Ban, Yasutoshi; Suzuki, Hideya*; Hotoku, Shinobu; Tsutsui, Nao; Tsubata, Yasuhiro; Matsumura, Tatsuro
Solvent Extraction and Ion Exchange, 37(7), p.489 - 499, 2019/11
A continuous counter-current experiment to separate minor actinides (MAs: Am and Cm) was performed with -hexaochyl nitrilotriacetamide (HONTA) as an extractant. Nitric acid of 0.08 M (mol/dm) containing MAs and rare earths (REs) recovered from high-level waste was used as the Feed, and the experiment was conducted for 14 h. The ratios of Am and Cm recovered into the MA fraction measured 94.9% and 78.9%, respectively. HONTA hardly extracted Y, La, and Eu in the Feed (99.9% for Y, 99.9% for La, and 96.7% for Eu), most of which were distributed to the RE fraction. A portion of Nd was extracted by HONTA, and consequently the ratio of Nd in the RE fraction was 83.5%. The concentrations of MAs and some REs in each stage were calculated using a simulation code, and the results are consistent with the experimental values. This code indicates that the ratios of MAs in the MA fraction and REs in the RE fraction could be 99% by optimizing separation conditions.
Ban, Yasutoshi; Suzuki, Hideya; Hotoku, Shinobu; Kawasaki, Tomohiro*; Sagawa, Hiroshi*; Tsutsui, Nao; Matsumura, Tatsuro
Solvent Extraction and Ion Exchange, 37(1), p.27 - 37, 2019/00
A continuous counter-current experiment using TDdDGA was performed using mixer-settler extractors installed in a hot cell. Nitric acid containing minor actinides (MAs: Am and Cm), rare earths (REs: Y, La, Nd, and Eu), and other fission products (Sr, Cs, Zr, Mo, Ru, Rh, and Pd) was fed to the extractor. TDdDGA effectively extracted MAs and REs from the feed, while other fission products were barely extracted. The extracted MAs and REs were back-extracted by bringing them in contact with 0.02 mol/dm nitric acid, and they were collected as the MA-RE fraction. The proportions of MA and RE in the MA-RE fraction were 98% and 86%, respectively. These results demonstrated the applicability of TDdDGA as an extractant for MAs and REs.
Analytical Sciences, 34(12), p.1345 - 1346, 2018/12
Solvent extraction is one of the most effective analytical methods for separation, purification, and removal of target metal ions (e.g. valuable metal ions, toxic metal ions and radioactive fission products) from aqueous solutions containing various metal ions. In this paper, we introduce the papers related to (1) novel extractant, (2) ionic liquids and deep eutectic solvents, (3) new extractors, among papers on solvent extraction published between 2016 and 2018.
Kusaka, Ryoji; Watanabe, Masayuki
Physical Chemistry Chemical Physics, 20(47), p.29588 - 29590, 2018/12
Mechanistic understanding of solvent extraction of uranyl ions (UO) by tributyl phosphate (TBP) will help improve the technology for the treatment and disposal of spent nuclear fuels. So far, it has been believed that uranyl ions in the aqueous phase are adsorbed to a TBP-enriched organic/aqueous interface, form complexes with TBP at the interface, and are extracted into the organic phase. Here we show that uranyl-TBP complex formation does not take place at the interface using vibrational sum frequency generation (VSFG) spectroscopy and propose an alternative extraction mechanism that uranyl nitrate, UO(NO), passes through the interface and forms the uranyl-TBP complex, UO(NO)(TBP), in the organic phase.
