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岡村 浩之
日本イオン交換学会誌, 35(1), p.1 - 8, 2024/01
イオン液体は従来の分子性液体とは大きく異なる特殊な性質を有することから、新たな機能性媒体としてさまざまな分野で注目されている。溶媒抽出における抽出媒体としてイオン液体を用いた場合は、"液状イオン交換体"としても働くため、従来の有機溶媒系よりも優れた抽出分離能を示すことが期待される。著者は、このようなイオン液体の特性に着目し、高性能溶媒抽出系の開発を目指して、イオン液体を抽出媒体とした金属イオンの抽出分離に関する研究を行ってきた。本稿では、金属イオン抽出におけるイオン液体の溶媒特性評価、イオン液体系での協同効果による希土類金属の分離、大環状抽出剤の開発とイオン液体に抽出された金属錯体の構造解析について紹介する。
大西 貴士; 小山 真一; 三村 均*
日本イオン交換学会誌, 31(3), p.43 - 49, 2020/10
Hybrid microcapsules (H-MCs) are being development for the column separation of Cs from high-level radioactive liquid waste (HLLW). In this paper, adsorption behavior of H-MCs has been evaluated by a batch method in single-element solution and a spent fuel solution prepared from irradiated MOX fuel. Distribution coefficients (
s) of various metal ion including Cs were determined for three types of H-MCs (AMP-SG (silica gel enclosing ammonium molybdophosphate), AMP-ALG (calcium alginate gel enclosing ammonium molybdophosphate) and AWP-ALG (calcium alginate gel enclosing ammonium tungstophosphate)) in the spent fuel solution. The three types of H-MCs exhibited higher s for Cs than those for the other elements in spent fuel solution. The difference of for the specific element (Cs) and the other elements was larger than one order of magnitude. Therefore, chromatographic separation of Cs in the spent fuel solution using a column packed with H-MCs is promising. It was the same tendency between the spent fuel solution and the single-element solution that the value for Cs of AWP-ALG was the largest followed by that of AMP-ALG and that of AMP-SG. Thus, the mechanism of adsorption of Cs onto these H-MCs would not be changed in the presence of FPs and MAs. Therefore, these types of H-MCs can be effective for separation of Cs in the spent fuel solutions.
-P adsorbent on extraction chromatography process渡部 創; 佐野 雄一; 三田 修平*; 桜井 翔太*; 新井 剛*
日本イオン交換学会誌, 30(1), p.8 - 16, 2019/01
In order to optimize operability of the adsorbents in the extraction chromatography system and to enhance the performance of the adsorbent, CMPO/SiO-P adsorbents with various pore and particle sizes were prepared, and characteristics of the adsorbents were evaluated through distribution coefficient, adsorption isotherm, adsorption rate, and breakthrough/elution behavior. Adsorption capacity was dominated not by the structure of the adsorbent but by amount of the extractant impregnated. The adsorbent with the largest pore size were revealed to show quick elution with short tail. Enlargement in the pore size must be one of the most effective improvements of the adsorbents to enhance the adsorption/elution performance. Adsorbent with particle size of more than 200 
m formed channeling or voids inside the bed. They are suspected to lead slow adsorption/elution behavior, and smaller adsorbents must be desirable in the respect of performance of the column.
渡部 創; 鈴木 英哉; 後藤 一郎*; 小藤 博英; 松村 達郎
日本イオン交換学会誌, 29(3), p.71 - 75, 2018/09
Chemical compounds containing scandium (Sc) are widely applied to various fields such as catalysts, alloys, lamps and etc. Sc is found in mineral ore, and it is necessary to develop efficient Sc separation and recovery technology for the industrial applications. So far, solvent extraction based processes were proposed as promising Sc recovery procedures. Our group has found that hexaoctyl nitrilotriacetic acid triamide (HONTA) has strong affinity to Sc. In this study, applicability of the extraction chromatography technology for the selective Sc recovery was experimentally evaluated through batch-wise adsorption/elution studies and column separation experiments.
