Solvent extraction behaviors of rhodium and palladium in nitric acid solutions using amide extractants

Ito, Kengo*; Morita, Misaki*; Araki, Yuta*; Kato, Chizu*; Fukutani, Satoshi*; Matsumura, Tatsuro; Fujii, Toshiyuki*

Solvent Extraction Research and Development, Japan, 32(1), p.53 - 62, 2025/00

https://doi.org/10.15261/serdj.32.53

Rhodium (Rh) and Palladium (Pd) in high-level radioactive waste are primarily fission products. This Study focused on understanding the extraction behavior of these platinum group elements (PGEs) using the novel extractants -hexaoctylnitriloacetamide (HONTA) and alkyl diamideamine (ADAAM). Both extractants showed affinity for Pd, with distribution coefficients significantly exceeding 1, demonstrating their effectiveness in Pd separation. In contrast, the distribution coefficients for Rh were consistently below 10 , indicating low extraction efficiency from nitric acid. However, by leveraging the salting-out effect with calcium nitrate hydrate, a distribution coefficient of 570 for Rh was achieved using HONTA. To overcome the difficult back-extraction of PGEs with HONTA, experiments were conducted using HEDTA and thiourea. Back-extraction with HEDTA in high-concentration nitric acid (2M) resulted in 90% extraction of Pd, while thiourea-based back-extraction with nitric acid yielded over 40% extraction for Rh, with the maximum of 62.7% achieved using hydrochloric acid.

Flexible waste management system for the future application of MA P&T technology to the current high-level liquid waste

Fukasawa, Tetsuo*; Suzuki, Akihiro*; Endo, Yoichi*; Inagaki, Yaohiro*; Arima, Tatsumi*; Muroya, Yusa*; Endo, Keita*; Watanabe, Daisuke*; Matsumura, Tatsuro; Ishii, Katsunori; et al.

Journal of Nuclear Science and Technology, 61(3), p.307 - 317, 2024/03

https://doi.org/10.1080/00223131.2023.2226673

A flexible waste management system (FWM) is being developed to apply future MA partitioning and transmutation (P&T) technology to current HLLW. This FWM system will store high-level waste (HLLW) in granular form until MA partitioning and transmutation technology is realized. The feasibility of the main process was essentially confirmed by basic experiments and preliminary thermal analysis for granule production by rotary kiln from simulated HLLW and for temporary storage (50 years) of HLW granules at the HLW storage facility, respectively. The granule production experiments revealed that relatively large particles can be produced by the rotary kiln. The results of the thermal analysis showed that the small diameter canisters could be used to safely store the granules at a higher storage density than vitrified HLW. The effectiveness of the FWM system in terms of potential radiotoxicity and repository area was also evaluated, and it was shown that FWM can reduce these factors and has significant advantages in the disposal of HLW generated in current reprocessing plants. Since LWR fuel is stored for a long period of time in Japan and the operation of a reprocessing plant is expected to start soon, the FWM system is considered to be an effective system for reducing the environmental burden of HLW disposal.

Study on the mechanism of radiolytic degradation of an extractant for minor actinides separation

Toigawa, Tomohiro; Kumagai, Yuta; Yamashita, Shinichi*; Ban, Yasutoshi; Matsumura, Tatsuro

UTNL-R-0502 (Internet), 2 Pages, 2022/04

This report summarizes the results obtained in FY2020 at the Electron Linac Facility of the University of Tokyo. The radiolysis process of -hexaoctyl nitrilotriacetamide (HONTA), which is expected to be used as an extractant in a separation process for minor actinides, diluted in dodecane was investigated by pulse radiolysis experiments. The radical cation and the triplet-excited state of HONTA were observed in the nanosecond time region. The transition from the radical cation to the triplet excited state was slowed down by adding electron scavengers, and further, the reactivity of the triplet excited state was also suppressed.

Radiation-induced effects on the extraction properties of hexa--octylnitrilo-triacetamide (HONTA) complexes of americium and europium

Toigawa, Tomohiro; Peterman, D. R.*; Meeker, D. S.*; Grimes, T. S.*; Zalupski, P. R.*; Mezyk, S. P.*; Cook, A. R.*; Yamashita, Shinichi*; Kumagai, Yuta; Matsumura, Tatsuro; et al.

Physical Chemistry Chemical Physics, 23(2), p.1343 - 1351, 2021/01

https://doi.org/10.1039/D0CP05720G

The candidate An(III)/Ln(III) separation ligand hexa--octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions using a solvent test loop in conjunction with cobalt-60 gamma irradiation. We demonstrate that HONTA undergoes exponential decay with increasing gamma dose to produce a range of degradation products which have been identified and quantified by HPLC-ESI-MS/MS techniques. The combination of HONTA destruction and degradation product ingrowth, particularly dioctylamine, negatively impacts the extraction and back-extraction of both americium and europium ions. The loss of HONTA was attributed to its reaction with the solvent (-dodecane) radical cation of (HONTA + R) = (7.61 0.82) 10 M s obtained by pulse radiolysis techniques. However, when this ligand is bound to either americium or europium ions, the observed -dodecane radical cation kinetics increase by over an order of magnitude. This large reactivity increase to additional reaction pathways occurring upon metal-ion binding. Lastly nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (100 ns) HONTA radical cation as well as a longer-lived (s) HONTA triplet excited state. These HONTA species are important precursors to the suite of HONTA degradation products observed.

