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Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*
Analytical Sciences, 39(9), p.1575 - 1583, 2023/09
Times Cited Count:0 Percentile:0(Chemistry, Analytical)Extraction of Rh from HCl can be performed by NTAamide(C6) (hexahexyl-nitrilotriacetamide) and other related compounds into n-dodecane. We use ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh behave as anion in hydrochloric acid and the tertiary nitrogen atom in extractant may be protonated to produce the quaternary amine in acidic condition. From the present work, the maximum distribution ratio of Rh(III) is 16. The D(Rh) values are changeable during preparation of the aqueous solutions because different Rh-Cl-HO complexes are formed in HCl media and show the slow exchange rate between Cl and HO. Using the UV spectrum, Rh-chloride solution having the peak of spectrum at 504 nm can be extracted effectively, where RhCl(HO) and RhCl(HO) exist mainly from DFT calculation. Stoichiometry of one-one complex of Rh and NTAamide is obtained from slope analysis, and 85 mM of concentrated Rh ion can be extracted.
Sasaki, Yuji; Morita, Keisuke; Matsumiya, Masahiko*; Ono, Ryoma*; Shiroishi, Hidenobu*
JOM, 73(4), p.1037 - 1043, 2021/04
Times Cited Count:3 Percentile:36(Materials Science, Multidisciplinary)The separation of Dy from Nd is studied from the viewpoint of recycling Dy from Nd magnets. Both metals are lanthanide elements, which means their mutual separation is difficult because of their similar chemical behaviors. All lanthanide elements can be extracted easily by using tetradodecyl-diglycolamide (TDdDGA) extractants, and it has a relatively high separation factor (SF) between Dy and Nd (SF over 10). In the present study, by performing eight extraction steps with the organic phase (0.1M TDdDGA in dodecane), ten steps with an aqueous phase (0.7 M HNO with metals), and six steps with another aqueous phase (0.7 M HNO without metals), approximately 99% Dy was recovered into the organic phase with 1% co-extraction of Nd.
Sasaki, Yuji; Ban, Yasutoshi; Morita, Keisuke; Matsumiya, Masahiko*; Ono, Ryoma*; Shiroishi, Hidenobu*
Solvent Extraction Research and Development, Japan, 27(1), p.63 - 67, 2020/00
Times Cited Count:6 Percentile:32.49(Chemistry, Multidisciplinary)Mutual separation technique of Dy and Nd in Nd magnet is studied. Dy is more valuable than Nd, then Dy might be isolated and reused. Lanthanide elements can be extracted thoroughly by diglycolamide (DGA) extractants, we use this reagent for the recovery and isolation of Dy. Tetradodecyl-DGA (TDdDGA) has relatively high separation factors(SF) between Dy and Nd (SF=17-18) in HNO extraction system, counter-current extraction using TDdDGA was applied for their mutual separation. From the present study, using the condition, four extraction stages, organic phase: 0.1M TDdDGA in n-dodecane, aqueous phase: 0.3M HNO, 92% Dy can be recovered with 0.7% co-extraction of Nd.
Sasaki, Yuji; Yoshimitsu, Ryo*; Nishihama, Shohei*; Shimbori, Yuma*; Shiroishi, Hidenobu*
Separation Science and Technology, 52(7), p.1186 - 1192, 2017/03
Times Cited Count:2 Percentile:9.23(Chemistry, Multidisciplinary)The new extractant, biuret(C8), is synthesized and tested for the solvent extraction of hard acid metals like actinides and soft acid metals. This compound has the similar central frame to malonamide but with 2-NH introduced into the central frame, then both amidic oxygen and nitrogen atoms may bond with metals. From the present work, not only hard acid metals, but also soft acid metals can be extracted by biuret(C8) from nitric or perchloric acids to n-dodecane. The extractability for biuret(C8) is compared with other representative extractants, malonamide, TODGA and MIDOA. It is clear that the distribution ratio(D) of U and Pu by biuret(C8) is similar to those for malonamide, but with lower values than those for TODGA and MIDOA, and D for soft acid metals and oxonium anions show higher values than those for TODGA and malonamide and lower than those for MIDOA.
Sasaki, Yuji; Yoshimitsu, Ryo*; Nishihama, Shohei*; Shimbori, Yuma*; Shiroishi, Hidenobu*
no journal, ,
no abstracts in English
Sasaki, Yuji; Ban, Yasutoshi; Morita, Keisuke; Matsumiya, Masahiko*; Ono, Ryoma*; Shiroishi, Hidenobu*
no journal, ,
Mutual separation technique of Dy and Nd in Nd magnet is noticed for the recycle of ranthanide elements. Both Dy and Nd belong to ranthanide elements, then the mutual separation is very hard. Lanthanide elements can be extracted thoroughly by diglycolamide (DGA) extractants, we use this reagent for the recovery and isolation of Dy. Tetradodecyl-DGA (TDdDGA) has relatively high separation factors (SF) between light and heavy ranthanides, this compound is useful for this purpose. In this work, the counter-current extraction using TDdDGA was applied for their separation, and the results will be discussed.
Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma*; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*
no journal, ,
We obtained relatively high D(Rh) of approximate 1 by iminodioctamide (IDOA) having tertially amino N atom from concentrated HCl solution. The reason is that IDOA is protonated, behaves as cationic extractant, and extracts anionic RhCl through ion-pair extraction. Up to now, there is less information on Rh(III) extraction, we investigate the behavior of Rh extraction and discuss with theoretical studies.
Kinoshita, Ryoma; Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*
no journal, ,
Many metal ions are stable in hydrochloric acid solutions as anionic species; diamidic-extractants containing tertiary amino nitrogen atom, such as NTAamide (hexaalkyl-nitrilotriacetamide), are normally protonated in acidic solutions and become cationic extractants. In this study, the ion-pair extraction reactions of metal chloride anions with cationic NTAamide(C6) extractant were investigated. In addition, we attempted to predict the distribution ratio by combining the stability constants of metal chloride complexes and DFT calculations, and compared the results with experimental values.