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Matsumura, Tatsuro; Takeshita, Kenji*
ACS Symposium Series, 933, p.261 - 273, 2006/07
Three TPEN isomers with different positon of nitrogen donor in pyridyl groups, t2pen, t3pen and t4pen, were synthesized and the extraction separation of Am(III) and Eu(III) with these ligands and a fatty acid, decanoic acid, was investigated. All isomers were similar in the complexation in the aqueous phase, such as the protonation and the formation of metal complex, however, they showed different extraction behavior of Am and Eu. The synergistic extraction effect for Am was observed for t2pen and the high separation factor about 100 was measured, when 1:2. The value is comparable to that for the extraction system with a famous nitrogen-donor extractant, BTP. On the other hand, the extractability of other isomers was very low and no separation of Am and Eu was observed. Only t2pen, in which nitrogen donor in pyridyl groups is positioned in the vicinity of the skeletal structure (N-C-C-N structure) of ligand, is available for the extraction separation of Am.
Mirvaliev, R.*; Watanabe, Masayuki; Matsumura, Tatsuro; Tachimori, Shoichi*; Takeshita, Kenji*
Journal of Nuclear Science and Technology, 41(11), p.1122 - 1124, 2004/11
Times Cited Count:20 Percentile:76.55(Nuclear Science & Technology)Transmutation is a technology aimed to reduce HLW from reprocessing process. Minor actinides in the HLW will be converted to short-lived nuclides. However, lanthanides in HLW adversely affects on the efficiency of the transmutation. It is well known that separating An(III) and Ln(III) is very difficult because of their similarity of chemical properties. Therefore, the separation is one of the essential subjects to establish the transmutation technology. Considerable efforts have been devoted to the development of new extractants for the separation. N,N,N',N'-tetrakis(2-methylpyridyl)ethylenediamine (TPEN) demonstrates 100-fold preference for Am(III) over Ln(III) between stability constants with the ions in the aqueous phase. We have reported that Am(III) was selectively extracted from the aqueous phase containing Ln(III) by TPEN in nitrobenzene system and synergistic system with TPEN and D2EHPA in octanol. This work presents our recent results that Am(III) is separated from Eu(III) by a synergistic extraction system with TPEN and decanoic acid diluted with 1-octanol.
Watanabe, Masayuki; Mirvaliev, R.*; Tachimori, Shoichi; Takeshita, Kenji*; Nakano, Yoshio*; Morikawa, Koshi*; Chikazawa, Takahiro*; Mori, Ryohei*
Solvent Extraction and Ion Exchange, 22(3), p.377 - 390, 2004/06
Times Cited Count:32 Percentile:65.75(Chemistry, Multidisciplinary)The synergistic extraction with N,N,N',N'-tetrakis(2-methylpyridyl)-ethylenediamine (TPEN) and di(2-ethylhexyl)phosphoric acid (D2EHPA) demonstrates a good selectivity for Am(III) over macro amount of Ln(III) in 1-octanol. The maximum apparent separation factor, which is defined as the ratio of the distribution ratio of Am(III) to that of Eu(III), is ca. 80 while the molar fraction between D2EHPA and TPEN is 2.0. This ratio is corresponding to the result of the spectrophotometric titration, which indicates that TPEN and D2EHPA form an aggregate in 1-octanol and two D2EHPA molecules coordinate to Eu(III) TPEN complex, [Eu(TPEN)]. In the present study, the association of D2EHPA and TPEN is one of the most important factors for the synergistic extraction and the complexation of TPEN and D2EHPA with Eu(III).
Watanabe, Masayuki; Mirvaliev, R.*; Tachimori, Shoichi; Takeshita, Kenji*; Nakano, Yoshio*; Morikawa, Koshi*; Mori, Ryohei*
Chemistry Letters, 31(12), p.1230 - 1231, 2002/12
Times Cited Count:40 Percentile:73.3(Chemistry, Multidisciplinary)Encapsulative semi-podand type ligand, N, N, N', N' #8211; tetrakis(2-methylpyridyl)ethylenediamine (TPEN) gives good selectivity of Am(III) over trivalent lanthanide by solvent extraction. This is the first robust extraction system which can separate Am(III) from trivalent lanthanide.
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JAERI-M 6673, 13 Pages, 1976/08
no abstracts in English
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JAERI-M 5305, 18 Pages, 1973/06
no abstracts in English
Kaneko, Masashi; Watanabe, Masayuki; Matsumura, Tatsuro
no journal, ,
In Japan Atomic Energy Agency, the extraction reagents for the inter- and intragroup separation of mainor-actinides from lanthanides have been developed in order to construct the partitioning and transmutation process. We aim to reveal the separation mechanism using various extraction materials at a molecular level and to design the novel extraction reagents. In this study, we design a novel TPEN-type extraction reagent in which carbonyl donors are introduced and predict its separation performance of Am(III) from Eu(III) using density functional calculations. We modeled molecular complexes by referring single crystal structures and compared the stability between Eu(III) and Am(III) complexes. As a result, the relative stability of Am complex to Eu complex increased and its separation factor was improved by an order from five to twenty compared to the prediction value by non-substituent TPEN ligand.