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.
Kaneko, Masashi; Suzuki, Hideya; Matsumura, Tatsuro
Inorganic Chemistry, 57(23), p.14513 - 14523, 2018/12
We elucidated the separation mechanism between Am(III) and Cm(III) ions by using two different types of diamide ligands, diglycolamide (DGA) and alkylated diamide amine (ADAAM), by means of the density functional theory technique and electron density analysis. The molecular geometries and formation reactions of the metal-ligand complexes were modeled by using [M(DGA)] and [M(ADAAM)(NO)(HO)]. We successfully reproduced Cm(III) selectivity over Am(III) with DGA and Am(III) selectivity over Cm(III) with ADAAM. Furthermore, we analyzed the bonding properties between the metal ion and the diamide-type ligands by using model complexes, [M(DGA)] and [M(ADAAM)(NO)(HO)], and revealed the differences in terms of the bond dissociation energy and the metal 5f-orbital participation in the covalency between the Am(III) and the Cm(III) complexes. It was suggested that the differences were key factors to understand the Am(III)/Cm(III) selectivity.
Fukaya, Yuji; Goto, Minoru; Ohashi, Hirofumi; Yan, X.; Nishihara, Tetsuo; Tsubata, Yasuhiro; Matsumura, Tatsuro
Journal of Nuclear Science and Technology, 55(11), p.1275 - 1290, 2018/11
To reduce environmental burden and thread of nuclear proliferation, multi-recycling fuel cycle with High Temperature Gas-cooled Reactor (HTGR) has been investigated. Those problems are solved by incinerating TRans Uranium (TRU) nuclides, which is composed of plutonium and Minor Actinoide (MA), and there is concept to realize TRU incineration by multi-recycling with Fast Breeder Reactor (FBR). In this study, multi-recycling is realized even with thermal reactor by feeding fissile uranium from outside of the fuel cycle instead of breeding fissile nuclide. In this fuel cycle, recovered uranium by reprocessing and natural uranium are enriched and mixed with recovered TRU by reprocessing and partitioning to fabricate fresh fuels. The fuel cycle was designed for a Gas Turbine High Temperature Reactor (GTHTR300), whose thermal power is 600 MW, including conceptual design of uranium enrichment facility. Reprocessing is assumed as existing Plutonium Uranium Redox EXtraction (PUREX) with four-group partitioning technology. As a result, it was found that the TRU nuclides excluding neptunium can be recycled by the proposed cycle. The duration of potential toxicity decaying to natural uranium level can be reduced to approximately 300 years, and the footprint of repository for High Level Waste (HLW) can be reduced by 99.7% compared with GTHTR300 using existing reprocessing and disposal technology. Suppress plutonium is not generated from this cycle. Moreover, incineration of TRU from Light Water Reactor (LWR) cycle can be performed in this cycle.
Kofuji, Hirohide; Watanabe, So; Takeuchi, Masayuki; Suzuki, Hideya; Matsumura, Tatsuro; Shiwaku, Hideaki; Yaita, Tsuyoshi
Progress in Nuclear Science and Technology (Internet), 5, p.61 - 65, 2018/11
Watanabe, So; Suzuki, Hideya; Goto, Ichiro*; Kofuji, Hirohide; Matsumura, Tatsuro
Nippon Ion Kokan Gakkai-Shi, 29(3), p.71 - 75, 2018/09
Fukaya, Yuji; Goto, Minoru; Ohashi, Hirofumi; Nishihara, Tetsuo; Tsubata, Yasuhiro; Matsumura, Tatsuro
Annals of Nuclear Energy, 116, p.224 - 234, 2018/06
Optimization of disposal method and scenario to reduce volume of High Level Waste (HLW) and the footprint in a geological repository for High Temperature Gas-cooled Reactor (HTGR) has been performed. It was found that HTGR has great advantages to reducing HLW volume and its footprint, which are high burn-up, high thermal efficiency and pin-in-block type fuel, compared with those of LWR and has potential to reduce those more in the previous study. In this study, the scenario is optimized, and the geological repository layout is designed with the horizontal emplacement based on the KBS-3H concept instead of the vertical emplacement based on KBS-3V concept employed in the previous study. As a result, for direct disposal, the repository footprint can be reduced by 20 % by employing the horizontal without change of the scenario. By extending 40 years for cooling time before disposal, the footprint can be reduced by 50 %. For disposal with reprocessing, the number of canister generation can be reduced by 20 % by extending cooling time of 1.5 years between the discharge and reprocessing. The footprint per electricity generation can be reduced by 80 % by extending 40 years before disposal. Moreover, by employing four-group partitioning technology without transmutation, the footprint can be reduced by 90 % with cooling time of 150 years.
