded with at least one of a conjugate and an organic conjugate is disclosed in JP-A-3-56783 in which a polyvalent metal hydroxide such as iron or titanium is dispersed in a phenol resin. It is disclosed.
[0004]
[Problems to be solved by the invention]
However, these adsorbents are loosely bonded in a dispersed state of the titanium in the adsorbent, so they easily fall off by physical action such as air agitation, and the dropped titanium oxide loses pressure loss during water flow. In addition, the radium concentration that flows out with radium may not be able to be processed to a strict regulation value of 0.037 Bq / L or less, and because the radium adsorption rate is slow, if it is processed at a high flow rate, The amount of processing is greatly reduced, and therefore, there is a problem that it is necessary to perform regeneration frequently and the regeneration cost becomes high.
The present invention provides a radium adsorbent that is excellent in radium adsorption ability and can be repeatedly used by regenerating with mineral acid, a method for producing the same, and a method for treating radium-containing wastewater using the same. It is intended.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventors have found that a radium adsorbent obtained by chemically binding a hydrous oxide of titanium and zirconium to a strongly acidic cation exchange resin has an excellent radium adsorption ability. Furthermore, the present inventors have found that it exhibits excellent radium adsorption ability even after regeneration treatment with a mineral acid, and reached the present invention.
That is, the first invention comprises a strongly acidic cation exchange resin and a hydrated oxide of titanium and zirconium, and the hydrated oxide of titanium and zirconium is chemically bonded to the strongly acidic cation exchange resin. The feature is a characteristic radium adsorbent.
The second invention is the production of the above-mentioned radium adsorbent, characterized in that after a strong acidic cation exchange resin is contacted with an acidic aqueous solution of a titanium compound and an acidic aqueous solution of a zirconium compound, heat treatment and alkali treatment are performed. The summary of the method is as follows.
Furthermore, the third invention is summarized as a method for treating radium-containing wastewater, wherein the radium adsorbent is brought into contact with radium-containing wastewater to adsorb radium on the adsorbent.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
As the strongly acidic cation exchange resin in the present invention, for example, a matrix resin formed from a solid water-insoluble organic polymer in a normal state is used as a base, and anion exchange groups sufficient to control ion exchange from an aqueous solution are provided. And an anion exchange group having a sulfonic acid group, specifically, a phenol / formalin type, styrene type or acrylic type polymer having a sulfonic acid group as an exchange group. If a carboxylic acid-based weakly acidic cation exchange resin is used instead of a strong acid cation exchange resin, the amount of titanium and zirconium bonds decreases, and chelate having an iminodiacetic acid-based or aminomethylphosphonic acid-based exchange group When the resin is used, titanium and zirconium are bonded well, but there is a problem that the radium adsorption activity of the bonded titanium and zirconium is lowered and the radium adsorption ability is deteriorated.
[0007]
Strongly acidic cation exchange resins are commercially available that differ in physical and chemical performance depending on the production conditions. In the present invention, any of these resins can be used. However, it is preferable to use a porous resin as the polymer base because the adsorbent radium is adsorbed quickly. The porous strongly acidic cation exchange resin is a polymer having a porous physical structure. For example, the porosity of the gel type is less than 1%, and the porosity of the porous type is 5 to 5. It is said to be 30%, and can be produced by adding a pore-forming agent such as tributyl phosphate, isododecane or methyl isobutyl ketone in the polymerization stage.
[0008]
The amount of the hydrous oxide of titanium chemically bonded to the strongly acidic ion exchange resin in the adsorbent is preferably 2 wt% or more, more preferably 2 to 20 wt%, particularly 5 to 15 wt% as titanium. % Is preferred. Further, the amount of the hydrous oxide of zirconium is preferably 0.3 wt% or more as zirconium, more preferably 0.3 to 5 wt%, and particularly preferably 0.5 to 3 wt%. When the amount of titanium is less than the above range, the amount of radium adsorbed tends to decrease significantly. When the amount of zirconium is less than the above range, the radium adsorption activity of titanium is reduced when the resin is regenerated using mineral acid or the like. It tends to decrease. Further, since the adsorption rate decreases when the amount of zirconium exceeds the amount of titanium, the amount of zirconium is preferably less than the amount of titanium. In addition, since the exchange capacity of a general ion exchange resin is about 0.5 to 2.5 eq / L, the maximum amount of binding between the ion exchange resin and titanium is about 20 wt%.