下条 晃司郎
日本イオン交換学会誌, 28(1), p.1 - 10, 2017/01
本総説は平成28年度日本イオン交換学会進歩賞の研究内容をまとめたものである。産業廃棄物などに含まれる有用金属の分離回収および有害金属の除去・検出を効率的に行うには、高い選択性を有する金属分離試薬の開発が必要である。我々は新規金属分離試薬として、ジグリコールアミド酸(DGAA)型配位子を開発した。この試薬はアミド基とカルボン酸をエーテル鎖で連結した三座配位構造を有し、市販の配位子より優れた金属分離能をもつ。また、1ステップで簡便に合成が可能でコストパフォーマンスにも優れている。本稿では、DGAA型配位子の56種の金属イオンに対する抽出特性、希土類金属の抽出分離、および有害金属の除去について解説する。さらに、DGAA型配位子と金結合性ペプチドを融合した配位子融合ペプチドを用いて、DGAA固定化金ナノ粒子をワンポットで合成する手法を開発し、有害金属イオンを色の変化で高感度に検出できるイオン交換比色センサーに展開したので紹介する。
名越 航平*; 新井 剛*; 渡部 創; 佐野 雄一; 竹内 正行; 佐藤 睦*; 及川 博史*
日本イオン交換学会誌, 28(1), p.11 - 18, 2017/01
抽出クロマトグラフィーによる高レベル放射性廃液からのマイナーアクチノイド分離回収プロセスへの適用が期待される含浸吸着材の改良を目的として、含浸吸着材の基体として用いる多孔質シリカ粒子に種々の表面処理を施すことで表面極性を変化させたTODGA含浸吸着材を作製し、硝酸水溶液中におけるNdの吸着溶離挙動を評価した。多孔質シリカ粒子の表面極性を変化させることで吸着分配係数、吸着速度、溶離性能のいずれも顕著に変化することを確認した。
柴田 卓弥; 瀬古 典明; 天田 春代; 笠井 昇; 佐伯 誠一; 保科 宏行; 植木 悠二
日本イオン交換学会誌, 26(1), p.9 - 14, 2015/01
It is important task for recovering of Cs from the contaminated area caused by the accident at the Fukushima Daiichi Nuclear Power Station. We developed a highly efficient Cs adsorbent by radiation grafting of ammonium 12-molybdophosphate (AMP) and crosslinking of grafted chains with a suitable crosslinker at the same time. As a result of the optimizaion, the Cs adsorbent with 1 mol% of polyethylene glycol dimethacrylate satisfied the specification as a water purifier. The resultant grafted Cs adsorbent could work to maintain the highly performance of Cs removal in the standard pH range for drinking water (from pH 5.8 to 8.6) and even in the presence of coexisting ions such as K, Ca, Mg, and Na.
大西 貴士; 小山 真一; Masud, R. S.*; 河村 卓哉*; 三村 均*; 新堀 雄一*
日本イオン交換学会誌, 25(4), p.220 - 227, 2014/11
環境負荷低減および資源有効利用を目的として、原子力機構と東北大学では高レベル放射性廃液中に含まれるCs, Pd, TcおよびMoを高純度で回収するための技術開発を実施している。その一環として、新規に合成した吸着剤(高機能性キセロゲル)を用いて、模擬高レベル放射性廃液(コールド試薬を用いて調製した溶液)中に含まれるCs, Pd, Re(Tcの代替元素)およびMoを、カラム法により選択的に分離できることを見出している。一方で、照射済燃料から調製され放射性元素を含む溶液を用いたカラム試験は実施されていない。よって、本研究では、照射済燃料を酸溶解して照射済燃料溶解液を調製し、その中に含まれるCs, Pd, TcおよびMoを、高機能性キセロゲル充填カラムに吸着/溶離させることを試みた。その結果、照射済燃料溶解液中のCs, Pd, TcおよびMoを吸着/溶離させる条件を見出した。さらに、Tcについては選択的に分離することに成功した。
佐伯 誠一; 柴田 卓弥; 保科 宏行; 植木 悠二; 笠井 昇; 瀬古 典明
日本イオン交換学会誌, 25(4), p.170 - 175, 2014/11
After Fukushima Daiichi Nuclear Power Plant accidents, a lot of contaminated wastes have been produced by decontamination works at contaminated areas around Fukushima prefecture, Japan. At some temporary storage sites, it was found that contaminated leaching water was accumulated under stacks of contaminated "plant" wastes. To handle the wastes and the solution properly, decontamination tests of the leaching water were examined with molybdophosphate type cesium adsorbents synthesized by radiation-induced grafting method. At batch adsorption tests, 75% of radioactive cesium was successfully removed with cesium adsorbents. At column adsorption tests, radioactivity concentration of the leaching water could be reduced under provisional limit value up to around 500 times volume as large as an adsorbent volume. For development of volume reduction method of contaminated plant wastes, radioactive cesium extraction tests from the wastes and removal tests from the extracts were executed using contaminated oil cakes of sunflower seeds as a model of contaminated plant wastes. As a result, 65% of radioactive cesium was successfully extracted from the oil cakes to liquid phase, and more than 65% of radioactive cesium could be collected from the extract by grafted cesium adsorbents. These results showed a possibility of an application of these processes to volume reduction method for contaminated plant wastes.