Kusaka, Ryoji; Watanabe, Masayuki
Physical Chemistry Chemical Physics, 20(4), p.2809 - 2813, 2018/01
Solvent extraction plays an integral part in the separation and purification of metals. Because extractants generally used as complexing agents for metal extractions, such as di-(2-ethylhexyl)phosphoric acid (HDEHP) for lanthanide extractions, are amphiphilic, they come to the organic/water interface, and the interface plays a crucial role as the site of the formation of metal complexes and subsequent transfer reaction to an organic phase. Despite the importance of the interface for solvent extractions, however, molecular-level structure of the interface is unclear because of experimental difficulty. Here we studied structure of a trivalent europium (Eu) complex with HDEHP formed at HDEHP monolayer/water interface by heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. The study on the HDEHP/water interface enables us to investigate the structure of the interfacial Eu complex by excluding the migration of Eu into an organic phase after the complex formation at the interface. The interface-selective vibrational Im spectra observed by HD-VSFG of HDEHP/Eu(NO) aqueous solution interface in the 2800-3500 cm region indicate that Eu at the HDEHP/water interface is bonded by HDEHP from the air side and by water molecules from the water side. To the best of our knowledge, such metal complex structures have not been identified in the organic or water solutions.
Sano, Yuichi; Watanabe, So; Nakahara, Masaumi; Aihara, Haruka; Takeuchi, Masayuki
Proceedings of International Nuclear Fuel Cycle Conference (GLOBAL 2017) (USB Flash Drive), 4 Pages, 2017/09
JAEA has been promoting MA recycle project using a FR fuel cycle named as SmART cycle concept. The SmART cycle contains the recovery of all actinides, in which total amount of MA is estimated to around 1-2g, at CPF from the FR Joyo spent fuel, the fabrication of MA bearing MOX fuel pellets and pins at AGF with recovered actinides, and the irradiation test of the fabricated fuels at the Joyo. In this paper, recent activities on actinides recovery in CPF, which will make a significant contribution to the SmART cycle, were summarized.
Tsutsui, Nao; Ban, Yasutoshi; Sagawa, Hiroshi; Ishii, Sho; Matsumura, Tatsuro
Solvent Extraction and Ion Exchange, 35(6), p.439 - 449, 2017/08
Solvent extraction of uranium from a nitric acid medium was performed with ,-di(2-ethylhexyl)octanamide (DEHOA) by a single-stage batch method, and the distribution ratio equation of U(VI) was derived as = 1.1. Furthermore, the nitric acid distribution was also evaluated, and the distribution ratio equation = 0.12 was obtained. Batch experiments to evaluate the time dependence of U(VI) extraction and the U(VI) loading capacity of DEHOA were also performed. It was revealed that U(VI) extraction by DEHOA reached an equilibrium state within a few minutes, and the loading capacity was 0.71 mol/dm (M) when the concentrations of DEHOA and nitric acid were 1.5 and 3.0 M, respectively.
Morita, Yasuji; Yamagishi, Isao
JAEA-Research 2017-006, 27 Pages, 2017/06
Separation of Pd by extraction with 5,8-diethyl-7-hydroxy-6-dodecanone oxime (DEHDO) was examined by batch and continuous tests for the purpose of developing Pd separation process. Batch extraction tests using n-dodecane solution of DEHDO revealed that Pd, Zr and Mo were extracted from simulated high-level radioactive liquid wastes (HLLW) and other elements were not, and also showed that the extraction rate was a little slow and a white precipitate appeared in the aqueous phase but its formation could be avoided by raising temperature. The extracted Pd was found to be back-extracted with sodium nitrite. In the continuous extraction tests with simulated HLLW without Zr and Mo, about 98% of Pd were extracted with DEHDO-n-dodecane and 95% of the extracted Pd were back-extracted with sodium nitrite and nitric acid. Continuous extraction test with simulated HLLW with Zr and Mo showed the possibility of the simultaneous separation of Pd and Mo by DEHDO extraction.
Sasaki, Yuji; Morita, Keisuke; Suzuki, Shinichi; Shiwaku, Hideaki; Ito, Keisuke; Takahashi, Yuya*; Kaneko, Masaaki*
Solvent Extraction Research and Development, Japan, 24(2), p.113 - 122, 2017/06
The solvent extraction of Se, Zr, Pd, and Cs from nitric acid into 1-octanol (OC) and dodecane has been performed. These elements include long-lived radionuclides in spent nuclear fuels, so a simple separation method is indispensable for the development of the treatment of high-level liquid radioactive waste. It was found that Se can be extracted using phenylenediamine, Zr can be extracted using tetraoctyl diglycolamide and di-2-ethylhexyl phosphoric acid, and Pd can be extracted using (methylimino)bis(dioctylacetamide) and hexaoctylnitrilotriacetamide. These elements can be recovered in over 90% yield by these extractants from nitric acid into OC. A distribution ratio of Cs of greater than 1 can be obtained using di-t-butyldibenzo-18-crown-6. It is clear that 90% recovery of Cs can be achieved using an extraction solvent with ten times the volume of the aqueous phase.