[0009]
Next, the manufacturing method of the radium adsorbent of this invention is demonstrated.
First, in the present invention, an acidic aqueous solution of a titanium compound and an acidic aqueous solution of a zirconium compound are brought into contact with a strong acidic cation exchange resin of a proton type or a salt type such as sodium or potassium dispersed in water, and titanium and zirconium are contacted. Is chemically bound to a strongly acidic cation exchange resin. When contacting, an acidic aqueous solution of a titanium compound and an acidic aqueous solution of a zirconium compound may be brought into contact with each other, or an acidic aqueous solution (mixed solution) containing a titanium compound and a zirconium compound may be contacted. It is preferable to use a solution because the ratio of titanium and zirconium bonded to the resin can be easily adjusted.
[0010]
Such acidic aqueous solutions include, for example, titanium halide (TiX 3 , TiX 4 ), titanium sulfate (Ti (SO 4 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 ), etc. as titanium compounds, and zirconium. It can be prepared by dissolving zirconium oxychloride (ZrOCl 2 ), zirconium oxynitrate (ZrO (NO 3 ) 2 ) or the like as a compound in water.
[0011]
The amount of the acidic aqueous solution to be contacted is preferably such that the amount of titanium in the adsorbent is 2 to 20 wt%, so that the amount of titanium is 0.3 to 30 with respect to the total exchange amount of the strongly acidic cation exchange resin. An amount that provides a double equivalent is preferred. In addition, since the amount of zirconium in the adsorbent is preferably 0.3 to 5 wt%, the amount of zirconium is 0.1 to 3 times equivalent to the total exchange capacity of the strongly acidic cation exchange resin. Is preferred.
The concentration of titanium in such an acidic aqueous solution is not particularly limited, but when a low concentration aqueous solution is used, titanium ions are hydrolyzed and become insoluble, so that it is 0.25 g / L or more. Is preferred. Further, the zirconium concentration is not particularly limited.
[0012]
The contact method can be either a batch method in which a strong acidic cation exchange resin and an acidic aqueous solution are stirred or shaken, or a column method in which a strong acidic cation exchange resin is packed in a resin tower and an acidic aqueous solution is passed through. It is. When the batch method is used, it is preferable to stir or shake for 2 hours or more. When the column method is used, it is preferable to circulate the acidic aqueous solution because the acidic aqueous solution can be effectively used.
[0013]
If excess titanium compound and zirconium compound remain in the resin bonded with titanium and zirconium, insoluble hydrous titanium oxide and zirconium are generated by the subsequent alkali treatment, and separation from the resin is necessary. It is preferable to wash the resin with water to separate the excess titanium compound and zirconium compound from the ion exchange resin. Washing with water is usually performed using 30 times the resin volume.
[0014]
Next, the resin bonded with titanium and zirconium in this manner is subjected to heat treatment and alkali treatment.
Examples of the heat treatment method include a dry heat treatment method using a hot air dryer or the like, and a hydrothermal treatment method performed while heating in water. In the method using the dry heat treatment, when the temperature reaches 150 ° C. or higher, decomposition of the ion exchange resin starts, dropping of the exchange group and decomposition of the copolymer base occur. Therefore, the treatment is performed at 80 to 150 ° C. for 0.5 to 8 hours. It is more preferable to perform the treatment at 100 to 120 ° C. for 2 to 4 hours. Moreover, in the method by a hydrothermal treatment, it is preferable to process for 0.5 to 10 hours at 60-100 degreeC, and it is more preferable to process for 1 to 6 hours at 70-95 degreeC. By performing the heat treatment, the bond between the ion exchange resin and titanium and zirconium can be strengthened.
[0015]
The alkali treatment is to convert titanium and zirconium bonded to the resin into a hydrous oxide by bringing the resin into contact with an alkali agent. Examples of the alkaline agent used at this time include hydroxides and carbonates of alkali metals such as lithium, potassium and sodium, and hydroxides and carbonates of alkaline earth metals such as calcium, magnesium, strontium and barium. An aqueous solution may be mentioned, but an aqueous solution of an alkali metal hydroxide is preferred from the viewpoint of economy and operability. As a contact method, it can carry out by a batch method or a column method. As the usage-amount of an alkaline agent, 0.3 equivalent times or more of the total exchange amount of the strong acidic cation exchange resin used is preferable, and 0.5-2 equivalent times is more preferable.