林 菜月*; 保科 宏行; 天田 春代; 山延 健*; 瀬古 典明
日本イオン交換学会誌, 25(4), p.105 - 108, 2014/11
A fibrous phosphoric acid adsorbents for scandium were synthesized by radiation graft polymerization of glycidyl methacrylate (GMA), subsequent chemical modification, and direct grafting with a phosphoric monomer having both vinyl and phosphoric groups onto a polypropylene coated by polyethylene nonwoven fabric. The resultant grafted fibrous phosphoric acid adsorbent (HMP-g) having long side grafted chains has high affinity for scandium (Sc) ions even under the coexistence with Fe ion. The breakthrough capacity for Sc of 0.5 ppm with Fe coexistence was 10.9 mol-Sc per kg-adsorbent for the GMA derivative phosphoric adsorbent, and 17.8 mol-Sc per kg-adsorbent for HMP-g, respectively.
保科 宏行; 笠井 昇; 天田 春代; 高橋 牧克*; 田中 和也*; 瀬古 典明
日本イオン交換学会誌, 25(4), p.248 - 251, 2014/11
An adsorbent for Scandium (Sc) recovery was developed with radiation-induced graft polymerization of phosphoric acids that have a high affinity for Sc onto polyethylene fabrics. The adsorption performance of Sc was evaluated with the Sc adsorption equipment, consisting of 155 mm internal diameter columns and a pump that were set up near Yukawa River in Kusatsu town. To achieve a practical use of Sc recovery, the adsorbent requires repeated use with maintaining its efficiency in terms of cost reduction. So, the reusability of the adsorbent was investigated by repeating adsorption and elution. The breakthrough curves of Sc adsorption showed similar behavior in all tests. The adsorbed Sc from the 19th adsorption test was 56 mg, which was comparable capacity to the average amount of the adsorbed Sc during the 19 tests. These results indicated that the adsorbent was used more than 19 times with maintaining high adsorption performance of Sc.
天田 春代; 高橋 牧克*; 保科 宏行; 瀬古 典明
日本イオン交換学会誌, 25(4), p.109 - 113, 2014/11
A large amount of arsenic waste solution which was dissolved in neutral aqueous media, was generated from the manufacturing process of gallium arsenide component in semiconductor industry. As for arsenic removal, an adsorbent was developed by radiation graft polymerization and subsequent chemical modification with N-methyl-D-glucamine (NMDG) as a functional group. Furthermore, the grafting and the modification were carried out using water based solvent instead of organic solvent in view of an environmental emission and a working environment. The solvents were comprised of water and surfactant, and the adsorption performances compared with a conventional method synthesized in 1,4-dioxane of organic solvent. Total amount of arsenic for arsenic(III) and arsenic(V) at pH 6.5 were 3.2 times and 2.1 times higher than our previous fibrous adsorbent. From the pH dependency studies, the developed grafted adsorbent gave high removal ratio in a neutral media area for both arsenic species. Breakthrough capacities in the column mode tests for arsenic(III) and arsenic(V) were 0.3 and 18 mg/g at pH 6.5, respectively.