Narita, Hirokazu*; Suzuki, Tomoya*; Motokawa, Ryuhei
Nippon Kinzoku Gakkai-Shi, 81(4), p.157 - 167, 2017/04
Maeda, Motoki*; Narita, Hirokazu*; Tokoro, Chiharu*; Tanaka, Mikiya*; Motokawa, Ryuhei; Shiwaku, Hideaki; Yaita, Tsuyoshi
Separation and Purification Technology, 177, p.176 - 181, 2017/04
Ishida, Takuya; Suzuki, Yoshitaka; Nishikata, Kaori; Yonekawa, Minoru; Kato, Yoshiaki; Shibata, Akira; Kimura, Akihiro; Matsui, Yoshinori; Tsuchiya, Kunihiko; Sano, Tadafumi*; et al.
KURRI Progress Report 2015, P. 64, 2016/08
no abstracts in English
Motokawa, Ryuhei; Endo, Hitoshi*; Nagao, Michihiro*; Heller, W. T.*
Solvent Extraction and Ion Exchange, 34(5), p.399 - 406, 2016/07
Tanase, Masakazu*; Fujisaki, Saburo*; Ota, Akio*; Shiina, Takayuki*; Yamabayashi, Hisamichi*; Takeuchi, Nobuhiro*; Tsuchiya, Kunihiko; Kimura, Akihiro; Suzuki, Yoshitaka; Ishida, Takuya; et al.
Radioisotopes, 65(5), p.237 - 245, 2016/05
no abstracts in English
Sasaki, Yuji; Morita, Keisuke; Shimazaki, Shoma*; Tsubata, Yasuhiro; Ozawa, Masaki*
Solvent Extraction Research and Development, Japan, 23(2), p.161 - 174, 2016/05
We examined the masking effects of 16 water-miscible reagents, on the extraction of Mo, Re, Ru, and Pd. The extractants, methylimino-dioctylacetamide (MIDOA) and hexaoctyl-nitrilotriacetamide (NTAamide(C8)), show significantly high distribution ratios for these metals, were employed in this study. Masking effects were observed as a decrease of distribution ratio with an increase of masking agent concentration in these extraction systems. The results showed that Pd and Ru can be masked by similar reagents including N- or S- donor atoms, which suppressed the extraction into the organic phase. In contrast, distribution ratio of Mo was only slightly masked by the above mentioned reagents. The masking of Mo was achieved using complexing agents having a central N(CHC(P)=O) framework that is important for this purpose. A masking agent for Re was not found in this study.
Sasaki, Yuji; Suzuki, Tomoya; Morita, Keisuke; Yoshizuka, Kazuharu*
Hydrometallurgy, 159, p.107 - 109, 2016/01
The novel tridentate extractant including soft donor has developed and examined. The extractant, tetraoctyl-thiodiglycolamide (S-DGA), is analogous structure to tetraoctyl-diglycolamide (TODGA), but with sulfur donor instead of ether oxygen of TODGA. S-DGA has unique property to extract silver from acidic solutions to n-dodecane with relatively high D values. We investigated the extraction behavior of Ag in various acids, HNO, HSO, and HClO.
