Partitioning Of Minor Actinides Research Articles

Endowing 2,6-bis-triazolyl-pyridine of poor extraction with superior efficiency for actinide/lanthanide separation at high acidity by anchoring to a macrocyclic scaffold

Exploring nitrogen-containing extractants for recovering hazardous minor actinides that are workable in solutions of high acidity has been a challenge in nuclear waste treatment. Herein, we report our findings that 2,6-bis-triazolyl-pyridine (PyTri), which is ineffective as a hydrophobic ligand for minor actinide separation, turns into an excellent extractant that exhibits unexpectedly high efficiency and selectivity (SFAm/Eu = 172, 1 M HNO3) when attaching to pillar[5]arene platform. Surprisingly, the distribution ratio of Am(III) (DAm) is 4300 times higher than that of the acyclic PyTri ligand. The solvent extraction performance of this pillar[5]arene-achored PyTri not only far exceeds the best known pillar[5]arene ligands reported to date, but also stays comparable to other reported outstanding extractants. Slope analysis indicates that each P[5]A-PyTri can bind two metal ions, which is further corroborated by spectroscopic characterizations. Thermodynamic studies imply that the extraction process is exothermic and spontaneous in nature. Complexation investigation via EXAFS technique and DFT calculations strongly suggest that each Eu(III) ion is coordinated to three PyTri arms through a nine-coordination mode. This work provides a N-donor extractant that can operate at high acidity for minor actinide partitioning and implicates a promising approach for transforming poor extractants into superior ones.

Fuel cycle considerations for uranium, plutonium and minor actinide partitioning and transmutation

This paper is written in memorial of the authors’ past collaborations with Max Salvatores in the area of advanced nuclear fuel cycle evaluation. In this regard, a summary is provided of the results from two international studies led by Max Salvatores in which the authors participated: (1) the expert group on Homogeneous versus Heterogeneous Recycling of Transuranics in Fast Nuclear Reactors, and (2) the expert group on Potential Benefits and Impacts of Advanced Nuclear Fuel Cycles with Actinide Partitioning and Transmutation. Both of these studies presented the authors with the opportunity to contribute the results of past and ongoing research in the U.S., facilitating engagement and discussion on these subjects with researchers from other countries and organizations, resulting in the creation of broad international views on the relative benefits and challenges of transuranic recycle (NEA, 2012a; NEA, 2012b), a testament to the leadership and capabilities of Max Salvatores.

Uncovering Heavy Actinide Covalency: Implications for Minor Actinide Partitioning.

Across the actinide period, the stability of the trivalent oxidation state predominates in the heavy actinides, making their chemical nature close to that of rare earth elements. The resemblance in their chemistry poses difficulties in separating heavy actinides from lanthanides, which is a vital separation in the minor actinide partitioning process. Actinide contraction has conventionally implied electrostatic actinide-ligand interactions among the heavy actinides. The present study challenges this conventional understanding and reveals increasing covalency in the actinide-ligand bond across Am to Cf. Complexes of Am, Cm, Bk, and Cf have been examined for their electronic structure with a focus on the nature of their interactions with different ligands within the framework of density functional theory, where the relativistic effects have been incorporated by using zero-order regular approximation and spin-orbit coupling. The choice of ligands selected for this study facilitates the effect of the donor atom as well as denticity to be accounted for. Hence, heavy actinide complexes of the N- and O-donor ligand dipicolinic acid, S and O mixed donor ligands of the Cyanex type, and an octadentate ligand N, N, N' N'-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylenediamine have been optimized and evaluated. In each case energy decomposition analysis has been used to explicitly decompose the metal-ligand interaction energy into components which have then been analyzed. Irrespective of the hard-soft characteristics of donor atoms or the denticity of the ligands, steadily increased covalency has been observed across Am to Cf. Inspection of the ligand highest energy occupied molecular orbitals and metal orbitals sheds light on the origin of the unexpected covalency. An overall increase in bonding and also the orbital contribution along the Am-Cf series is clearly due to the enhancement in covalency, which is complementary to the orbital degeneracy induced covalency proposed very recently by Batista and co-workers.