植木 悠二; 佐伯 誠一; 瀬古 典明
日本イオン交換学会誌, 25(4), p.99 - 104, 2014/11
The dynamic adsorption/elution properties of an ethyl p-styrenesulfonate (EtSS)-based fibrous graft adsorbent having sulfonic acid (SO
H) groups were evaluated by column-mode adsorption/elution tests for various cations. The EtSS-based fibrous graft adsorbent could work to capture various cations rapidly even under high flow rate conditions, compared with a commercial granular resin. The reason for this difference of adsorption rates was thought to be that the target ions were easily and rapidly transported near the SOH groups of graft chains by fluid convection. The affinity order of the fibrous graft adsorbent for cations depended on the cationic size and valence. It was found that the EtSS-based fibrous graft adsorbent preferentially adsorbed more multiply-charged cations having a larger cationic radius. The adsorbed cations could be easily eluted and concentrated by 1 M HNO aqueous solution, and the recovery of each cation was reached over 90%. Based on the above results, it was found that the EtSS-based fibrous graft adsorbent could be available as a sophisticated metal adsorbent in the industrial processes.
山田 裕久*; 横山 信吾*; 渡部 雄二郎*; 鈴木 正哉*; 鈴木 伸一; 八田 珠郎*
日本イオン交換学会誌, 25(4), p.207 - 211, 2014/11
We investigate the Cs-adsorption behavior of weathered biotites collected from Domiki, Mankei, Tozawa, and Yatsuzaku (in Fukushima) by changing the initial concentration of Cs in a solution. The degree of weathering of the samples increased in the following order: Domeki sample 
Tozawa Mankei Yatsuzaku. A characteristic feature of the Domeki sample was distortion of the biotite layer. The Tozawa sample had an even greater degree of distortion of the biotite layer. In the Mankei sample, hydrobiotite and randomly interstratified biotite-vermiculite were observed with distorted biotite. The Yatsuzaku sample contained vermiculite with hydrobiotite and distorted biotite. The Cs adsorption ratio was associated with the initial Cs concentration of the solution. The Cs adsorption ratio of samples in an initial solution of 1 to 100 ppm Cs was about 99%; it decreased with increasing Cs concentration in the solution. Dependency of Cs adsorption behavior on the degree of weathering of biotite was clearly observed in the Cs concentration range of 300 to 1000 ppm. With increasing degree of weathering, the rate of decrease in Cs adsorption ratio with increasing initial Cs concentration in the solution became slower and the maximum amount of Cs adsorbed by the sample increased. These results confirm that weathered phyllosilicates, vermiculite, interstratified biotite-vermiculite, and distorted biotite play important roles in Cs adsorption.
瀬古 典明; 玉田 正男
日本イオン交換学会誌, 23(2), p.51 - 58, 2012/05
放射線の高エネルギーを利用して化学反応を開始させる加工技術の一つである放射線グラフト重合は、既存の材料の形状や特性を生かしながら、目的とする機能を付与できる。本技術を駆使して、既存の高分子材料から水処理捕集材料を作製する技術開発を進め、新規な技術の実用化を目指し、さまざまな可能性を生み出した。本稿では、工業化に不可欠である生産コストの低減化、環境に優しい捕集材等の開発など、実用化や水環境における環境浄化、資源確保のような実用化研究を展開した成果について述べる。
三村 均*; 山岸 功
日本イオン交換学会誌, 23(1), p.6 - 20, 2012/02