Nakamura, Shoji; Kimura, Atsushi; Hales, B. P.; Iwamoto, Osamu; Tsubata, Yasuhiro; Matsumura, Tatsuro; Shibahara, Yuji*; Uehara, Akihiro*; Fujii, Toshiyuki*
JAEA-Conf 2017-001, p.15 - 22, 2018/01
Neutron nuclear data of long lived fission products (LLFPs) have been required as basic data for the technology of reduce environmental impact involved in high level radioactive wastes (HLW). The innovative large project called by "Impusing Paradigm Change through Disruptive Technologies Program: ImPACT" have been started from October, 2014. In the ImPACT project, some research groups of JAEA engaged in the Project No.2 (Nuclear Reaction Data Measurements), and have started measurements of neutron capture cross-section at J-PARC/MLF/ANNRI. In our research, we selected cesium-135 (Cs) nuclide (half life: 2.310 yr.) among LLFPs in the HLW, and decided to measure the neutron capture cross-sections of Cs. When measurement, the Cs sample might contained cecium-137 (Cs) as impurities because it's impossible to chemically separate each other. To measure the cross-sections of Cs, there should be also needed to know the cross-sections of Cs. In this work, sample maintenance also has been examined especially for selen-79 (Se) nuclide among LLFPs having difficulty in sample preparations. In this oral session, the outline of our research project will be presented together with a research motivation, situations of past reported data, total schedules, progress, future plans, and some of high light data for neutron capture cross-section measurements.
Suzuki, Hideya; Tsubata, Yasuhiro; Kurosawa, Tatsuya*; Sagawa, Hiroshi*; Matsumura, Tatsuro
Journal of Nuclear Science and Technology, 54(11), p.1163 - 1167, 2017/11
A highly practical diamide-type extractant, which is an alkyl diamide amine with 2-ethylhexyl alkyl chains (ADAAM(EH)), was investigated for mutual separation of Am(III) and Cm(III). ADAAM(EH) is a multidentate ligand with one soft N-donor atom and two hard O-donor atoms in its central frame. This tridentate arrangement of donor atoms provides selective binding to Am(III) compared to that with Cm(III) in highly acidic media, resulting in separation factors of up to 5.5. A continuous liquid-liquid extraction and stripping test was conducted using a multistage countercurrent mixer-settler extractor with ADAAM(EH) in n-dodecane. In this test, separation of Am(III) and Cm(III) was achieved with very high yield.
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.
Kibe, Satoshi; Fujisaku, Kazuhiko*; Sakamoto, Atsushi; Sano, Yuichi; Takeuchi, Masayuki; Suzuki, Hideya; Tsubata, Yasuhiro; Matsumura, Tatsuro
JAEA-Research 2016-024, 40 Pages, 2017/02
The Japan Atomic Energy Agency has been developing some flowsheets with TDdDGA (N,N,N,Ntetradodecyldiglycolamide) extractant to recover MA (minor actinide) from raffinate. In this study, countercurrent experiments with the improved flowsheet, e.g. the addition of alcohol into the solvent for preventing the precipitation, were performed using miniature centrifugal contactors in order to compare the extraction/stripping behavior of each element with the mixer-settler type. As a result, no entrainments were observed and sufficient phase separation was achieved by centrifugal contactors without any abnormal fluid behavior, such as overflow. The extraction and stripping of Ln(III) which show the similar tendencies as MA could be achieved successfully, especially their stripping proceeded more efficiently in centrifugal contactors. This might be due to the increase in stripping rates by improving the flowsheet and to superior phase separation performance of centrifugal contactors.
Suzuki, Hideya; Tsubata, Yasuhiro; Matsumura, Tatsuro
Analytical Sciences, 33(2), p.239 - 242, 2017/02
Alkyl diamide amine (ADAAM), a new high-performance reagent with a simple structure, was examined for the mutual separation of Am(III) and Cu(III). The combination of ADAAM and Tetraethyldiglycolamide (TEDGA) as a masking agent shows selectivity for Am(III) over Cm(III) in highly acidic media with separation factors up to 41.
Ban, Yasutoshi; Hotoku, Shinobu; Tsutsui, Nao; Suzuki, Asuka; Tsubata, Yasuhiro; Matsumura, Tatsuro
Procedia Chemistry, 21, p.156 - 161, 2016/12
A continuous counter-current experiment was carried out to demonstrate the validity of a process using -dialkylamides for recovering U and Pu. This process consisted of two cycles, and the 1st cycle and the 2nd cycle employed -di(2-ethylhexyl)-2,2-dimethylpropanamide and -di(2-ethylhexyl)butanamide as extractants, respectively. The feed solution for the 1st cycle was 5.1 mol/dm (M) nitric acid containing 0.92 M U, 1.6 mM Pu, and 0.6 mM Np. The raffinate collected in the 1st cycle was used as the feed for the 2nd cycle. The ratios of U recovered in the U fraction and U-Pu fraction were 99.1% and 0.8%, respectively. The ratio of Pu recovered in the U-Pu fraction was 99.7%. The concentration ratio of U with respect to Pu in the U-Pu fraction was 9, and this indicated that Pu was not isolated. The decontamination factor of U with respect to Pu in the U fraction was obtained as 4.510. These results supported the validity of the proposed process.
