核燃料循环中镅的氧化分离研究进展

镅离子在溶液中主要以三价形式(Am(III))存在,因其离子半径与三价镧系离子Ln(III)接近,化学特性相似,使得Am(III)与Ln(III)的有效分离被认为是核燃料循环领域最具挑战性的课题之一。利用镅的多价态特性,采用不同氧化方法可将Am(III)氧化成高价态的AmO_2~+和AmO_2~(2+)形式,再通过溶剂萃取、沉淀等方法进行分离,是实现Am与Ln分离的一种新思路。本文综述了不同氧化方法对水溶液环境中Am(III)的氧化分离研究进展,描述了相关机理,指出了不同氧化方法的优劣并展望了未来发展趋势,以期为发展新型镧系与锕系元素分离技术提供参考。     

Adsorption behavior of trivalent americium and rare earth ions onto a macroporous silica-based isobutyl-BTP/SiO2-P adsorbent in nitric acid solution

To separate minor actinides from high level liquid waste (HLLW) of PUREX reprocessing, a silica-based macroporous isobutyl-BTP/SiO₂-P adsorbent was synthesized by impregnating isobutyl-BTP (2,6-di(5,6-diisobutyl-1,2,4-triazin-3-yl)pyridine) extractant into the macroporous SiO₂-P support with a mean diameter of 60 μm. A partitioning process using extraction chromatography for the treatment of HLLW was designed consisting five separation columns. As a partly work focused on isobutyl-BTP/SiO₂-P separation column, adsorption behavior of ²⁴¹Am and trivalent rare earth (RE) from simulated HLLW onto silica-based isobutyl-BTP/SiO₂-P adsorbent was investigated by batch method. Meanwhile, the chemical and radiolytic stabilities of isobutyl-BTP/SiO₂-P adsorbent against 0.01 M HNO₃ solution and γ-ray irradiation were studied. It was found that isobutyl-BTP/SiO₂-P adsorbent exhibited good adsorption selectivity for ²⁴¹Am over RE(III) in 0.01 M HNO₃ solution and showed weak or no adsorption affinity to light and middle RE(III) groups. In addition, in stability experiments, isobutyl-BTP adsorbent showed excellent stability against 0.01 M HNO₃ solution and γ-ray irradiation over 4 months contact time.     

Radiation stability of benzyldibutylamine and benzyldimethyldodecylammonium nitrate in the extraction of lanthanides and americium

The radiation stability was investigated of organic phases containing tertiary benzyldialkylamines and quaternary benzyltrialkylammonium salts which are sultable for the separation of lanthanides and americium from irradiated nuclear fuel. Attention was paid to changes of the extraction properties in Eu(III) and Am(III) extraction. The influence of the individual components forming the organic phase (extractant, solvent, solubilizer and nitric acid) on the decrease of the extraction capacity of the organic phase after irradiation is discussed. The greatest changes in the distribution coefficients D_Eu and D_Am after irradiation were shown for extraction in the presence of nitric acid. As regards the absorbed dose, these systems can be considered as stable in comparison with organophosphorus extractans.     

Selective recognition of americium by peptide-based reagents

The separation of lanthanides from minor actinides such as americium and curium is an important step during the recycling process in the treatment of nuclear waste. However, the similar chemistry and ionic size of lanthanide and actinide ions make the separation challenging. Here, we report that a peptide-based reagent can selectively bind trivalent actinides over trivalent lanthanides by means of introducing soft-donor atoms into a peptide known as a lanthanide-binding tag (LBT). Fluorescence spectroscopy has been used to measure the dissociation constant of each metal/peptide complex. A 10-fold selectivity was obtained for Am(3+) over the similarly sized lanthanide cation, Nd(3+), when the asparagine on the fifth position of a LBT was mutated to a cysteine and further functionalized by a pyridine moiety.     

