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論文

Effect of the central frames and substituents attached to N atoms on extraction ability of podand-type extractants

佐々木 祐二; 北辻 章浩; 須郷 由美; 津幡 靖宏; 鈴木 智也; 木村 貴海; 森田 泰治

Proceedings of 20th International Solvent Extraction Conference (ISEC 2014), p.431 - 435, 2014/09

ポダンド系を含む8種の異なる抽出剤を開発し、アクチノイド元素に対する分配比を比較した。抽出に関して化合物の中心骨格が大きく影響し、この中でジグリコールアミド(DGA)化合物が最も高い分配比を示した。加えて、DGA化合物の窒素原子に結合する置換基の効果について検討した。立体障害や水素結合などを持つような化合物によるアクチノイドの分配比は低いことが示唆された。

論文

Transient extraction behavior analysis of plutonium in reprocessing

内山 軍蔵; 阿部 仁

Proceedings of 20th International Solvent Extraction Conference (ISEC 2014), p.1167 - 1172, 2014/09

再処理分離工程の抽出廃液貯槽における臨界事故の発生シナリオkの検討に資するため解析研究及び実験研究を行った。解析研究では、抽出解析コードESSCARを用いてPuの過渡抽出挙動と還元液の流量などのプロセスパラメーターとの関係を調べた。Pu洗浄工程の有機相及び水相中のPu濃度は還元液の流量の異常減少とともに上昇することがわかった。実験研究では、Pu抽出挙動に影響を及ぼす亜硝酸及びDBPの抽出挙動を$$gamma$$線照射条件下のミキサセトラ型抽出器を用いて測定した。実験の結果、亜硝酸の有機相及び水相の各濃度は それぞれ1$$times$$10$$^{-4}$$M, 2$$times$$10$$^{-5}$$Mであった。また、DBPの有機相及び水相の各濃度は それぞれ5$$times$$10$$^{-4}$$M, 8$$times$$10$$^{-5}$$Mであった。

論文

Intramolecular cooperative effect of a macrocyclic receptor bearing $$beta$$-diketone fragments on the extraction of strontium into an ionic liquid

岡村 浩之; 長縄 弘親; 井村 久則*; 下条 晃司郎

Proceedings of 20th International Solvent Extraction Conference (ISEC 2014), p.1046 - 1051, 2014/09

The macrocyclic receptor (H$$_{2}$$$$beta$$DA18C6) composed of diaza-18-crown-6 and two molecules of 4-acyl-5-pyrazolone was synthesized for the extraction of Sr(II) into ionic liquids (ILs). The extraction performance of H$$_{2}$$$$beta$$DA18C6 in 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C$$_{n}$$mim][Tf$$_{2}$$N]) was remarkably enhanced by the intramolecular cooperative effect compared with that in chloroform. From the equilibrium analysis, the neutral complex, Sr($$beta$$DA18C6), was extracted into [C$$_{2}$$mim][Tf$$_{2}$$N]. The shortening of the average Sr-O distance in the Sr-$$beta$$DA18C6 complex in the IL was revealed from the extended X-ray absorption fine structure spectroscopy. This is the cause of the intramolecular cooperative effect in the IL.

論文

Comprehensive extraction separation study of metal ions using $$N,N$$-dioctyldiglycolamic acid DODGAA

下条 晃司郎; 長縄 弘親

Proceedings of 20th International Solvent Extraction Conference (ISEC 2014), p.1052 - 1057, 2014/09

We report on the feasibility of $$N,N$$-dioctyldiglycolamic acid (DODGAA) as a novel extractant for selective separation of varioius metal ions in industrial solvent extraction processes. DODGAA can be synthesized simply and readily in a single step. This extractant enables the quantitative partitioning of all rare-earth metal ions (RE$$^{3+}$$) from moderately acidic solutions, while showing selectivity for heavier lanthanides, and provides remarkably high extraction separation performance for RE$$^{3+}$$ compared with commercial extractants. In fact, the mutual separation abilities of DODGAA for light lanthanides are higher than those of organophosphorus extractants. Furthermore, we found that DODGAA is useful for the separation of RE$$^{3+}$$ from base metal ions. For other metal ions, DODGAA posesses great potential for the selective recovery of a noble metal ion Pd(II) from Pt(IV) and Rh(III), the removal of toxic metai ions, such as Hg(II) and Pb(II), and the recycling of In(III) from the group-13 elements.

口頭

Cesium separations with crown ether derivatives containing aromatic groups

宮崎 有史; 小林 徹; 鈴木 伸一; 塩飽 秀啓; Awual, M. R.; 岡本 芳浩; 元川 竜平; 矢板 毅

no journal, , 

We have developed crown ether derivative compounds for cesium separation, and furthermore studied the relationship between structure and complexation ability for Cs. In this present study, the developed benzo-crown ethers were simple structures, but relatively high Cs selectivity than K was observed. The DFT calculation result suggested that electron donation from aromatic ring would also enhance Cs selectivity and we are re-considering the model for Cs selectivity. The other coordination properties of these crown ether derivatives with Cs were studied by NMR, UV-Vis spectroscopy and so on, and will be presented in this talk.

口頭

Lanthanide separation by functionalized mesoporous silica-transportation and coordination

Awual, M. R.; 小林 徹; 塩飽 秀啓; 宮崎 有史; 元川 竜平; 鈴木 伸一; 岡本 芳浩; 矢板 毅

no journal, , 

A novel separation material for lanthanide was designed using O and N donor ligand immobilized mesoporous silica. The specific lanthanide transportation based on solution pH, sorption capacity, and recovery by stripping agents was performed. The interaction mechanism and lanthanide coordination after adsorption of specific Ln$$^{3+}$$ at the solid interface have been studied by EXAFS. The proposed materials possessed sufficient loading and releasing capacities for specific lanthanide in repeated processes after sorption-recovery operations. The successful development of potential materials can serve as promising applications and time- and cost-effective tool for selective lanthanide sorption and recovery in separation technologies on an industrial scale.

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