Development of Technologies and Safety Systems for Pressurized Heavy Water Reactors in India

The technology of pressurized heavy water reactors (PHWRs) which was developed with prime objectives of using natural uranium fuel, implementing on power fuelling, utilizing mined uranium most effectively, and achieving excellent neutron economy has demonstrated impressive performance in terms of high capacity factors and an impeccable safety record. The safety features and several technology advancements evolved over the years in which Indian contributions that are considerable are briefly discussed in the first part of the paper. Unique features of PHWR such as flexibility of fuel management, distribution of pressure boundaries in multiple pressure tubes (PTs), and a large inventory of coolant-moderator heat sink in close proximity of the core provide inherent safety and fuelling options to these reactors. PHWRs, in India have demonstrated to have the advantage of lower capital cost per megawatt even in small size reactors. Low burn up associated with natural uranium fuel, higher level of tritium in the heavy water coolant, and a slightly positive coolant void coefficient in present generation PHWRs have all been addressed in the design of advanced heavy water reactor (AHWR). The merit of adopting closed fuel cycle with partitioning of minor actinides in reducing the burden of radio-toxicity of nuclear waste and of deploying light water reactors (LWRs) in tandem with PHWRs in the evolving nuclear fuel cycle in India are also discussed.

Evaluation of hydrodynamic suitability of N,N-didodecyl N′,N′-di-octyl diglycolamide: a potential candidate for minor actinide partitioning

An unsymmetrical diglycolamide namely N,N, didodecyl-N′,N′-dioctyl diglycolamide developed in our laboratory is evaluated for its hydrodynamic suitability by determining the changes in its physical properties such as density and viscosity as a function of temperature and compared with those of tri n-butyl phosphate and N,N,N′,N′-tetraoctyl diglycolamide. The effect of irradiation on density, viscosity and interfacial tension, up to a dose of 1000 kGy are also measured. In addition, the activation energy for the viscous flow (E vis) were obtained for these pure solvents and their binary mixtures with n-dodecane in the temperature range 20–65 °C using the Andrade’s equation.

Studies on evaluation of modified TRUEX solvent for the partitioning of minor actinides

An attempt to modify the TRUEX solvent has been initiated by replacing TBP with long-chain alcohols such as isodecanol. Solvent extraction experiments have been carried out determining distribution ratios for Am(III) as a function of concentrations of nitric acid and isodecanol. Acid uptake constant for the combined organic phase has also been arrived at which strongly suggests the interaction of CMPO and isodecanol. The suitability of the organic phase was tested for simulated high-level waste solutions.

Feasibility of Using Di-Dodecyl-Di-Octyl Diglycolamide for Partitioning of Minor Actinides from Fast Reactor High-Level Liquid Waste

The unsymmetrical diglycolamide, di-dodecyl-di-octyl diglycolamide (D3DODGA) is a modifier-free extractant proposed for partitioning of trivalent actinides from nitric acid medium. D3DODGA has been evaluated for the feasibility of using it in the absence of a phase modifier, for the partitioning of minor actinides from fast reactor high-level liquid waste (FR-HLLW). The extraction behavior of various metal ions present in the simulated FR-HLLW was studied in a solution of 0.1 M D3DODGA/n-dodecane from nitric acid medium. The distribution ratio of about 20 metal ions was measured as a function of concentration of nitric acid and other interfering ion. The extraction was found to be strongly dependent on the oxidation state of the metal ion. The extraction of Am(III) from 3–4 M nitric acid medium was quantitative in a single contact. However, it was accompanied by the quantitative extraction of fission products such as trivalent lanthanides (Ln(III)), Y(III), and Zr(IV). The extraction of Sr(II), Pd(II), and Ru(III) in 0.1 M D3DODGA/n-dodecane was not insignificant, but quite low. The extraction of Ba(II), Ni(II), Mo(VI), and Fe(III) was marginal and the extraction of Co(II), Sb(III), Mn(II), and Cs(I) in 0.1 M D3DODGA/n-dodecane was negligible. Our results indicated that 0.1 M D3DODGA/n-dodecane is a promising candidate for the separation of trivalent actinides from fast reactor high-level liquid waste containing significant quantities of trivalent lanthanides and actinides.

Single-cycle method for partitioning of trivalent actinides using completely incinerable reagents from nitric acid medium