On-line separation of Pu(III) and Am(III) using extraction and ion chromatography

An on-line method developed for separating plutonium and americium was developed. The method is based on the use of HPLC pump with three analytical chromatographic columns. Plutonium is reduced throughout the procedure to trivalent oxidation state, and is recovered in the various separation steps together with americium. Light lanthanides and trivalent actinides are separated with TEVA resin in thiocyanate/formic acid media. Trivalent plutonium and americium are pre-concentrated in a TCC-II cation-exchange column, after which the separation is performed in CS5A ion chromatography column by using two different eluents. Pu(III) is eluted with a dipicolinic acid eluent, and Am(III) with oxalic acid eluent. Radiochemical and chemical purity of the eluted plutonium and americium fractions were ensured with alpha-spectrometry.     

Various flowsheets of actinides recovery with diamides of heterocyclic dicarboxylic acids

Solvents on the base of diamides of heterocyclic dicarboxylic acids are promising alternatives for studied Grouped ActiNide EXtraction (GANEX) solvents. Advantage of these ligands is the possibility of simultaneous extraction not only of residual uranium and plutonium, but also minor actinides—neptunium, americium and curium. Two flowsheets on the base of diamides of heterocyclic dicarboxylic acids for separation of actinides form acidic solutions were developed, tested in laboratory scale and compared. Both flowsheets allow separation of more than 99.95% of actinides from raffinates with high content of lanthanides.     

Americium preferred: lanmodulin,a natural lanthanide-binding protein favors an actinide over lanthanides

The separation and recycling of lanthanides is an active area of research with a growing demand that calls for more environmentally friendly lanthanide sources. Likewise, the efficient and industrial separation of lanthanides from the minor actinides (Np, Am–Fm) is one of the key questions for closing the nuclear fuel cycle; reducing costs and increasing safety. With the advent of the field of lanthanide-dependent bacterial metabolism, bio-inspired applications are in reach. Here, we utilize the natural lanthanide chelator lanmodulin and the luminescent probes Eu³⁺ and Cm³⁺ to investigate the inter-metal competition behavior of all lanthanides (except Pm) and the major actinide plutonium as well as three minor actinides neptunium, americium and curium to lanmodulin. Using time-resolved laser-induced fluorescence spectroscopy we show that lanmodulin has the highest relative binding affinity to Nd³⁺ and Eu³⁺ among the lanthanide series. When equimolar mixtures of Cm³⁺ and Am³⁺ are added to lanmodulin, lanmodulin preferentially binds to Am³⁺ over Cm³⁺ whilst Nd³⁺ and Cm³⁺ bind with similar relative affinity. The results presented show that a natural lanthanide-binding protein can bind a major and various minor actinides with high relative affinity, paving the way to bio-inspired separation applications. In addition, an easy and versatile method was developed, using the fluorescence properties of only two elements, Eu and Cm, for inter-metal competition studies regarding lanthanides and selected actinides and their binding to biological molecules.

In need of environmentally friendly methods for the separation and recycling of lanthanides and actinides, the binding of the protein lanmodulin to lanthanides and actinides was studied using time resolved laser induced fluorescence spectroscopy.     

Separation of AM(III) by extraction from nitrate solutions using some quaternary benzylammonium salts

Benzyldimethyldodecylammonium nitrate and benzyltrioctylammonium nitrate were used for the extraction of Am(III) from aqueous nitrate solutions. The dependence of the extraction performance for Am(III) on the concentration of nitric acid, the kind and concentration of salting-out agents in the aqueous phase, and the kind of solvent was investigated. Americium is extracted by the above quarternary salts as a R₄NAm(NO₃)₄ associate. The extraction of Am(III) is compared with the extraction of lanthanides. The high differences in the distribution coefficients for lanthanides and americium can be utilized for the separation of lanthanides and americium.     