東日本大震災により発生した福島第一原子力発電所事故においては、海水等冷却材の原子炉注入により、原子炉及びタービン建屋内の地下の溜まり水や、敷地内のトレンチなどに放射性物質を多く含んだ数万トン規模の高レベル汚染水が発生し、作業障害や環境汚染を起こしており、今後20万トン以上になると予想されている。2011年12月の時点で、循環注水冷却システムにより冷温停止が達成されているが、固体廃棄物(ゼオライト,不溶性フェロシアン化物スラッジ,結晶性シリコチタネート(CST))の処理及び処分は未定である。特に、汚染水中のセシウムの高除染用吸着剤として使用されている不溶性フェロシアン化物及び結晶性シリコチタネート(CST)の処理・処分に関しては、過去にもほとんど実績がないことから、今後の重要な課題となっている。本稿では、循環注水冷却システムの構成と進捗状況、及びセシウムの高除染用吸着剤としての不溶性フェロシアン化物及びCSTの物性及びCsに対する選択的な吸着特性について紹介し、これら固体廃棄物の処理・処分及び今後の課題について述べる。
下条 晃司郎; 後藤 雅宏*
日本イオン交換学会誌, 22(2), p.65 - 72, 2011/06
イオン液体は水や有機溶媒と異なる特徴を持つため、第3の液体として注目を浴びている。われわれはイオン液体の特異的な性質に注目し、イオン液体を抽出媒体とした液-液抽出法の開発を重ねてきた。本稿では環状化合物のサイズ認識を利用したイオン液体-水二相系における金属イオン及びタンパク質の抽出について解説する。さらに、イオン液体に抽出されたタンパク質を生体触媒反応へ応用し、イオン液体の生体触媒反応場としての可能性についても議論する。
和田 剛*; 石原 量*; 三好 和義*; 梅野 太輔*; 斎藤 恭一*; 浅井 志保; 山田 伸介*; 廣田 英幸*
日本イオン交換学会誌, 22(2), p.47 - 52, 2011/01
無機イオンを分析する際には、ターゲットとなるイオンの濃縮や精製が必要となる。これらの操作を迅速に行うためには動的吸着容量が大きいことが有利である。本研究では、架橋した高分子鎖を多孔性高分子の細孔表面へ修飾することにより、動的吸着容量に優れた分離材料の開発を目指した。基材には細孔径1mのポリエチレン製多孔体を採用し、放射線グラフト重合によってイミノ二酢酸基を持つ架橋高分子鎖を付与した。本材料では、多孔体細孔表面に付与した高分子鎖へ効率よくターゲットが接触でき、さらに、架橋することによって、イミノ二酢酸基に捕捉されたターゲットの高分子鎖相内における拡散が抑制され、非架橋型の多孔体に比べて動的吸着容量が向上する。イミノ二酢酸基だけでなく、イオン交換基の場合でも、架橋によって同様の効果が期待される。
保科 宏行; 瀬古 典明; 植木 悠二; 玉田 正男; 弥富 洋介
日本イオン交換学会誌, 21(3), p.153 - 156, 2010/09
The adsorbent was prepared by radiation induced graft polymerization of glycidyl methacrylate onto nonwoven polyethylene fabric in aqueous medium, and following chemical modification with N-methyl-D-glucamine. The adsorbents were packed into the column, 10 cm in internal diameter. The volume of adsorbent in column was 2,000 cm
. The column was set into the adsorption equipment which consisted of pump, pre-filters and a fraction collector. The groundwater was pumped up from neutralization tank and was 1.2 ppm of boron concentration. After removed of in/organic compound by pre-filters, the groundwater was pumped into the column at various flow rates. As a result, the bed volume (BV) at breakthrough point were 1,400 and 1,250 at space velocity (SV) 50 and 100 h
, respectively. These values correspond to 0.7 and 0.5 mmol/g-adsorbent. However, the BV at breakthrough point significant decreased at SV 200 h. In the case of SV 100 h, the adsorption equipment with the graft adsorbent can treat to remove boron from 4,800 liters of groundwater a day.
Phiriyatorn, S.*; 保科 宏行; 瀬古 典明; 玉田 正男
日本イオン交換学会誌, 21(3), p.157 - 160, 2010/09
An adsorbent containing hydroxamic acid groups was synthesized by radiation-induced graft polymerization of methyl acrylate (MA) onto nonwoven fabric composed of polyethylene-coated polypropylene fiber. Graft polymerization was carried out in emulsified MA solution containing sodium dodecyl sulfate as an emulsifier in the presence of water. Conversion of the ester groups in the grafted MA moiety into the hydroxamic groups was performed by treatment with an alkaline solution of hydroxylamine. The adsorbent containing hydroxamic acid groups was investigated. The adsorbent (approximately 0.01g) can adsorb 99% of U, 99% of V, 97% of Cd, and 97% of Pb at pH, 5, 4, 7, and 6 respectively after contacted with 100 ml of 100 ppb metal solution for 24 hour. The breakthrough capacities were 1000, 1100, 5300, and 7600 bed volume for Cd, V, U, and Pb, respectively with 100 ppb metal solution at the space velocity of 200 h. These values correspond to 0.006, 0.013, 0.014, and 0.022 mmol/g-adsorbent. The selectivity for metal ions of hydroxamic acid type adsorbent was Pb 
U V Cd.