Abstract A new approach, namely “Single-cycle method for partitioning of Minor Actinides using completely incinerable ReagenTs” (SMART), has been explored for the separation of Am(III) from Eu(III) present in nitric acid medium. The extraction behavior of Am(III) and Eu(III) in a solution of an unsymmetrical diglycolamide, N,N,-didodecyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (D3DODGA), and an acidic extractant, N, N-di-2-ethylhexyl diglycolamic acid (HDEHDGA), in n-dodecane was studied. The distribution ratio of both these metal ions in D3DODGA-HDEHDGA/n-dodecane initially decreased with increase in the concentration of nitric acid reached a minimum at 0.1 M nitric acid followed by increase. Synergic extraction of Am(III) and Eu(III) was observed at nitric acid concentrations above 0.1 M and antagonism at lower acidities. Contrasting behavior observed at different acidities was probed by the slope analysis of the extraction data. The study revealed the involvement of both D3DODGA and HDEHDGA during synergism and increased participation of HDEHDGA during antagonism. The stripping behavior of Am(III) and Eu(III) from the loaded organic phase was studied as a function of nitric acid, DTPA, and citric acid concentrations. The conditions needed for the mutual separation of Am(III) and Eu(III) from the loaded organic phase were optimized. Our studies revealed the possibility of separating trivalent actinides from HLLW using these completely incinerable reagents.

Radiolytic stability of N,N-didodecyl-N’,N’-diethylhexyl diglycolamide

The radiolytic degradation of N,N-di-dodecyl-N′,N′-di-2-ethylhexyl-3-oxapentane-1,5-diamide (D3DEHDGA) was studied at various absorbed doses of γ-radiation. The degradation was assessed by measuring the variation in the extraction behavior of Am(III) in irradiated solvent systems composed of neat D3DEHDGA or 0.1 M D3DEHDGA/n-dodecane in the presence and absence of nitric acid. The distribution ratio of americium (DAm(III)) decreased with increase of absorbed dose. The presence of n-dodecane and nitric acid enhanced the radiolytic degradation of the solvent. The third phase formation behavior of Nd(III) decreased with increase of absorbed dose and the third phase was not observed at absorbed doses above 100 kGy. The recovery of Am(III) from the irradiated system was near quantitative in five contacts. The study revealed that the extraction and stripping behavior of the irradiated solvent was quite satisfactory for partitioning of minor actinides from real wastes.

Evaluation of radiation stability of N,N-didodecyl N′,N′-di-octyl diglycolamide: a promising reagent for actinide partitioning

The radiation stability of N,N-di-dodecyl-N′,N′-di-octyl-3-oxapentane-1,5-diamide (D3DODGA) was studied by γ-irradiation of the solvent up to a absorbed dose of 1,000 kGy. The effect of γ-irradiation on the radiolytic degradation of D3DODGA was assessed by measuring the distribution ratio of Am(III) (DAm(III)) as well as the third phase formation in the irradiated D3DODGA-n-dodecane solution. The DAm(III) in the irradiated solution decreased with increase of absorbed dose. The critical aqueous concentration of Nd(III) above which the third phase forms, increased with increase of absorbed dose. However, the limiting organic concentration of Nd(III) remained at ~25 mM irrespective of the absorbed dose. Recovery of Am(III) from the radiolytically degraded organic phase showed that back extraction of Am(III) was quantitative in a few contacts using dilute nitric acid. Our studies clearly indicated that radiolytic degradation of D3DODGA in n-dodecane is marginal even at the absorbed dose of 1,000 kGy, and therefore D3DODGA is a potential candidate for minor actinide partitioning.

ChemInform Abstract: Does Covalency Increase or Decrease Across the Actinide Series? Implications for Minor Actinide Partitioning.

AbstractReview: 57 refs.

BTBPs versus BTPhens: Some Reasons for Their Differences in Properties Concerning the Partitioning of Minor Actinides and the Advantages of BTPhens

Two members of the tetradentate N-donor ligand families 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO-LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO-LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol(-1)) energy barrier to rotation about the central biaryl C-C axis in order to achieve the cis-cis conformation that is required to form a complex, whereas the cis-cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10-coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.

Utilizing electronic effects in the modulation of BTPhen ligands with respect to the partitioning of minor actinides from lanthanides

Effects of bromine substitution at the 5 and 5,6-positions of the 1,10-phenanthroline nucleus of BTPhen ligand on their extraction properties for Ln(III) and An(III) cations have been studied. Compared to C5-BTPhen, electronic modulation in BrC5-BTPhen and Br2C5-BTPhen enabled these ligands to be fine-tuned in order to enhance the separation selectivity of Am(III) from Eu(III).