Challenges to develop single-column MA(III) separation from HLLW using R-BTP type adsorbents

In order to directly separate trivalent minor actinides(MA:Am,Cm) from fission products(FP) containing rare earths(RE) in high level radioactive liquid waste(HLLW),the authors have challenged to develop a simplified MA separation process by extraction chromatography using a single column.Attention has been paid to a new type of nitrogen-donor ligands,R-BTP(2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl) pyridine,R:alkyl group) as an extractant because it shows high extraction selectivity for Am(Ⅲ) over RE(Ⅲ).It is known that the R-BTP ligands show different properties such as adsorbability and stability by having different alkyl groups.Therefore,some novel adsorbents were prepared by impregnating different types of R-BTP ligands(isohexyl-,isoheptyl-and cyheptyl-BTP) and a similar ligand to the R-BTP,ATP(2,6-bis(1-aryl-1H-tetrazol-5-yl)pyridines),into the porous silica/polymer support(SiO2-P particles).This work deals with comparison in adsorption and desorption properties of Am and some FP in HNO 3 solution onto such R-BTP type adsorbents,as well as chemical and radiolytic stability of the adsorbents.Then the possibility of a single-column separation of MA from main FP was pursued by evaluating the results of column experiments using the most promising adsorbent(isohexyl-BTP/SiO2-P) under temperature control.In addition,elution behaviors of U and Pd were also estimated.     

Effect of gamma-radiation on the extraction of europium and americium by benzyldimethyldodecylammonium nitrate

Previously it was found that in the extraction separation on lanthanides and americium from acidic nitrate solutions of nuclear fission products, benzyldimethyldodecylammonium nitrate gives high values of separation coefficients. The change in the extraction capacity of this agent and its solutions in benzene in the extraction of Eu(III) and Am(III) was investigated as a function of the adsorbed dose of ionizing radiation. The slight reduction in the extraction of both metals is caused mainly by the radiolysis products of nitric acid in the organic phase that enter into secondary reactions with both the solvent and the extractant. Comparison of the radiation stability of benzyldimethyldodecylammonium nitrate systems with tertiary amines show that the changes in distribution coefficients in the range of investigated absorbed doses are significantly lower in the former case. The investigated system may be characterized as radiation stable up to about 100 kGy even in the presence of nitric acid.     

Studies on Am(III) separation from simulated high-level waste using cobalt bis(dicarbollide) (1? ) ion derivative covalently bound to N,N′-di-n-octyl diglycol diamide as extractant and DTPA as stripping agent

The separation of minor actinides from high level liquid waste (HLLW) belongs to the principal challenges in current nuclear treatment. A derivative based on two cobalt bis(dicarbollide) (1^?) ions covalently bound to the N,N??-di-n-octyl diglycolyl amide platform via diethyleneglycol chain with the formula {[(N,N??-(8-(OCH₂ CH₂)₂-1,2-C₂B₉H₁₀)(1??,2??-C₂B₉H₁₁)-3,3??-Co)(N,N??-n-C₈H₁₇)NCOCH₂]₂O}Na₂ (TODGA-COSAN), dissolved in low polar mixture of hexyl methyl ketone and n-dodecane, was used as an extractant for efficient Am(III)/Eu(III) separation from PUREX HLLW. Am(III) could be selectively stripped from loaded organic phase by using a stripping agent composed from 0.05?M DTPA and 1?M citric acid as a buffer and 1?M NaNO₃ at pH?3.0. Separation factor between europium and americium of 13 was achieved. The europium remaining in the organic phase could be consecutively effectively stripped by using solution of ammonium citrate or ammonium citrate with ammonium DTPA at pH~7.     

The EURO-GANEX Process: Current Status of Flowsheet Development and Process Safety Studies

A new hydrometallurgical grouped actinide extraction process has been developed to separate the transuranic actinide ions from dissolved spent fuel solution (after an initial uranium extraction cycle). This “EURO-GANEX” process is aimed towards the homogeneous recycling of plutonium and minor actinides in a future closed fuel cycle. The separation process is based on the co-extraction of actinides and lanthanides from aqueous nitric acid into an organic phase followed by selective co-stripping of actinides. A suitable organic phase has been formulated and distribution ratios determined for lanthanides, actinides and some problematic fission products under extraction and stripping conditions. The process flowsheet has been proven on surrogate feed solutions as well as with spent fast reactor fuel; excellent recoveries of the actinides and good decontamination factors from the lanthanides and other fission products were obtained. A variation on the EURO-GANEX flowsheet (the “TRU-SANEX” process) has now been designed to produce separate Pu+Np and Am+Cm products for heterogeneous recycling. Progress on underpinning process chemistry and safety studies as well as flowsheet tests are summarized.     