Ban, Yasutoshi; Hotoku, Shinobu; Tsutsui, Nao; Tsubata, Yasuhiro; Matsumura, Tatsuro
Solvent Extraction and Ion Exchange, 34(1), p.37 - 47, 2016/01
The extraction properties of -di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA) and -di(2-ethylhexyl)butanamide (DEHBA) for Np(V) and Np(VI) were studied by a batch method using various nitrate ion concentrations. The distribution ratios of Np(VI) obtained with DEHDMPA and DEHBA exceeded unity when the nitrate ion concentration was 3 mol/L. DEHDMPA and DEHBA barely extracted Np(V), and the maximum distribution ratios were 0.4 and 0.2 when DEHDMPA and DEHBA were used as extractants, respectively. A continuous counter-current experiment was performed to evaluate the behavior of Np in a process comprising two cycles. The ratio of Np recovered to the U fraction and U-Pu fraction were 63.7% and 29.1%, respectively. The behavior of Np suggested that the valence state of Np changed from Np(V) to Np(IV) or Np(VI) after the 1st experimental cycle. The recoveries of U and Pu to the U fraction stream and the U-Pu fraction stream were 99.9% and 99.8%, respectively.
Sasaki, Yuji; Sugo, Yumi; Morita, Keisuke; Nash, K.*; Nash, K. L.*
Solvent Extraction and Ion Exchange, 33(7), p.625 - 641, 2015/10
The effect of alkyl substituents at amidic N atoms in diglycolamide (DGA) compounds on solvent extraction was investigated. The solubility in water and n-dodecane, loading capacity, and distribution ratio (D) of lanthanides and actinides for various DGA compounds were monitored. DGA derivatives with short alkyl chains, for example methyl and ethyl groups, are highly water soluble, while DGA derivatives with long alkyl chains are highly soluble in n-dodecane. The loading capacity correlats with their alkyl chain lengths. The results of masking effect and solubility tests indicate that TEDGA(tetraethyl-diglycolamide) is the best actinide masking agent among the water-soluble DGA derivatives. Actinide extractions were performed using ten DGA compounds in six diluents (nitrobenzene, 1,2-dichloroethane, 1-octanol, chloroform, toluene, and n-dodecane), in which it was observed that DGA derivatives with shorter alkyl chains show higher D values.
Sasaki, Yuji; Tsubata, Yasuhiro; Shirasu, Noriko; Morita, Keisuke; Suzuki, Tomoya
Nippon Genshiryoku Gakkai Wabun Rombunshi, 14(3), p.202 - 212, 2015/09
We have been developing the new partitioning method of high-level radioactive waste by single-cycle extraction process. This process is composed of extraction of actinides (An) and fission products (FP, e.g., Pd, Ru, Mo and Tc), and mutual separation by back-extraction. The extractant employed in this process is required to extract soft, hard acid metals and oxonium anions simultaneously. The NTAamide (hexaoctyl-nitrilotriacetamide) is one of the candidate extractants. After extraction of An and FP, the mutual separation by back-extraction should be set up. Pd and Ru extracted by NTAamide can be back-extracted by complexing agents such as thiourea, systeine, diethylenetriamine, and trisaminoethylamine, and the back-extraction of Mo can be performed by methylimino-diethylacetamide (MIDEA), NTAamide(C2) and iminodimethylphosphoric acid, and Re can be done by aqueous phase with high pH.
Ban, Yasutoshi; Hotoku, Shinobu; Tsubata, Yasuhiro; Tsutsui, Nao; Matsumura, Tatsuro
Proceedings of 21st International Conference & Exhibition; Nuclear Fuel Cycle for a Low-Carbon Future (GLOBAL 2015) (USB Flash Drive), p.1147 - 1152, 2015/09
Extraction properties of -di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA), -di(2-ethylhexyl)butanamide (DEHBA), and some of their degradation products for the metal elements Zr, Mo, Ru, Rh, and Pd were studied using a single-stage batch method, and the results showed that the degradation products barely extracted these metal elements. Furthermore, separation performance of DEHDMPA and DEHBA for U and Pu in a continuous counter-current process was evaluated using a calculation code, and it was confirmed that the calculated values of U concentration in the U fraction and U and Pu concentrations in the U-Pu fraction were similar to those measured experimentally. These results supported the applicability of DEHDMPA and DEHBA as extractants for separation processes and the validity of the calculation code for estimating the separation performance of the process.