The Application Research of Concentration & Denitration Technology in Advanced Reprocessing Process

The proper management of spent fuel arising from nuclear power production is a key issue for the sustainable development of nuclear energy. While conventional reprocessing process, PUREX process, was successful to recover uranium and plutonium, in recent years some countries have turned to focus on advanced reprocessing process, which features of partitioning of minor actinides (MA) and long-lived fission products(LLFP). Most advanced reprocessing processes under development involve new extractants and additional extraction cycles. In China, TRPO extraction process has been developed to partition MA/LLFP from high-level liquid waste(HLLW) since early 1980’s. In parallel to R&D work on separation technologies, studies on concentration & denitration process have been evolved to prepare feed solutions to suit qualifications of extraction. Industrially, concentration & denitration is the internationally recognized standard to treat HLLW released from PUREX before vitrification. It enables to minimize the volume of interim storage, to restrain the corrosion of storage tank, to recover nitric acid in HLLW and to reduce the required evaporation duty of the vitrification process. Generally, the constitution of concentrated HLLW has little impact on the following vitrification process. But when concentration & denitration acts as pretreatment process of partitioning, the composition of actinides, fission products, and nitric acid in concentrated HLLW solution plays significant role in extraction process. A series of technical issues relevant to the connection between concentration ﹠denitration and extractions should be solved. This paper describes current status of concentration & denitration technology utilized in industry and under reprocessing plants. The specific separation requirements in advanced reprocessing process and challenges to apply concentration & denitration process are addressed. Besides, concentration & denitration process was tested in laboratory to adjust feed solutions for TRPO and Cyanex301 partitioning. Results demonstrate its promising prospect in advanced reprocessing process.

A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate

Abstract The selective partitioning (P) of long-lived minor actinides fromhighly active waste solutions and their transmutation (T) to short-lived or stable isotopes by nuclear reactions will reduce the long-term hazard of the high-level waste and significantly shorten the time needed to ensure their safe confinement in a repository. The present paper summarizes the on-going research activities at Forschungszentrum Jülich (FZJ), Karlsruher Institut für Technologie (KIT) and Institute for Transuranium Elements (ITU) in the field of actinide partitioning using innovative solvent extraction processes. European research over the last few decades, i.e. in the NEWPART, PARTNEW and EUROPART programmes, has resulted in the development of multi-cycle processes for minor actinide partitioning. These multi-cycle processes are based on the co-separation of trivalent actinides and lanthanides (e.g. by the DIAMEX process), followed by the subsequent actinide(III)/lanthanide(III) group separation in the SANEX process. The current direction of research for the development of innovative processes within the recent European ACSEPT project is discussed additionally. This paper is focused on the development of flow-sheets for recovery of americium and curium from highly active waste solutions. The flow-sheets are verified by demonstration processes, in centrifugal contactors, using synthetic or genuine fuel solutions. The feasibility of the processes is also discussed.

Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning

A covalent chemical bond carries the connotation of overlap of atomic orbitals between bonded atoms, leading to a buildup of the electron density in the internuclear region. Stabilization of the valence 5f orbitals as the actinide series is crossed leads, in compounds of the minor actinides americium and curium, to their becoming approximately degenerate with the highest occupied ligand levels and hence to the unusual situation in which the resultant valence molecular orbitals have significant contributions from both actinide and the ligand yet in which there is little atomic orbital overlap. In such cases, the traditional quantum-chemical tools for assessing the covalency, e.g., population analysis and spin densities, predict significant metal-ligand covalency, although whether this orbital mixing is really covalency in the generally accepted chemical view is an interesting question. This review discusses our recent analyses of the bonding in AnCp3 and AnCp4 (An = Th-Cm; Cp = η(5)-C5H5) using both the traditional tools and also topological analysis of the electron density via the quantum theory of atoms-in-molecules. I will show that the two approaches yield rather different conclusions and suggest that care must be taken when using quantum chemistry to assess metal-ligand covalency in this part of the periodic table. The implications of this work for minor actinide partitioning from nuclear wastes are discussed; minor actinide extractant ligands based on nitrogen donors have received much attention in recent years, as have comparisons of the extent of covalency in actinide-nitrogen bonding with that in analogous lanthanide systems via quantum-chemical studies employing the traditional tools for assessing the covalency.