The order of such heat treatment and alkali treatment is not particularly limited because the same adsorbent can be obtained from either operation.
[0016]
Next, the processing method of the radium containing wastewater of this invention is demonstrated.
In the radium adsorbent of the present invention, the hydrous oxides of titanium and zirconium are chemically and stably bonded to the ion exchange resin, and the amount of radium adsorbed is large and the adsorption rate is high. By contacting it, the radium-containing wastewater can be easily treated. As a method for contacting, either a batch method or a column method may be used, but a column method capable of taking advantage of a high adsorption rate is preferable. When this adsorbent is packed in a column and wastewater containing 5 Bq / L of radium is treated at a high flow rate with a space velocity of 40 h −1 , the adsorbent concentration when the breakthrough concentration of radium is 0.037 Bq / L Since the processing time until breakthrough is as long as about 125 hours, the regeneration interval becomes long, and the cost required for regeneration can be reduced.
[0017]
The adsorbent after adsorbing radium can be desorbed by treatment with a mineral acid such as hydrochloric acid or sulfuric acid or a mixed solution of mineral acid and alkaline earth metal salt. The radium adsorbent of the present invention has very little elution because the hydrous oxides of titanium and zirconium bonded to the ion exchange resin remain stable even when treated with these solutions, and further reduces the adsorption activity. Since there is almost no repetitive use, it is not necessary to replace the resin over a long period of time, and radium can be stably adsorbed and removed.
[0018]
【Example】
Next, the present invention will be specifically described with reference to examples.
Example 1
600 mL of a strongly acidic cation exchange resin PK-212 (manufactured by Mitsubishi Chemical) having a hydrogen type and a porous type at the end of the exchange group was packed into a glass column with an inner diameter of 30 mmφ together with water, and 1000 g / L TiCl 4 and 150 g / 380 mL of an aqueous solution containing L ZrOCl 2 was circulated at 400 mL / min for 20 hours. After this column was washed with 18 L of ion exchange water, the resin was transferred to a glass container, 5 L of ion exchange water was added, and the mixture was heated to 85 ° C. and stirred for 4 hours. Thereafter, the resin is refilled with water into a glass column having an inner diameter of 30 mmφ, 225 mL of 160 g / L of caustic soda solution is circulated at 400 mL / min for 2 hours, and then washed with 18 L of ion-exchanged water to wash the radium adsorbent ( (Hereinafter referred to as R1 adsorbent). The titanium and zirconium contents of this R1 adsorbent were determined by fluorescent X-ray method and found to be 12 wt% and 0.8 wt%, respectively.
[0019]
Next, this R1 adsorbent was used to treat radium-containing water.
R1 adsorbent (300 mL) was packed in a glass column with water diameter of 20 mmφ together with water, and the solution containing 5 Bq / L of 226 Ra at pH 6.5 was flowed downward at a flow rate of 200 mL / min (space velocity 40 h −1 ). The solution was passed for 150 hours, the treated water was collected every 25 hours, and the radium concentration of the treated water was measured by the emanation method.
The results are shown in Table 1.
[0020]
[Table 1]
As is apparent from Table 1, when a solution containing radium at 5 Bq / L was passed at a space velocity of 40 h −1 , the breakthrough time was 125 hours, assuming that the radium breakthrough concentration was 0.037 Bq / L. It was.
Radium was desorbed by passing 1.5 L of a solution containing 2 vol% HCl and 100 g / L MgCl 2 at 10 mL / min through the R1 adsorbent after the radium adsorption treatment. All of the treated water was collected and the radium desorption rate and the elution rate of titanium and zirconium were measured. As a result, 98% of the adsorbed radium was desorbed, the elution rate of titanium was 0.4%, and the elution rate of zirconium was 0. .1% or less.
[0022]
Example 2
After washing 300 mL of R1 adsorbent adsorbed and desorbed with radium in Example 1 with 9 L of ion-exchanged water, it was refilled into a glass column with an inner diameter of 30 mmφ together with water, and 200 mL of 122.5 mL of 160 g / L sodium hydroxide solution was added. After circulating for 2 hours at / min, the adsorbent was regenerated by washing with 9 L of ion exchange water.