Modeling and Flowsheet Design of an Am Separation Process Using TODGA and H4TPAEN

Recycling americium from spent fuels is an important consideration for the future nuclear fuel cycle, as americium is the main contributor to the long-term radiotoxicity and heat power of the final waste, after separation of uranium and plutonium using the PUREX process. The separation of americium alone from a PUREX raffinate can be achieved by co-extracting lanthanide (Ln(III)) and actinide (An(III)) cations into an organic phase containing the diglycolamide extractant TODGA, and then stripping Am(III) with selectivity towards Cm(III) and lanthanides. The water soluble ligand H₄TPAEN was tested to selectively strip Am from a loaded organic phase.Based on experimental data obtained by Jülich, NNL and CEA laboratories since 2013, a phenomenological model has been developed to simulate the behavior of americium, curium and lanthanides during their extraction by TODGA and their complexation by H₄TPAEN (complex stoichiometry, extraction and complexation constants, kinetics). The model was gradually implemented in the PAREX code and helped to narrow down the best operating conditions. Thus, the following modifications of initial operating conditions were proposed:

• •An increase in the concentration of TPAEN as much as the solubility limit allows.
• •An improvement of the lanthanide scrubbing from the americium flow by adding nitrates to the aqueous phase.

A qualification of the model was begun by comparing on the one hand constants determined with the model to those measured experimentally, and on the other hand, simulation results and experimental data on new independent batch experiments.A first sensitivity analysis identified which parameter has the most dominant effect on the process. A flowsheet was proposed for a spiked test in centrifugal contactors performed with a simulated PUREX raffinate with trace amounts of Am and Cm. If the feasibility of the process is confirmed, the results of this test will be used to consolidate the model and to design a flowsheet for a test on a genuine PUREX raffinate. This work is the result of collaborations in the framework of the SACSESS European Project.     

Role of ligand softness and diluent on the separation behaviour of Am(III) and Eu(III)

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is a challenging task in the nuclear fuel cycle due to their similar charge and chemical behaviour. Some soft donor ligands show selectivity for An(III) over Ln(III) due to the formation of stronger covalent bonds with the former. The extraction behaviour of Am(III) and Eu(III) is studied in the present work with a mixture of Cyanex-301 (bis(2,4,4-trimethylpentyl)di-thiophosphinic acid) with several various ??N??, ??O?? or ??S?? donor neutral ligands. Comparison of the data was done with that of the oxygen donor analogue of Cyanex-301, i.e. Cyanex-272 (bis(2,4,4-trimethylpentyl)phosphinic acid). Effect of the organic diluent on the extraction behaviour of Am(III) using Cyanex-301 in presence of ??N?? donor synergists was also studied. Ab initio molecular orbital calculations were carried out using GAMESS software and charges on the donor atoms were calculated which helped in understanding the co-ordination chemistry of the ligands and explained the separation behaviour.     

Separation of Trivalent Actinides from High-Active Waste

A typical high-active waste (HAW) arising from reprocessing of (U0.3Pu0.7)C fuel irradiated to the burn-up of 155 GWd/Te in a fast breeder test reactor (FBTR) was characterized. Partitioning of trivalent actinides from HAW was demonstrated using a solvent, 0.2 M n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) – 1.2 M tri-n-butylphosphate (TBP) in n-dodecane (n-DD), in a mixer settler. The results established quantitative separation of trivalents (Am(III) + Ln(III)) from HAW and recovery (> 99%) using a citric acid-nitric acid formulation. The mutual separation of lanthanides and actinides from the stripped product was studied by using bis(2-ethylhexyl)diglycolamic acid (HDEHDGA), synthesized in our laboratory.     