Study on the mechanism of radiolytic degradation of an extractant for minor actinides separation

Toigawa, Tomohiro; Murayama, Rin*; Kumagai, Yuta; Yamashita, Shinichi*; Suzuki, Hideya; Ban, Yasutoshi; Matsumura, Tatsuro

UTNL-R-0501, p.24 - 25, 2020/12

This report summarizes the results obtained in FY2019 at Electron Linac Facility of University of Tokyo. The radiolysis process of a diglycolamide extractant, which is expected to be used in the separation process of minor actinides (MA), in dodecane and octanol solutions was investigated by pulse radiolysis. As a result, it was suggested that by adding alcohol, the decomposition process of the diglycolamide extractant was different from the decomposition processes in the single solvent of dodecane considered that the decomposition occurred via a radical cation species of the extractant.

Production of the minor actinide sources using the electrodeposition method

Nakamura, Satoshi; Kimura, Takahiro; Ban, Yasutoshi; Tsubata, Yasuhiro; Matsumura, Tatsuro

JAEA-Technology 2020-009, 22 Pages, 2020/08

JAEA-Technology-2020-009.pdf:2.92MB

Partitioning and transmutation technology division is planning to measure fission rate ratios that contribute to validate nuclear data of minor actinides (MA). For this purpose, MA sources for fission chambers were prepared using electrodeposition method. The radioactivity of each MA source was quantified, and its uncertainty was evaluated. Seven types of MA sources with different radioactivity were prepared using four nuclides of Np, Am, Am, and Cm. A Cm source solution of which radioactivity was quantified by isotope dilution method was used to prepare working standard sources of Cm. The radioactivities were quantified as 1461 Bq, 2179 Bq, and 2938 Bq for Np sources, 1.428 MBq for Am source, 370.5 kBq and 89.57 kBq for Am sources, and 2.327 MBq for Cm source with, the uncertainty of 0.35% (1). This report summarizes the method for preparation and quantification of MA sources, and uncertainty evaluation.

Sorption properties of aluminum hexacyanoferrate for platinum group elements

Mishima, Ria; Inaba, Yusuke*; Tachioka, Sotaro*; Harigai, Miki*; Watanabe, Shinta*; Onoe, Jun*; Nakase, Masahiko*; Matsumura, Tatsuro; Takeshita, Kenji*

Chemistry Letters, 49(1), p.83 - 86, 2020/01

https://doi.org/10.1246/cl.190741

Separation of platinum group metals (PGMs) from high-level liquid waste generated from the reprocessing of spent nuclear fuels is important to produce good quality vitrified glass for final disposal. A new sorbent, Aluminum hexacyanoferrate (AlHCF), was synthesized and the general sorption behavior of PGMs from concentrated nitric acid was examined. Nitric acid caused substantial elution of AlHCF but the sorption of Pd stabilized the structure. Consequently, Rh was sorbed in the presence of Pd, whereas single Rh sorption caused complete dissolution of AlHCF. Relation between sorbed mount of Pd vs eluted Al and Fe revealed that the elution ratio of Al and Fe was not the same as molar ratio of synthesized AlHCF, indicating the re-sorption of Fe resulted in formation of new structure. The sorption mechanism of PGMs by this new sorbent, AlHCF, not only the simple ion exchange, but also oxidation reduction reaction as well as kinetics play important rule. Understanding the general sorption and dissolution behavior will help improve the sorption performance of PGMs by AlHCF.

No secondary waste recycle technology for rare metals using the hydrophilic extraction with phase transfer phenomena

Tsukahara, Takehiko*; Saga, Kaname*; Suzuki, Hideya*; Matsumura, Tatsuro

Kurin Tekunoroji, 29(12), p.4 - 7, 2019/12

no abstracts in English

Zr separation from high-level liquid waste with a novel hydroxyacetoamide type extractant

Morita, Keisuke; Suzuki, Hideya; Matsumura, Tatsuro; Takahashi, Yuya*; Omori, Takashi*; Kaneko, Masaaki*; Asano, Kazuhito*

Proceedings of International Nuclear Fuel Cycle Conference / Light Water Reactor Fuel Performance Conference (Global/Top Fuel 2019) (USB Flash Drive), p.464 - 468, 2019/09

High level liquid waste (HLLW) contains several radionuclides with half-lives longer than 10 year. For reduce environmental burden of waste disposal, minor actinoids and long-lived fission products will to be partitioned and transmuted. JAEA and Toshiba developed process for recovering Se, Zr, Pd and Cs from HLLW. Solvent extraction for Zr with novel extractant, -didodecyl-2-hydroxyacetoamide (HAA) was detailed. The HAA system showed high selectivity for Zr, as indicated by the extraction order of Zr Mo Pd Ag Sb Sn Lns Fe. The extracted species was determined as Zr(HAA)(NO)(HNO). A continuous countercurrent extraction with HAA was applied to a simulated, concentrated HLLW after Pd, Se, and Cs removal, where the quantitative extraction of Zr and Mo was effectively demonstrated.

Direct temperature-swing extraction of rare-earth elements from acidic solution using the hydrophobic interactions of poly(-isopropylacrylamide) with diglycolamide-typed ligands

Saga, Kaname*; Suzuki, Hideya; Matsumura, Tatsuro; Tsukahara, Takehiko*

Analytical Sciences, 35(4), p.461 - 464, 2019/04

https://doi.org/10.2116/analsci.18N023

The phase transition-based gelification phenomenon of poly--isopropylacrylamide (PNIPAAm) in aqueous solutions has a great potential in developing new waste-free extraction processes of metal ions. By using hydrophobic diglycolamide-typed ligands in gelification extraction, a one-step complete extraction of all the RE ions from a nitric acid solution was successfully realized.