New Insight into the Partitioning of Minor Actinides I: Extraction of Palladium and Some Typical Metals with a Multidentate Soft-Ligand 2,6-Bis(5,6-dinonyl-1,2,4-triazine-3-yl)pyridine

A new multidentate soft-ligand 2,6-bis(5,6-dinonyl-1,2,4-triazine-3-yl)pyridine (NonBTP) was synthesized. The solvent extraction of Pd(II) and some typical metals Ru(III), Mo(VI), Fe(III), Co(II), Zr(IV), and Ni(II) with NonBTP/30 % 1-octanol–70 % 1-dodecane was investigated at 298 K. It was performed by examining the effects of contact time and the concentration of HNO3 in the range of (0.42 to 5.11) M. NonBTP showed a strong extraction ability and high selectivity for Pd(II) over the tested metals, which had very weak or almost no extraction. The optimum acidity in the extraction of Pd(II) was around 3.0 M HNO3. It was ascribed to the complexation of Pd(II), a weak Lewis acid and an electron-pair acceptor, with nitrogen inside NonBTP, a weak Lewis base and an electron-pair donor. The extraction of NonBTP for Pd(II) was an exothermic reaction. The composition of the extracted species was determined to be Pd(NO3)2·2NonBTP. Considering the excellent complexation of minor actinides MAs(III) with NonBTP, the...

Preparation of a macroporous silica–pyridine multidentate material and its adsorption behavior for some typical elements

AbstractA new macroporous silica‐based‐polymer (SiO2‐P) soft ligand composite material, 2,6‐bis(5,6‐di(iso‐butyl)‐1,2,4‐triazine‐3‐yl)pyridine (BDIBTP/SiO2‐P), was synthesized by impregnation and immobilization of BDIBTP and 1‐octanol molecules into the pores of the SiO2‐P particles. The impact of some typical alkali metal and alkaline earths Cs(I), Na(I), K(I), Rb(I), Sr(II), and Ba(II) containing in highly active liquid waste (HLW) on the adsorption of Pd(II) onto BDIBTP/SiO2‐P was studied. It was performed by examining the effects of contact time and the HNO3 concentration in the range of 0.3–7.0 M. BDIBTP/SiO2‐P showed strong adsorption ability and high selectivity for Pd(II) over all the tested metals. The chromatographic partitioning of Pd(II) from a simulated HLW solution was conducted by BDIBTP/SiO2‐P packed column. Pd(II) was effectively eluted with 0.2 M thiourea–0.1 M HNO3. The others showed no adverse impact on separation of Pd(II). The results are beneficial to partitioning of minor actinides and Pd(II) together from HLW by BDIBTP/SiO2‐P in the MPS process developed. © 2012 American Institute of Chemical Engineers AIChE J, 2012

Recovery of Uranium, Plutonium, and Neptunium from High-Level Waste Solutions prior to Actinide Partitioning

AbstractThe prior removal of uranium along with plutonium and neptunium from high-level waste (HLW) can simplify the subsequent actinide partitioning steps. In this context, extraction and stripping behavior of uranium, plutonium, and neptunium was investigated employing 1.1-M solutions of tri-n-butyl phosphate (TBP) and N,N-dihexyl octanamide (DHOA) dissolved in n-dodecane as extractants in the presence of 6 g/L U relevant to pressurized heavy-water reactor (PHWR) high-level waste (HLW) conditions. Reductants such as acetohydroxamic acid (AHA) and hydroxyurea (HU) were evaluated for selective stripping of plutonium and neptunium over uranium from the loaded organic phases. These studies indicated the possibility of quantitative recovery of U(VI), Pu(IV), and Np(IV) from HLW solution employing either DHOA or TBP as extractant. Integration of this step in the minor actinide partitioning simplifies the treatment of HLW with the specially designed extractants like octyl(phenyl)- N, N-diisobutyl carbamoyl me...

Main Results of the French Program on Partitioning of Minor Actinides, a Significant Improvement Towards Nuclear Waste Reduction

In the framework of the successive 1991 and 2006 Waste Management Act, French government supported a very significant R&D program on partitioning and transmutation of minor actinides (MA). This program aims to study potential solutions for still minimizing the quantity and the hazardousness of final waste, by MA recycling. Indeed, MA recycling can reduce the heat load and the half-life of most of the waste to be buried to a couple of hundred years, overcoming the concerns of the public related to the long-life of the waste. Within this framework, this paper aims to present the most recent progress obtained in CEA on the development of innovative actinide partitioning hydrometallurgical processes in support of their recycling, either in an homogeneous mode (MA are recycled at low concentration in all the standard reactor fuel) or in an heterogeneous mode (MA are recycled at higher concentration in specific targets, at the periphery of the reactor core). Recovery performances obtained on recent tests in high active conditions of the so-called GANEX and DIAMEX-SANEX process will be presented and discussed in light of the potential P&T scenarios. Finally, recent developments regarding the recycling of the sole Am will be presented as well as the results obtained on highly active solutions for this so-called EXAM process. This set of results gives to the French government a portfolio of potential recycling processes which could be separately and progressively implemented if decided.