Next, a solution containing 5Bq / L of 226 Ra at pH 6.5 was passed through the column at a flow rate of 200 mL / min (space velocity 40 h −1 ) for 150 hours in a downward flow, and treated water was passed every 25 hours. The radium concentration was collected and measured in the same manner as in Example 1.
The results are shown in Table 2.
[0023]
[Table 2]
As is apparent from Table 2, when a solution containing radium at 5 Bq / L is passed at a space velocity of 40 h −1 , the breakthrough time is 125 hours when the breakthrough concentration of radium is 0.037 Bq / L. The same performance as the unused adsorbent was retained.
[0025]
Comparative Example 1
600 mL of a strongly acidic cation exchange resin PK-212 having a hydrogen type and a porous type at the end of the exchange group is packed in a glass column with an inner diameter of 30 mmφ together with water, and 380 mL of 1000 g / L TiCL 4 solution is added at 400 mL / min. Circulated for 20 hours. After this column was washed with 18 L of ion exchange water, the resin was transferred to a glass container, 5 L of ion exchange water was added, and the mixture was heated to 85 ° C. and stirred for 4 hours. Thereafter, the resin is refilled with water into a glass column having an inner diameter of 30 mmφ, 225 mL of 160 g / L of caustic soda solution is circulated at 400 mL / min for 2 hours, and then washed with 18 L of ion-exchanged water to wash the radium adsorbent ( (Hereinafter referred to as R2 adsorbent). When the titanium content of this R2 adsorbent was determined in the same manner as in Example 1, it was 10 wt%.
Next, this R2 adsorbent was used to treat radium-containing water in the same manner as in Example 1.
The results are shown in Table 3.
[0026]
[Table 3]
When radium was desorbed from the R2 adsorbent after the radium adsorption treatment in the same manner as in Example 1, the adsorbed radium was 98% desorbed and the elution rate of titanium was 0.5%.
The R2 adsorbent that had absorbed and desorbed radium was regenerated in the same manner as in Example 2, and then the regenerated R2 adsorbent was used to treat radium-containing water in the same manner as in Example 2.
The results are shown in Table 4.
[0028]
[Table 4]
As is apparent from Table 4, when a solution containing radium at 5 Bq / L is passed at a space velocity of 40 h −1 , and the radium breakthrough concentration is 0.037 Bq / L, the breakthrough concentration is reduced from the beginning of the passage. The value was exceeded, and a decrease in performance was observed.
As is clear from the above results, the radium adsorbent (R1 adsorbent) of the present invention has an excellent radium adsorbing ability even after the resin is regenerated using mineral acid, whereas titanium With a radium adsorbent (R2 adsorbent) that retains only the hydrous oxide, the radium adsorbability is significantly reduced by the regeneration treatment.
[0030]
【The invention's effect】
The radium adsorbent of the present invention has high radium adsorption ability, is stable to physical action such as backwashing with air, and is capable of desorbing radium while retaining titanium and zirconium hydrous oxides. Even after desorption treatment, it exhibits excellent radium adsorption ability and can be used repeatedly.
Moreover, according to the manufacturing method of the radium adsorbent of this invention, such a radium adsorbent can be manufactured easily.
Furthermore, according to the method for treating radium-containing wastewater of the present invention, radium-containing wastewater can be treated efficiently.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06971498A JP3831107B2 (en) | 1998-03-19 | 1998-03-19 | Radium adsorbent, method for producing the same, and method for treating radium-containing wastewater using the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP06971498A JP3831107B2 (en) | 1998-03-19 | 1998-03-19 | Radium adsorbent, method for producing the same, and method for treating radium-containing wastewater using the same |
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| Publication Number | Publication Date |
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| JPH11262661A JPH11262661A (en) | 1999-09-28 |
| JP3831107B2 true JP3831107B2 (en) | 2006-10-11 |
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| WO2021002275A1 (en) * | 2019-07-02 | 2021-01-07 | 日本メジフィジックス株式会社 | METHOD FOR PURIFYING 226Ra-CONTAINING SOLUTION, METHOD FOR PRODUCING 226Ra TARGET AND METHOD FOR PRODUCING 225Ac |
| CN113694874B (en) * | 2021-09-02 | 2022-07-12 | 南京大学 | Titanium-zirconium adsorbent and preparation method and application thereof |
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