Evaluation study on properties of isohexyl-BTP/SiO2-P resin for direct separation of trivalent minor actinides from HLLW

In order to develop a direct separation process for trivalent minor actinides from fission products in high level liquid waste (HLLW) by extraction chromatography, a novel macroporous silica-based 2,6-bis(5,6-diisohexyl)-1,2,4-triazin-3-yl)pyridine resin (isohexyl-BTP/SiO₂-P resin) was prepared. The content of isohexyl-BTP extractant in the resin was as high as 33.3 wt%. The resin exhibited much higher adsorption affinity for Am(III) in 2–3 M (mol/L) HNO₃ solution over U and FP which are contained in HLLW. The kinetic data were analyzed using pseudo-second-order equation. The results suggested that the Eu(III), Gd(III), and Dy(III) adsorption was well explained by the pseudo-second-order equation. Quantitative desorption for adsorbed elements was achieved by using H₂O or thiourea as eluting agents. However, the kinetics of adsorption and desorption were rather slow and this drawback needs to be resolved. Stability of the resin against HNO₃ was also examined. It was found that the resin was considerably stable against ≤4 M HNO₃ solution for the reasons of an extremely small leakage of the extractant into the solution from the resin and the adsorption performance keeping for rare earths in 3 M HNO₃ solution.     

Americium(III) coordination chemistry: An unexplored diversity of structure and bonding

The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic goups, namely the aminotriacetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH₃)₆][M(NTA)₂(H₂O)]·8H₂O with M = Nd, Yb and Am, and [Co(NH₃)₆]₂K[M₃(Cit)₄(H₂O)₃]·18H₂O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents.     

Separation of neptunium, plutonium, americium and curium from uranium with di-(2-ethylhexyl)-phosphoric acid (HDEHP) for radiometric and ICP-MS analysis

The possibility of using di-(2-ethylhexyl)-phosphoric acid (HDEHP) in solvent extraction for the separation of neptunium, plutonium, americium and curium from large amounts of uranium was studied. Neptunium, plutonium, americium and curium (as well as uranium) were extracted from HNO₃, whereafter americium and curium were back-extracted with 5M HNO₃. Thereafter was neptunium back-extracted in 1M HNO₃ containing hydroxylamine hydronitrate. Finally, plutonium was back-extracted in 3M HCl containing Ti(III). The method separates²³⁸Pu from²⁴¹Am for α-spectroscopy. For ICP-MS analysis, the interferences from²³⁸U are eliminated: tailing from²³⁸U, for analysis of²³⁷Np, and the interference of²³⁸UH⁺ for analysis of²³⁹Pu. The method has been used for the analysis of actinides in samples from a spent nuclear fuel leaching and radionuclide transport experiment.     

2,6-Bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine as a ligand for efficient actinide(III)/lanthanide(III) separation

The N-donor complexing ligand 2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine (C5-BPP) was synthesized and screened as an extracting agent selective for trivalent actinide cations over lanthanides. C5-BPP extracts Am(III) from up to 1 mol/L HNO(3) with a separation factor over Eu(III) of approximately 100. Due to its good performance as an extracting agent, the complexation of trivalent actinides and lanthanides with C5-BPP was studied. The solid-state compounds [Ln(C5-BPP)(NO(3))(3)(DMF)] (Ln = Sm(III), Eu(III)) were synthesized, fully characterized, and compared to the solution structure of the Am(III) 1:1 complex [Am(C5-BPP)(NO(3))(3)]. The high stability constant of log β(3) = 14.8 ± 0.4 determined for the Cm(III) 1:3 complex is in line with C5-BPP's high distribution ratios for Am(III) observed in extraction experiments.     

Extraction of actinides with heterocyclic dicarboxamides

Extraction of actinides from aqueous nitric acid by three different heterocyclic dicarboxamides (2,6-pyridinedicarboxamide, 2,2′-bipyridine-6,6′-dicarboxamide and 1,10-phenanthroline-2,9-dicarboxamides) was studied. It was shown that all studied ligands extract actinides at different oxidation states (U(VI), Np(V), Pu(IV), Am(III), Cm(III)) from acidic solutions. All studied diamides extract Am(III) better than Cm(III). Et(pHexPh)ClPhen contains electron-withdrawing chlorine atoms at the positions 4 and 7 of the phenanthroline moiety (SF_Am/Cm = 4–6) and possesses the highest separation factor Am(III)/Cm(III). The studied ligands possess high extraction ability to all actinides present in HLW and therefore they could be used for simultaneous extraction of actinides in the GANEX-type process.