Kaneko, Masashi; Watanabe, Masayuki; Matsumura, Tatsuro
Dalton Transactions, 45(43), p.17530 - 17537, 2016/11
Relativistic density functional calculations were applied to study the separation behaviors of Am(III) ion from Eu(III) ion by diglycolamide (DGA) and nitrilotriacetamide (NTA) ligands in order to understand the difference in the separation mechanism of their reagents. The complexation reaction was modeled on the basis of previous experimental studies. The calculated energies based on stabilization by complex formation at the ZORA-B2PLYP/SARC level predicted that the DGA reagent preferably coordinated to Eu(III) ion when compared with Am(III) ion. In contrast, the NTA reagent selectively coordinated to Am(III) ion when compared with Eu(III) ion. These results reproduced the experimental selectivity of DGA and NTA ligands toward Eu(III) and Am(III) ions. Mulliken's population analyses implied that the difference in the contribution of the bonding property between the f-orbital of Am and donor atoms determined the comparative stability of Eu and Am complexes.
Suzuki, Tomoya; Morita, Keisuke; Sasaki, Yuji; Matsumura, Tatsuro
Separation Science and Technology, 51(17), p.2815 - 2822, 2016/09
To understand the adsorption properties of styrene-divinylbenzene copolymer functionalized with -trimethylglycine, AMP03, the adsorption behaviors for platinoid ions (Ru(III), Rh(III), and Pd(II)) were examined. Furthermore, we performed adsorption experiments using sample solutions with adding triethylamine, thiourea, and -trimethylglycine. Based on the adsorption data obtained in this study, we performed chromatographic experiments. The results indicated that all platinoid ions in the feed solution completely adsorbed on AMP03, and almost 80% of the adsorbed platinoid ions were recovered. These results show that AMP03 has the potential to recover Ru(III), Rh(III), and Pd(II) from high-level liquid waste.
Suzuki, Tomoya; Morita, Keisuke; Sasaki, Yuji; Matsumura, Tatsuro
Bulletin of the Chemical Society of Japan, 89(5), p.608 - 616, 2016/05
In a previous study, we found that AMP03 adsorbs Rh(III) from the HNO solution with pH = 1.7 - 2.2. In this study, to understand the Rh(III) adsorption properties of AMP03 and clarify conditions for efficient recovery, we investigated the adsorption behaviors of Rh(III) from the HNO solution. As a result, it was found that Rh(III) is effectively adsorbed from aqueous solution containing low H and high NO concentration. Considering the adsorption mechanism of Rh(III), we found that Rh in aqueous solution is adsorbed with two betaine groups in AMP03 and three NO.
Suzuki, Hideya; Tsubata, Yasuhiro; Kurosawa, Tatsuya; Shibata, Mitsunobu; Kawasaki, Tomohiro; Urabe, Shunichi*; Matsumura, Tatsuro
Analytical Sciences, 32(4), p.477 - 479, 2016/04
An impeccable, high-performance new reagent called alkyl diamide amine (ADAAM) was examined from the viewpoint of mutual separation of Am(III) and Eu(III). ADAAM has three donor atoms, one soft N-donor atom and two hard O-donor atoms, in the central frame. The combination of soft and hard atoms affords a tridentate donor set of atoms that ensures remarkable extractability and selectivity of Am(III) and Eu(III) in highly acidic media.
Kibe, Satoshi; Fujisaku, Kazuhiko*; Ambai, Hiromu; Sakamoto, Atsushi; Sano, Yuichi; Takeuchi, Masayuki; Suzuki, Hideya; Tsubata, Yasuhiro; Matsumura, Tatsuro
JAEA-Research 2015-021, 40 Pages, 2016/02
The flowsheet with TDdDGA extractant has been being developed for recovering MA from PUREX raffinate. In the previous study, the yields of MA and other elements in countercurrent extraction/stripping experiments using mixer-settlers were not enough for the target and it would be due to the insufficient phase (aqueous/organic) separation. In this study, we carried out countercurrent experiments with surrogate PUREX raffinate using centrifugal contactors which had superior phase separation ability, and evaluated the extraction/stripping behavior of each element. During the operation, abnormal fluid behavior, such as overflow and entrainment, was not observed, and sufficient phase separation was achieved by centrifugal contactors. Extraction behavior of lanthanides was similar to that in mixer-settlers, but their stripping efficiencies decreased. This would be due to shorter residence time in mixing zone.
Tsutsui, Nao; Ban, Yasutoshi; Hakamatsuka, Yasuyuki; Matsumura, Tatsuro
Separation Science and Technology, 51(6), p.961 - 967, 2016/02
Quantitative evaluation of the two-phase separation between ,-di(2-ethylhexyl)butanamide (DEHBA) and tri--butyl phosphate (TBP) diluted with -dodecane and uranyl nitrate solution in nitric acid medium was achieved using turbidity measurements. The turbidities of DEHBA were relatively high, particularly at high DEHBA concentrations, while that of TBP rapidly decreased irrespective of nitric acid concentration. A high concentration of DEHBA, nitric acid, and uranium increased the turbidities in the organic phase, which could be ascribed to the increase in viscosity. Distribution ratios of uranium were also measured, and it was indicated that turbidity did not have a critical effect on the distribution ratio when the turbidity was below a certain value.
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.